CN111378173A

CN111378173A - Force-responsive crosslinked polymer

Info

Publication number: CN111378173A
Application number: CN201910003000.XA
Authority: CN
Inventors: 不公告发明人
Original assignee: Weng Qiumei
Current assignee: Xiamen Tiance Material Technology Co ltd
Priority date: 2019-01-01
Filing date: 2019-01-01
Publication date: 2020-07-07

Abstract

The invention discloses a force-responsive cross-linked polymer, which contains a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response. The polymer can be widely applied as a stress induction material, an ion detection material, a sensor material, a biological analysis material and the like.

Description

Force-responsive crosslinked polymer

Technical Field

The invention relates to a force-responsive polymer, in particular to a force-responsive crosslinked polymer containing force sensitive groups.

Background

The progress of material science and technology greatly promotes the development and the transition of the human society. Although the material technology has been developed rapidly in recent decades, it still cannot meet the development needs of the human society. People are therefore continuously pursuing to create new materials with more novel structures and more excellent performance. Polymer materials are an important branch of materials and play a very important role in activities such as human life and industrial production. In polymer applications, many times the polymer is subjected to mechanical forces. Therefore, the construction of polymers with sensitive response to mechanical force has multiple theoretical and practical meanings.

Disclosure of Invention

Against the above background, a force-responsive crosslinked polymer containing a force-sensitive group is provided. The force-induced response cross-linked polymer has good stability, can have good stress response under general mild conditions, and generates chemical and/or physical changes of the structure, thereby directly and/or indirectly generating chemical and/or physical signal changes and generating new groups/new substances.

The invention can be realized by the following technical scheme:

the invention relates to a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein said crosslinked network comprises a polymer segment structure of at least two different types of chemical structures; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response crosslinked polymer is provided, which contains a force-sensitive group and only contains a crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein said crosslinked network comprises a polymer segment structure of at least two different types of chemical structures; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is a carbon chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response crosslinked polymer is provided, which contains a force-sensitive group and only contains a crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is a carbon chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the cross-linked network is a carbon heterochain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response crosslinked polymer is provided, which contains a force-sensitive group and only contains a crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the cross-linked network is a carbon heterochain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a carbon element chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response crosslinked polymer is provided, which contains a force-sensitive group and only contains a crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a carbon element chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is a carbon hetero element chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response crosslinked polymer is provided, which contains a force-sensitive group and only contains a crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is a carbon hetero element chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is an element organic heterochain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response crosslinked polymer is provided, which contains a force-sensitive group and only contains a crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is an element organic heterochain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is a non-polyorganosiloxane organic chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response crosslinked polymer is provided, which contains a force-sensitive group and only contains a crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is a non-polyorganosiloxane organic chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

In an embodiment of the present invention, the force-responsive crosslinked polymer has the following structure:

the first network structure: the force-induced response crosslinked polymer contains a homolytic force sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force sensitive group, and the crosslinking degree of the force sensitive group crosslinking is above the gel point of the force sensitive group;

the second network structure: the force-induced response crosslinked polymer contains a reversible free radical type force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is above the gel point of the force-sensitive group;

the third network architecture: the force-induced response cross-linked polymer contains a biaryl cyclic ketone force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

fourth network architecture: the force-induced response crosslinked polymer contains a biaryl cyclopentenedione force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is above the gel point of the force-sensitive group;

fifth network architecture: the force-induced response crosslinked polymer contains a bisaryl chromene force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is above the gel point of the force-sensitive group;

sixth network architecture: the force-responsive crosslinked polymer contains a dicyano tetraarylethane force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is above the gel point of the force-sensitive group;

seventh network architecture: the force-induced response cross-linked polymer contains a biaryl furanone force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

eighth network architecture: the force-induced response cross-linked polymer contains an aryl pinacol force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

ninth network architecture: the force-responsive crosslinked polymer contains a tetracyanoethane force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is above the gel point of the force-sensitive group;

tenth network architecture: the force-induced response crosslinked polymer contains a bifluorene force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the bifluorene force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is above the gel point of the bifluorene force-sensitive group;

an eleventh network architecture: the force-induced response cross-linked polymer contains a heterolytic force sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force sensitive group, and the cross-linking degree of the force sensitive group cross-linking is above the gel point of the force sensitive group;

a twelfth network architecture: the force-responsive crosslinked polymer contains a triaryl sulfonium salt series force-sensitive groups, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive groups, and the crosslinking degree of the force-sensitive groups is above the gel point of the force-sensitive groups;

a thirteenth network architecture: the force-responsive crosslinked polymer contains a reverse cyclization force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is above the gel point of the force-sensitive group;

a fourteenth network architecture: the force-induced response crosslinked polymer contains a cyclobutane reverse cyclization force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is above the gel point of the force-sensitive group;

a fifteenth network architecture: the force-responsive crosslinked polymer contains a dioxetane reverse cyclization force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is above the gel point of the force-sensitive group;

a sixteenth network architecture: the force-induced response crosslinked polymer contains a DA series reverse cyclization force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is above the gel point of the force-sensitive group;

a seventeenth network architecture: the force-induced response crosslinked polymer contains a hetero DA series reverse cyclization force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the hetero DA series reverse cyclization force-sensitive group, and the crosslinking degree of force-sensitive group crosslinking is above the gel point of the hetero DA series reverse cyclization force-sensitive group;

eighteenth network architecture: the force-induced response crosslinked polymer contains a [4+4] cycloaddition series reverse cyclization force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is above the gel point of the force-sensitive group;

nineteenth network architecture: the force-induced response cross-linked polymer contains an electrocyclic force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

a twentieth network configuration: the force-induced response cross-linked polymer contains a six-membered ring series force-sensitive groups, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive groups, and the cross-linking degree of the force-sensitive groups is above the gel point of the force-sensitive groups;

a twenty-first network architecture: the force-induced response cross-linked polymer contains a spiropyran force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

a twenty-second network architecture: the force-responsive crosslinked polymer contains a spirothiopyran force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is above the gel point of the force-sensitive group;

a twenty-third network architecture: the force-induced response cross-linked polymer contains a spirooxazine force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

a twenty-fourth network architecture: the force-induced response cross-linked polymer contains a five-membered ring series force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

a twenty-fifth network architecture: the force-induced response cross-linked polymer contains a rhodamine force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

a twenty-sixth network architecture: the force-responsive crosslinked polymer contains a bending-activated force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is above the gel point of the force-sensitive group;

a twenty-seventh network architecture: the force-responsive crosslinked polymer contains a force-sensitive group of an adduct series of anthracene and Triazolinedione (TAD), wherein the degree of crosslinking of ordinary covalent crosslinks is above its gel point, and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point;

a twenty-eighth network architecture: the force-induced response cross-linked polymer contains a dithiomaleimide series force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

a twenty-ninth network architecture: the force-induced response cross-linked polymer contains a dual-nitroso series force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

a thirtieth network configuration: the force-responsive cross-linked polymer is a non-covalent force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

a thirty-first network architecture: the force-induced response cross-linked polymer is a supermolecular complex force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

a thirty-second network architecture: the force-induced response cross-linked polymer is a carbene-metal coordination bond force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

a thirty-third network architecture: the force-induced response cross-linked polymer is a ligand-lanthanide metal ion complexing force sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force sensitive group, and the cross-linking degree of the force sensitive group cross-linking is above the gel point of the force sensitive group;

a thirty-fourth network architecture: the force-induced response cross-linked polymer is a hydrogen bonding force sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force sensitive group, and the cross-linking degree of the force sensitive group cross-linking is above the gel point of the force sensitive group;

a thirty-fifth network architecture: the force-induced response crosslinked polymer contains a homolytic force sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force sensitive group, and the crosslinking degree of the force sensitive group crosslinking is below the gel point of the force sensitive group;

a thirty-sixth network architecture: the force-induced response cross-linked polymer contains a reversible free radical type force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is below the gel point of the force-sensitive group;

thirty-seventh network architecture: the force-induced response cross-linked polymer contains a biaryl cyclic ketone force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is below the gel point of the force-sensitive group;

a thirty-eighth network architecture: the force-induced response crosslinked polymer contains a biaryl cyclopentenedione force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is below the gel point of the force-sensitive group;

thirty-ninth network architecture: the force-induced response cross-linked polymer contains a bisaryl chromene force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is below the gel point of the force-sensitive group;

fortieth network architecture: the force-responsive crosslinked polymer contains a dicyano tetraarylethane force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is below the gel point of the force-sensitive group;

forty-first network architecture: the force-induced response cross-linked polymer contains a biaryl furanone force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is below the gel point of the force-sensitive group;

forty-second network architecture: the force-responsive crosslinked polymer contains a tetracyanoethane force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is below the gel point of the force-sensitive group;

a forty-third network configuration: the force-induced response crosslinked polymer contains a bifluorene force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the bifluorene force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is below the gel point of the bifluorene force-sensitive group;

a forty-fourth network configuration: the force-induced response cross-linked polymer contains an aryl pinacol force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is above the gel point of the force-sensitive group;

a forty-fifth network configuration: the force-induced response cross-linked polymer contains a heterolytic force sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force sensitive group, and the cross-linking degree of the force sensitive group cross-linking is below the gel point of the force sensitive group;

a forty-sixth network configuration: the force-responsive crosslinked polymer contains a triarylsulfonium salt series force-sensitive groups, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive groups, and the crosslinking degree of the force-sensitive groups is below the gel point of the force-sensitive groups;

a forty-seventh network configuration: the force-responsive crosslinked polymer contains a reverse cyclization force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is below the gel point of the force-sensitive group;

forty-eight network architectures: the force-induced response crosslinked polymer contains a cyclobutane reverse cyclization force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is below the gel point of the force-sensitive group;

a forty-ninth network configuration: the force-responsive crosslinked polymer contains a dioxetane reverse cyclization force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is below the gel point of the force-sensitive group;

fifty-th network architecture: the force-induced response crosslinked polymer contains a DA series reverse cyclization force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is below the gel point of the force-sensitive group;

fifty-first network architecture: the force-induced response crosslinked polymer contains a hetero DA series reverse cyclization force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the hetero DA series reverse cyclization force-sensitive group, and the crosslinking degree of force-sensitive group crosslinking is below the gel point of the hetero DA series reverse cyclization force-sensitive group;

fifty-second network architecture: the force-induced response crosslinked polymer contains a [4+4] cycloaddition series reverse cyclization force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is below the gel point of the force-sensitive group;

a fifty-third network architecture: the force-responsive crosslinked polymer contains an electrocyclic force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is below the gel point of the force-sensitive group;

fifty-fourth network architecture: the force-induced response cross-linked polymer contains a six-membered ring series force-sensitive groups, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive groups, and the cross-linking degree of the force-sensitive groups is below the gel point of the force-sensitive groups;

fifty-fifth network architecture: the force-responsive crosslinked polymer contains a spiropyran force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is below the gel point of the force-sensitive group;

fifty-sixth network architecture: the force-responsive crosslinked polymer contains a spirothiopyran force-sensitive group, wherein the crosslinking degree of common covalent crosslinking is above the gel point of the force-sensitive group, and the crosslinking degree of the force-sensitive group crosslinking is below the gel point of the force-sensitive group;

fifty-seventh network architecture: the force-induced response cross-linked polymer contains a spirooxazine force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is below the gel point of the force-sensitive group;

fifty-eight network architectures: the force-induced response cross-linked polymer contains a five-membered ring series force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is below the gel point of the force-sensitive group;

fifty-ninth network architecture: the force-induced response cross-linked polymer contains a rhodamine force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is below the gel point of the force-sensitive group;

sixty network architectures: the force-responsive crosslinked polymer contains a bending-activated force-sensitive group, wherein the degree of crosslinking of ordinary covalent crosslinking is above its gel point and the degree of crosslinking of the force-sensitive group crosslinking is below its gel point;

sixty-fourth network architecture: the force-responsive crosslinked polymer contains a force-sensitive group of an adduct series of anthracene and Triazolinedione (TAD), wherein the degree of crosslinking of ordinary covalent crosslinks is above its gel point and the degree of crosslinking of force-sensitive group crosslinks is below its gel point;

sixty-second network architecture: the force-induced response cross-linked polymer contains a dual-nitroso series force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is below the gel point of the force-sensitive group;

sixty-third network architectures: the force-responsive cross-linked polymer is a non-covalent force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is below the gel point of the force-sensitive group;

sixty-fourth network architecture: the force-induced response cross-linked polymer is a supermolecular complex force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is below the gel point of the force-sensitive group;

sixty-fifth network architecture: the force-induced response cross-linked polymer is a carbene-metal coordination bond force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is below the gel point of the force-sensitive group;

sixty-sixth network architectures: the force-induced response cross-linked polymer is a ligand-lanthanide metal ion complexing force sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force sensitive group, and the cross-linking degree of the force sensitive group cross-linking is below the gel point of the force sensitive group;

sixty-seventh network architecture: the force-responsive cross-linked polymer is a hydrogen bonding force-sensitive group, wherein the cross-linking degree of common covalent cross-linking is above the gel point of the force-sensitive group, and the cross-linking degree of the force-sensitive group cross-linking is below the gel point of the force-sensitive group.

The invention also relates to a force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups based on a homolytic mechanism, covalent force sensitive groups based on a heterolytic mechanism, covalent force sensitive groups based on a reverse cyclization mechanism and covalent force sensitive groups based on a bending activation mechanism; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response crosslinked polymer is provided, which contains a force-sensitive group and only contains a crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups based on a homolytic mechanism, covalent force sensitive groups based on a heterolytic mechanism and covalent force sensitive groups based on a bending activation mechanism; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from non-covalent force sensitive groups; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response crosslinked polymer is provided, which contains a force-sensitive group and only contains a crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from non-covalent force sensitive groups; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive group is selected from covalent force sensitive groups of a three-membered ring electrocyclization mechanism; wherein, the force sensitive group can generate biological change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response crosslinked polymer is provided, which contains a force-sensitive group and only contains a crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive group is selected from covalent force sensitive groups of a three-membered ring electrocyclization mechanism; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a five-membered ring electrocyclization mechanism; wherein, the force sensitive group can generate biological change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response crosslinked polymer is provided, which contains a force-sensitive group and only contains a crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a five-membered ring electrocyclization mechanism; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

The invention also relates to a force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a six-membered ring electrocyclization mechanism; the force sensitive groups can perform biological change under the action of mechanical force, so that the polymer can realize force-induced response; wherein the six-membered ring force sensitive group motif in the covalent force sensitive group of the six-membered ring electrocyclization mechanism is selected from the following structures:

wherein X is selected from oxygen atom, sulfur atom, selenium atom, tellurium atom, C-R, N-R, preferably oxygen atom; y is selected from C-R and nitrogen atom; r is each independentlyAnd is any suitable atom, substituent, substituted polymer chain; m is a metal atom selected from Be, Zn, Cu, Co, Hg, Pb, Pt, Fe, Cr, Ni, preferably Be, Zn, Cu, Co;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.

The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response crosslinked polymer is provided, which contains a force-sensitive group and only contains a crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a six-membered ring electrocyclization mechanism; the force sensitive groups can generate chemical and/or physical changes under the action of mechanical force, so that the polymer realizes force-induced response; wherein the six-membered ring force sensitive group motif in the covalent force sensitive group of the six-membered ring electrocyclization mechanism is selected from the following structures:

wherein X is selected from oxygen atom, sulfur atom, selenium atom, tellurium atom, C-R, N-R, preferably oxygen atom; y is selected from C-R, nitrogen atom(ii) a Each R is independently any suitable atom, substituent, substituted polymer chain; m is a metal atom selected from Be, Zn, Cu, Co, Hg, Pb, Pt, Fe, Cr, Ni, preferably Be, Zn, Cu, Co;

Can be linked to form a ring, on different atoms

wherein X is selected from oxygen atom, sulfur atom, selenium atom, tellurium atom, C-R, N-R, preferably oxygen atom; y is a nitrogen atom; each R is independently any suitable atom, substituent or substituted polymerAn object chain;

Can be linked to form a ring, on different atoms

wherein X is selected from oxygen atom, sulfur atom, selenium atom, tellurium atom, C-R, N-R, preferably oxygen atom; y is a nitrogen atom; each R is independently any suitable atom, substituent, substituted polymer chain;

Can be linked to form a ring, on different atoms

wherein X is selected from the group consisting of a sulfur atom, a selenium atom, a tellurium atom, C-R, N-R, preferably from a sulfur atom; y is C-R; each R is independently any suitable atom, substituent, substituted polymer chain;

Can be linked to form a ring, on different atoms

May be linked to form a ring, different atomsOn

wherein, X, X₁Selected from oxygen atoms; y is C-R; y is₁Selected from C-R, nitrogen atom; each R is independently any suitable atom, substituent, substituted polymer chain; z₁Is selected from C- (R)₂Nitrogen atom, sulfur atom, oxygen atom, tellurium atom, preferably C- (R)2, nitrogen atom; z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂Nitrogen atom, preferably C- (R)₂A nitrogen atom; when Z is₁Or Z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂When connected to it

Number ofIs 0;

an aromatic ring having an arbitrary number of elements; n is the total number of hydrogen atoms, substituent atoms, substituents, and substituent polymer chains bonded to the atoms constituting the ring, and is 0, 1, or an integer greater than 1; the aromatic ring can be any aromatic ring or aromatic heterocyclic ring, and the ring-forming atoms are respectively and independently carbon atoms or hetero atoms; the heteroatom can be selected from nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom and boron atom; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; it can be a single ring structure, a multi-ring structure, a spiro structure, a fused ring structure, a bridged ring structure, or a nested ring structure.

Can be linked to form a ring, on different atoms

wherein, X, X₁Selected from oxygen atoms; y is C-R; y is₁Selected from C-R, nitrogen atom; each R is independently any suitable atom, substituent, substituted polymer chain; z₁Is selected from C- (R)₂Nitrogen atom, sulfur atom, oxygen atom, tellurium atom, preferably C- (R)₂A nitrogen atom; z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂Nitrogen atom, preferably C- (R)₂A nitrogen atom; when Z is₁Or Z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂When connected to it

The number is 0;

Can be linked to form a ring, on different atoms

wherein, X, X₁Selected from oxygen atoms; y is C-R; each R is independently any suitable atom, substituent, substituted polymer chain; z₁Is selected from C- (R)₂Nitrogen atom, sulfur atom, oxygen atom, tellurium atom, preferably C- (R)₂A nitrogen atom; z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂Nitrogen atom, preferably C- (R)₂A nitrogen atom; when Z is₁Or Z₂Selected from the group consisting of sulfur atoms,Oxygen atom, selenium atom, tellurium atom, C- (R)₂When connected to it

The number is 0;

Can be linked to form a ring, on different atoms

wherein, X, X₁Selected from oxygen atoms; y is C-R; each R is independently any suitable atom, substituent, substituted polymer chain; z₁Is selected from C- (R)₂Nitrogen atom, sulfur atom, oxygen atom, tellurium atom, preferably C- (R)₂A nitrogen atom; z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂Nitrogen atom, preferably C- (R)₂A nitrogen atom; when Z is₁Or Z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂When connected to it

The number is 0;

Can be linked to form a ring, on different atoms

In embodiments of the present invention, the force-responsive crosslinked polymer morphology may be a common solid, an elastomer, a gel (including hydrogels, organogels, oligomer-swollen gels, plasticizer-swollen gels, ionic liquid-swollen gels), a foam, and the like.

In an embodiment of the present invention, a force-responsive crosslinked polymer, the raw material components constituting the polymer further include any one or two of the following additives: auxiliaries/additives, fillers;

wherein, the additive can be selected from any one or more of the following: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, chain extenders, toughening agents, coupling agents, lubricants, mold release agents, plasticizers, foaming agents, antistatic agents, emulsifiers, dispersing agents, colorants, fluorescent whitening agents, delustering agents, flame retardants, rheological agents, thickeners, leveling agents, and antibacterial agents;

wherein, the filler which can be added is selected from any one or more of the following fillers: inorganic non-metallic fillers, organic fillers, organometallic compound fillers.

The force-responsive crosslinked polymer described in the embodiments of the present invention is applied to the following articles: ion detection materials, stress detection materials, sensor materials, biological analysis materials, toy materials, elastic materials and energy storage device materials.

Compared with the prior art, the invention has the following beneficial effects:

(1) the force-responsive crosslinked polymer of the present invention contains a force-sensitive group and a common covalent bond double crosslink, which contains a force-sensitive group. In the polymer, the crosslinking degree of common covalent crosslinking is above the gel point, and the crosslinking degree of force sensitive group crosslinking is above or below the gel point; common covalent crosslinking can be responsible for the equilibrium structure of the polymer, while force sensitive groups can be responsible for force-induced response, and even if the force sensitive groups are subjected to activation and fracture, the degradation of a crosslinked network cannot be caused; in addition, a common covalent cross-linked network formed by at least two polymer chain segments with different types of chemical structures can generate stronger mechanical property, promote the mechanical force to be transmitted to the force sensitive groups and improve the probability and degree of activation of the force sensitive groups; when the polymer chain segment with a single chemical structure is adopted, the structure and the performance with more specific applicability can be obtained so as to meet various specific and abundant requirements.

(2) The force-sensitive groups in the force-responsive cross-linked polymer can be selected from various types and structures, and different stress responsiveness can be realized by combining different force-sensitive groups with different polymer cross-linked structures. By controlling the ratio of the covalent crosslinking and the force sensitive groups, the force-induced response crosslinked polymer with good and various performances such as mechanical strength, thermal stability, creep resistance, stress response and the like can be prepared. This is difficult to achieve in conventional polymer systems.

(3) In the invention, when the force sensitive group is a covalent force sensitive group with dynamic covalent characteristics or a supermolecular complex non-covalent force sensitive group, the polymer also has super toughness, certain self-repairing characteristics, shape memory, especially shape memory induced by mechanical force, plasticity performance, force-induced crosslinking, force-induced enhancement and the like, so the polymer also has multifunctionality besides force responsiveness.

These and other features and advantages of the present invention will become apparent with reference to the following description of embodiments, examples and appended claims.

Detailed Description

For simplicity of description, in the description of the present invention, the term "and/or" is used to indicate that the term may include three cases selected from the options described before the conjunction "and/or," or selected from the options described after the conjunction "and/or," or selected from the options described before and after the conjunction "and/or.

It should be noted that, in the present invention, the terms "group", "series", "subline", "class", "subclass", "species" used to describe various structures are used to describe groups having a greater scope than the series, a greater scope than the subline, a greater scope than the class, a greater scope than the subclass, and a greater scope than the species, i.e., a group may have a plurality of series, a series may have a plurality of sublines, a subline may have a plurality of classes, a class may have a plurality of subclasses, and a subclass may have a plurality of subclasses.

The term "polymerization" reaction/action as used in the present invention, unless otherwise specified, refers to a process in which a reactant of lower molecular weight forms a product of higher molecular weight by polycondensation, polyaddition, ring-opening polymerization, or the like, i.e., a chain extension process/action other than crosslinking. The reactant may be a monomer, oligomer, prepolymer, or other compound having a polymerization ability (i.e., capable of polymerizing spontaneously or under the action of an initiator or an external energy). The product resulting from the polymerization of one reactant is called a homopolymer. It is to be noted that the "polymerization" referred to in the present invention includes a linear growth process, a branching process, a ring formation process, etc. of a reactant molecular chain other than the crosslinking process of the reactant molecular chain; in an embodiment of the present invention, "polymerization" refers to a chain growth process caused by the bonding of covalent bonds.

The term "crosslinking" reaction/action as used in the present invention refers to the process of intermolecular and/or intramolecular formation of a product having a three-dimensional infinite network type by covalent bonds. During the crosslinking process, the polymer chains generally grow continuously in two/three dimensions, gradually form clusters (which may be two-dimensional or three-dimensional), and then develop into a three-dimensional infinite network. Thus, crosslinking can be considered a special form of polymerization. The degree of crosslinking, just before a three-dimensional infinite network is reached during crosslinking, is called the gel point, also called the percolation threshold. A crosslinked product above the gel point (inclusive, the same applies hereinafter) having a three-dimensional infinite network structure, the crosslinked network constituting a whole and spanning the entire polymer structure; the crosslinked product below the gel point, which is only a loose inter-chain linking structure, does not form a three-dimensional infinite network structure, and does not belong to a crosslinked network that can constitute a whole across the entire polymer structure. Unless otherwise specified, the crosslinked structure in the present invention is a three-dimensional infinite network structure above the gel point, and the non-crosslinked structure includes linear and nonlinear structures with a degree of crosslinking of zero and a two-dimensional/three-dimensional cluster structure below the gel point.

The term "common covalent bond" as used herein refers to a conventional covalent bond, which is an interaction between atoms through a pair of common electrons, is difficult to break at a common temperature (generally not higher than 100 ℃) and a common time (generally less than 1 day) and has no specific response to mechanical force, and includes, but is not limited to, common carbon-carbon bonds, carbon-oxygen bonds, carbon-hydrogen bonds, carbon-nitrogen bonds, carbon-sulfur bonds, nitrogen-hydrogen bonds, nitrogen-oxygen bonds, hydrogen-oxygen bonds, nitrogen-nitrogen bonds, etc.

In the present invention, "backbone" refers to a structure in the chain length direction of a polymer chain. For crosslinked polymers, the term "backbone" refers to any segment present in the backbone of the crosslinked network, i.e., the backbone chain in the crosslinked network that connects adjacent crosslinks. For polymers of non-crosslinked structure, the "backbone", unless otherwise specified, refers to the chain with the most mer. Wherein, the side chain refers to a chain structure which is connected with the main chain of the polymer and is distributed beside the main chain; the "branched chain"/"branched chain" may have a side chain or other chain structure branched from any chain. Wherein, the "side group" refers to a chemical group which is connected with any chain of the polymer and is arranged beside the chain. Wherein, the "terminal group" refers to a chemical group attached to any chain of the polymer and located at the end of the chain. Unless otherwise specified, a pendant group refers specifically to groups and subgroups thereof having a molecular weight of not more than 1000Da attached to the side of the backbone of the polymer chain. When the molecular weight of the side chain, branched chain, does not exceed 1000Da, itself and the groups thereon are considered side groups. For simplicity, when the molecular weight of the side chain, branched chain, exceeds 1000Da, they are collectively referred to as side chains unless otherwise specified. The "side chain" and "side group" may have a multi-stage structure, that is, the side chain/side group may be continued to have a side chain/side group, and the side chain/side group of the side chain/side group may be continued to have a side chain/side group. In the present invention, for hyperbranched and dendritic chains and their related chain structures, the outermost polymer segment may be regarded as a side chain, and the rest as a main chain.

In the invention, the force-response cross-linked polymer has one cross-linked network and contains common covalent cross-linking and force-sensitive group cross-linking, wherein the common covalent cross-linking is above the gel point of the force-sensitive group cross-linking, and the cross-linking degree of the force-sensitive group cross-linking is above or below the gel point of the force-sensitive group cross-linking, preferably above the gel point, so that the cross-linking degree of the polymer system is higher, and the material with high mechanical property and high stress sensitivity can be obtained.

In the present invention, the force-sensitive group refers to an entity containing a mechanical force-sensitive moiety (i.e., force-sensitive moiety), wherein the force-sensitive moiety includes, but is not limited to, covalent chemical groups, supramolecular complexes, supramolecular assemblies, compositions, aggregates, which undergo chemical and/or physical changes of structure under mechanical force, including, but not limited to, chemical bond breaking, bonding, isomerization, decomposition, and physical dissociation, disassembly, and separation, thereby directly and/or indirectly undergoing chemical and/or physical signal changes, generating new groups/new substances, including, but not limited to, color, luminescence, fluorescence, spectral absorption, magnetism, electricity, conductance, heat, nuclear magnetism, infrared, raman, pH, catalysis, redox, addition, condensation, substitution, exchange, elimination, decomposition, polymerization, Crosslinking, coordination, hydrogen bonding, host-guest binding, ionic bonding, change of pi-pi stacking signal/performance, ionic bonding, degradation, change of viscosity signal/performance, release of new molecules, generation of new reactive groups, achieving specific response to mechanical force and obtaining force-induced response performance/effect.

In the present invention, the force-sensitive moiety includes covalent type and non-covalent type. Wherein, the covalent type force sensitive element is mainly related to chemical changes such as breaking, elimination, bonding, isomerization and the like of covalent bonds under the action of mechanical force, and comprises but not limited to heterolysis, reverse cyclization, electrocyclic ring opening, bending activation, elimination, addition and isomerization; the non-covalent force sensitive element mainly relates to physical changes such as dissociation of a supramolecular complex, disassembly and assembly of an assembly body, separation of a composition, separation of an aggregate and the like under the action of mechanical force.

In the present invention, the mechanical force source includes, but is not limited to, stretching, compressing, expanding, ultrasound, rubbing, scraping, shearing, cutting, swelling (for cross-linked polymers), bending, twisting, i.e. the force-induced response is obtained by providing a mechanical force including, but not limited to, stretching, compressing, expanding, ultrasound, rubbing, scraping, shearing, cutting, swelling (for cross-linked polymers), bending, twisting.

In the present invention, the force-sensitive group comprises only one mechanical force-sensitive moiety, which includes covalent force-sensitive groups and non-covalent force-sensitive groups. The force sensitive element contained in the covalent force sensitive group mainly relates to chemical changes of breaking, eliminating, bonding, isomerization and the like of a covalent bond under the action of mechanical force, and the chemical changes include but are not limited to heterolysis, reverse cyclization, electrocyclic ring opening, bending activation, elimination, addition and isomerization. The force sensitive elements contained in the non-covalent force sensitive groups mainly relate to physical changes such as dissociation of supramolecular complexes, disassembly of assemblies, separation of compositions, separation of aggregates and the like under the action of mechanical force.

In the present invention, even if the force-sensitive groups have the same structure of force-sensitive moiety, differences in their properties may be caused due to differences in the linker, substituent, isomer, complex structure, etc. In the present invention, unless otherwise specified, force-sensitive groups having the same structure of force-sensitive moiety but different structures due to a linker, a substituent, an isomer, a complex structure, etc. are regarded as different structures.

In the present invention, the division is made by a force activation reaction mechanism, and the covalent force sensitive groups include, but are not limited to, the following groups: covalent force sensitive groups based on homolytic mechanisms, covalent force sensitive groups based on heterolytic mechanisms, covalent force sensitive groups based on reverse cyclization mechanisms, covalent force sensitive groups based on electrocyclization mechanisms, covalent force sensitive groups based on flexural activation mechanisms, and covalent force sensitive groups based on other mechanisms.

In the present invention, covalent force sensitive groups based on the homolytic mechanism include, but are not limited to, the following series: peroxide series, disulfo/polysulfide series, diselenide/polyselenide series, azonitrile series, bisarylfuranone series, bisarylcyclic ketone series, bisarylcyclopentenedione series, bisarylchromene series, arylbiimidazole series, arylethane series, dicyanotetrarylethane series, arylpinacol series, chain transfer series, cyclohexadienone series, tetracyanoethane series, cyanoacylethane series, adamantane-substituted ethane series, bifluorene series, allylsulfide series, thio/seleno ester series covalent force sensitive groups.

In the present invention, the covalent force-sensitive group of the peroxide series homolysis mechanism refers to a force-sensitive group containing a peroxide force-sensitive element, and the structural general formula thereof includes but is not limited to the following classes:

wherein the content of the first and second substances,

each independently linked to a substituted polymer chain that participates in force activation.

A typical structure of the formula 1-A-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the covalent force-sensitive group of the disulfide/polysulfide series homolytic mechanism refers to a force-sensitive group containing disulfide/polysulfide force-sensitive elements therein, and the structural formula thereof includes but is not limited to the following types:

wherein m is the number of sulfur atoms connected by a single bond, and the value of m is a certain specific integer value of more than or equal to 2, preferably 2-20, and more preferably 2-10; wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom;

wherein the content of the first and second substances,

indicates that n is connected with

An aromatic ring of (2); wherein the value of n is 0, 1 or an integer greater than 1; the symbols are the sites connected with other structures in the formula, and if not specifically noted, the symbols appearing hereinafter have the same meaning and are not repeated; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. At different positions

Are the same or different; in order to increase the conjugation effect and the steric hindrance, promote the homolytic fracture of the force sensitive group under the action of the mechanical force, facilitate the stabilization of the formed free radical and obtain the reversible force-activated characteristic,

preferably at least one of the following structures, but the invention is not limited thereto:

said

Further preferred is at least one of the following structures, but the present invention is not limited thereto:

wherein L is₁Are divalent linking groups, each independently selected from, but not limited to:

l in different positions₁Are the same or different; wherein L is₂Are divalent linking groups, each independently selected from, but not limited to: a direct bond,

L in different positions₂Are the same or different;

wherein R is¹、R²、R³、R⁴Each independently selected from any suitable atom (including hydrogen atoms), substituent; the substituent contains a heteroatom or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure of the substituent is not particularly limited, and the substituent includes a linear structure, a branched structure or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring and combinations thereof, preferably an aliphatic ring and an aromatic ring. In general terms, R¹、R²、R³、R⁴Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C_1-20Hydrocarbyl radical, C_1-20Heterohydrocarbyl, substituted C_1-20Hydrocarbyl or substituted C_1-20Heterohydrocarbyl, and combinations of two or more of the foregoing. In order to increase the steric hindrance of the nitrogen atom in the force-sensitive group, promote the homolytic cleavage of the force-sensitive group under the action of mechanical force, facilitate the stabilization of the formed free radical, and promote the coupling of said free radical or the reversible cross-linking of the force-sensitive groupAlternatively, good reversibility is obtained, R¹、R²、R³、R⁴Each independently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C_1-20Alkyl radical, C_1-20Heteroalkyl, cyclic structure C_1-20Alkyl, C of cyclic structure_1-20Heteroalkyl group, C_1-20Aryl radical, C_1-20A heteroaryl group; in general terms, the structures in the general formulae 1-B-5, 1-B-7

said

More preferably at least one of the following structures, but the present invention is not limited thereto:

wherein the content of the first and second substances,

is a nitrogen-containing aliphatic heterocyclic ring, the number of ring-forming atoms of the ring is not particularly limited, and is preferably from 3 to 10, more preferably from 5 to 8; except that at least one of the ring-forming atoms of the aliphatic ring is a nitrogen atom, the rest of the ring-forming atoms are selected from but not limited to carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms, and hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; in order to increase the steric hindrance of the nitrogen atom in the force-sensitive group, promote homolytic cleavage of the force-sensitive group under the action of mechanical forces, facilitate stabilization of the free radicals formed, and promote coupling of said free radicals

said

wherein the content of the first and second substances,

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation. It is to be expressly noted that, when in a structure "

Each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain which may or may not participate in force activation, "at least one of the left and right sides of the activatable bond in the structure or a force-sensitive group comprising the structure

To substituted polymer chains participating in the activation of forces by which the forces are transmitted to the polymer chains

Acting on the force sensitive groups, wherein the included angle formed by the acting forces on the left side and the right side is not higher than 180 degrees, and preferably smaller than 180 degrees; unless otherwise indicated, appear hereinafter "

Each independently linked to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation "have the same meaning and are not repeated.

Typical structures of the general formulae 1-B-1 to 1-B-7 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.

Specifically, the typical structures of the formulae 1-B-1 to 1-B-7 may be further exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent force sensitive group of the diselenide/polyselene series homolysis mechanism refers to a force sensitive group containing diselenide/polyselene force sensitive elements, and the structural general formula of the covalent force sensitive group includes but is not limited to the following groups:

wherein m is the number of selenium atoms connected by a single bond, and the value of m is a certain specific integer value greater than or equal to 2, preferably 2-20, and more preferably 2-10; wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein R is¹、R²、R³、R⁴The definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-5; wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-6;

Typical structures of the formulae 1-C-1 to 1-C-7 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Specifically, typical structures of the formulae 1-C-1 to 1-C-7 may be further exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent force sensitive group of the azonitrile series homolytic mechanism refers to a force sensitive group containing azonitrile force sensitive elements, and the structural general formula of the covalent force sensitive group includes but is not limited to the following types:

wherein R is⁵、R⁶、R⁷、R⁸Each independently selected from, but not limited to, a hydrogen atom, a halogen atom, a heteroatom group, C_1-20Hydrocarbyl/heterohydrocarbyl, substituted C_1-20Hydrocarbyl/heterohydrocarbyl groups, and combinations of two or more of the foregoing, preferably selected from hydrogen atoms, halogen atoms, C_1-20Alkyl radical, C_1-20Heteroalkyl group, more preferably selected from hydrogen atom, C_1-5Alkyl radical, C_1-5Heteroalkyl, more preferably selected from cyano, methyl, ethyl, propyl, butyl;

A typical structure of the formula 1-D-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent force sensitive group of the bisaryl furanone series homolytic mechanism refers to a force sensitive group containing bisaryl furanone force sensitive elements, and the structural general formula of the covalent force sensitive group comprises but is not limited to the following types:

wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; w₁Is a divalent linking group, each of which is independently selected from, but not limited to

Is preferably selected from

Each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of the same ring structure

With or without looping.

Wherein the structure represented by formula 1-E-1 is preferably selected from at least a subset of the following general structures:

wherein each G is independently selected from

Said

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein W, W1,

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1;

wherein the content of the first and second substances,

to be connected with n

An aromatic ring of (2); wherein the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure, and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or the substituent group is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent group and heteroatom-containing substituent group; at different positions in the same general formula

Are the same or different; by way of example, the

May be selected from at least one of the following structures, but the invention is not limited thereto:

said

wherein L is₁、L₂The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.

A typical structure of the formula 1-E-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein, W, W₁、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.

Specifically, the typical structure of the formula 1-E-1 can be further exemplified as follows, but the present invention is not limited thereto:

wherein, W, W₁The definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;

In the invention, the covalent force sensitive group of the homolytic mechanism of the diaryl cyclic ketone series refers to a force sensitive group containing a diaryl cyclic ketone force sensitive element, and the structural general formula of the covalent force sensitive group includes but is not limited to the following types:

wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; w₂Is a divalent linking group, each of which is independently selected from, but not limited to

Is preferably selected from

With or without looping.

Wherein the structure represented by formula 1-F-1 is preferably selected from at least a subset of the following general structures:

wherein, W, W₂、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-F-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;

the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4.

A typical structure of the formula 1-F-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein, W, W₂、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-F-1; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.

Specifically, the typical structure of the formula 1-F-1 can be further exemplified as follows, but the present invention is not limited thereto:

wherein, W, W₂、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-F-1; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;

In the invention, the covalent force sensitive group of the diarylcyclopentenedione series homolytic mechanism refers to a force sensitive group containing diarylcyclopentenedione force sensitive elements, and the structural general formula of the covalent force sensitive group includes but is not limited to the following groups:

wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom;

With or without looping.

Wherein the structure represented by formula 1-G-1 is preferably selected from at least a subset of the following general structures:

wherein, W,

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-G-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;

A typical structure of the formula 1-G-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein, W,

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-G-1; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.

Specifically, the typical structure of the general formula 1-G-1 can be further exemplified as follows, but the present invention is not limited thereto:

wherein, the definition, the selection range and the preferable range of W are the same as those of the general formula 1-G-1; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;

In the invention, the covalent force sensitive group of the bisaryl chromene series homolytic mechanism is a force sensitive group containing bisaryl chromene force sensitive elements, and the structural general formula of the covalent force sensitive group comprises but is not limited to the following groups:

wherein W3 is a divalent linking group, each of which is independently selected from but not limited to

Is preferably selected from

V, V' are each independently selected from carbon atoms, nitrogen atoms; when V, V 'is a nitrogen atom, V, V' is linked to

Is absent;

With or without looping.

Wherein the structure represented by formula 1-H-1 is preferably selected from at least a subset of the following general structures:

wherein, W₃、V、V’、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-H-1;

Among them, the structure represented by the general formula 1-H-1 further preferably has a structure represented by the following formula:

wherein, W₃、V、V’、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-H-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;

A typical structure of the formula 1-H-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein, W₃、

The definition, selection range and preferred range of (1-H-1) are the same; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.

Specifically, the typical structure of the formula 1-H-1 can be further exemplified as follows, but the present invention is not limited thereto:

wherein, W₃The definition, selection range and preferable range of (A) are the same as those of the general formula 1-H-1; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;

In the invention, the covalent force sensitive group of the aryl biimidazole series homolytic mechanism refers to a force sensitive group containing aryl biimidazole force sensitive elements, and the structural general formula of the covalent force sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

represents that the ring has a conjugated structure; wherein the content of the first and second substances,

is a five-membered nitrogen heterocyclic structure with a conjugated structure; wherein the content of the first and second substances,

is formed by carbon and carbon between two five-membered nitrogen heterocycles through respective one ring-forming atomA single bond, a carbon-nitrogen single bond or a nitrogen-nitrogen single bond; according to different

The linkage, formula 1-I-1 includes but is not limited to one or more of the following isomers:

it should be noted that under appropriate conditions, interconversion between the various isomers can occur, and therefore, the six isomer motifs are regarded as the same structural motif in the present invention;

With or without looping.

Wherein the structure represented by the general formula 1-I-1 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of the formula (I) are the same as those of the general formula 1-I-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;

The typical structure of the formula 1-I-1 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

the definition, selection range and preferable range of the formula (I) are the same as those of the general formula 1-I-1; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.

Specifically, the typical structure of the general formula 1-I-1 can be further exemplified as follows, but the present invention is not limited thereto:

wherein L is₁The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;

In the present invention, the covalent force-sensitive group of the aryl ethane series homolysis mechanism refers to a force-sensitive group containing aryl ethane force-sensitive elements, and the structural general formula includes but is not limited to the following classes:

wherein R is₂Each independently selected from any suitable atom (including a hydrogen atom), substituent selected from hydroxy, phenyl, phenoxy, C, and substituted polymer chain with or without participation in force activation_1-10Alkyl radical, C_1-10Alkoxy radical, C_1-10Alkoxyacyl group, C_1-10Alkyl acyloxy, trimethyl siliconOxy, triethylsiloxy; wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein the content of the first and second substances,

A typical structure of the formula 1-J-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein R is₂The definition, selection range and preferable range of (A) are the same as those of the general formula 1-J-1; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;

In the invention, the covalent force-sensitive group of the dicyano tetraarylethane series homolytic mechanism refers to a force-sensitive group containing dicyano tetraarylethane force-sensitive elements, and the structural general formula of the covalent force-sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

A typical structure of the formula 1-K-1 may be exemplified as follows, but the present invention is not limited thereto:

In the invention, the covalent force sensitive group of the aryl pinacol series homolysis mechanism refers to a force sensitive group containing an aryl pinacol force sensitive element, and the structural general formula of the covalent force sensitive group includes but is not limited to the following groups:

wherein, W₄Is a divalent linking group, each of which is independently selected from, but not limited to, a direct bond,

Preferably from a direct bond,

A typical structure of the formula 1-L-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein, W₄The definition, selection range and preferable range of (A) are the same as those of the general formula 1-L-1;

In the present invention, the covalent force-sensitive group of the chain transfer series homolytic mechanism refers to a force-sensitive group containing a chain transfer force-sensitive element, and the structural general formula thereof includes but is not limited to the following classes:

wherein R is₂And

the definition, selection range and preferable range of (A) are the same as those of the general formula 1-J-1; w₄The definition, selection range and preferable range of (A) are the same as those of the general formula 1-L-1; r¹、R²、R³、R⁴The definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-5;

wherein R is₁Each independently selected from atoms (including hydrogen atoms), substituents, R at different positions₁Are the same or different in structure; wherein the substituent contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably the number of carbon atoms is 1 to 20, more preferably 1 to 10, the structure of the substituent is not particularly limited, and the substituent includes but is not limited to a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; in general terms, R₁Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C_1-20Hydrocarbyl/heterohydrocarbyl, substituted C_1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing. In order to promote the homolytic fracture of the force sensitive group under the action of mechanical force, increase the oxidation resistance of the formed carbon free radical, stabilize the formed carbon free radical, facilitate the coupling of the further free radical or participate in other free radical reactions, and obtain the reversible force-induced activation characteristic, the self-repairing performance and the self-enhancing performance, R₁Each independently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C_1-20Alkyl radical, C_1-20Aryl radical, C_1-20Heteroaromatic hydrocarbon group and acyl, acyloxy, oxyacyl, sulfuryl, phenylene substituted C_1-20Hydrocarbyl/heterohydrocarbyl; r₁Further preferably selected from the group consisting of a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, phenyl group, hydroxyl group, cyano group, carboxyl group, methyloxyacyl group, ethyloxyacyl group, propyloxyacyl group, butyloxyacyl group;

wherein, V₃Selected from tellurium atoms, antimony atoms, bismuth atoms; wherein k is and V₃Connected to each other

The number of (2); when V is₃In the case of tellurium atoms, k is 1, meaning that there is only one

And V₃Connecting; when V is₃When it is an antimony atom or a bismuth atom, k is 2, which means that there are two

And V₃Are connected with two

Are the same or different in structure;

wherein, L 'is a divalent linking group, and the structures of L' at different positions are the same or different; wherein the divalent linking group contains a hetero atom or does not contain a hetero atom, the number of carbon atoms is not particularly limited, preferably the number of carbon atoms is 1 to 20, more preferably 1 to 10, the structure is not particularly limited,including but not limited to linear structures, pendant-containing branched structures, or cyclic structures selected from the group consisting of aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof, with aliphatic and aromatic rings being preferred. In general terms, each of said L' is independently selected from the group consisting of a heteroatom linking group, a heteroatom group linking group, a divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing. Wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. In order to promote homolytic cleavage of the force sensitive group under the action of mechanical force, increase oxidation resistance of the formed carbon free radical, stabilize the formed carbon free radical, facilitate further coupling of the free radical or participate in other free radical reactions, and obtain reversible force-induced activation property, self-repairing property and self-enhancing property, L' is respectively and independently preferably selected from acyl, acyloxy, acylthio, oxyacyl, sulfuryl, phenylene and divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20Hydrocarbyl/heterohydrocarbyl; wherein said substituted divalent C_1-20The structure of the substituent group in the hydrocarbon/heterohydrocarbon group is preferably an acyl group, an acyloxy group, an acylthio group, an oxyacyl group, a thioacyl group, a phenylene group, and more preferably the substituted divalent C_1-20The hydrocarbyl/heterohydrocarbyl group being linked to R via said substituent group₁To the carbon atom(s) of (a);

in general terms, of the formulae 1-M-1 to 1-M-8

Preferably, the present invention is not limited to one selected from the following structures:

wherein R is selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; wherein R represents the number of R connected with a benzene ring, and the value of R is an integer selected from 0 to 5; wherein m is the number of repeating units, which can be a fixed value or an average value;

said

wherein, the definitions, selection ranges and preferred ranges of R, R and m are as described in the primary structure;

wherein the content of the first and second substances,

A typical structure of the formula 1-M-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein R is₂The definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-1;

Typical structures of the general formula 1-M-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-2;

Typical structures of the general formulae 1 to M-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein, W₄The definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-3;

Typical structures of the general formulae 1 to M-4 may be exemplified as follows, but the present invention is not limited thereto:

wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-4;

Typical structures of the general formulae 1 to M-5 may be exemplified as follows, but the present invention is not limited thereto:

wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-5;

Typical structures of the general formulae 1 to M-6 may be exemplified as follows, but the present invention is not limited thereto:

wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-6;

each independently linked to a substituted polymer chain that participates in force activation. Typical structures of the general formulae 1 to M-7 may be exemplified as follows, but the present invention is not limited thereto:

wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-7;

each independently linked to a substituted polymer chain that participates in force activation. Typical structures of the formulae 1 to M-8 may be illustrated below, but the present invention is not limited thereto:

wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-8;

In the invention, the covalent force sensitive group of the cyclohexadienone series homolytic mechanism refers to a force sensitive group containing cyclohexadienone force sensitive elements, and the structural general formula of the covalent force sensitive group comprises but is not limited to the following types:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4;

Typical structures of the formulae 1-N-1 to 1-N-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent force-sensitive group of the tetracyanoethane series homolysis mechanism refers to a force-sensitive group containing tetracyanoethane force-sensitive elements, and the structural general formula of the covalent force-sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

Wherein the structure represented by formula 1-O-1 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferred range of (1)General formula 1-B-3;

A typical structure of formula 1-O-1 can be exemplified as follows, but the present invention is not limited thereto:

In the present invention, the covalent force-sensitive group of the cyanoacyl ethane series homolysis mechanism refers to a force-sensitive group containing cyanoacyl ethane force-sensitive elements, and the structural general formula thereof includes but is not limited to the following types:

wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; wherein, W₅Is a divalent linking group, each of which is independently selected from, but not limited to, a direct bond,

Is preferably selected from

Each independently andany two of any suitable atoms (including hydrogen atoms), substituents, and substituted polymer chains with or without participation in force activation may be linked together in the same ring structure

With or without looping.

Wherein the structure represented by formula 1-P-1 is preferably selected from at least a subset of the following general structures:

wherein, W, W₅、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-P-1.

A typical structure of the formula 1-P-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent force sensitive group of the adamantane substituted ethane series homolytic mechanism refers to a force sensitive group containing adamantane substituted ethane force sensitive elements, and the structural general formula of the covalent force sensitive group includes but is not limited to the following types:

wherein Ad is selected from the group consisting of bivalent or multivalent adamantyl and dimeric or multimeric derivatives thereof; by way of example, the Ad is selected from, but not limited to:

wherein the content of the first and second substances,

A typical structure of the formula 1-Q-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent force sensitive group of the bifluorene series homolysis mechanism refers to a force sensitive group containing bifluorene force sensitive elements, and the structural general formula of the covalent force sensitive group includes but is not limited to the following types:

wherein R is₃Each independently selected from cyano, C_1-10Alkoxyacyl group, C_1-10Alkyl acyl radical, C_1-10An alkylaminoacyl group, a phenyl group, a substituted phenyl group, an aromatic hydrocarbon group, a substituted aromatic hydrocarbon group, wherein the substituent atom or the substituent group is not particularly limited and is selected from any one or more of a halogen atom, a hydrocarbon group substituent group, and a heteroatom-containing substituent group; wherein the content of the first and second substances,

Typical structures of the general formula 1-R-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the covalent force-sensitive group of the allylic sulfide series homolysis mechanism refers to a force-sensitive group containing allylic sulfide force-sensitive elements, and the structural general formula includes but is not limited to the following classes:

wherein, C¹、C²、C³Represents carbon atoms, and the numbers at the upper right corner of the carbon atoms are used for distinguishing carbon atoms at different positions so as to facilitate the accuracy and the conciseness of description;

wherein R is₁ ¹、R₁ ²、R₁ ³、R₁ ⁴Each independently selected from atoms (including hydrogen atoms), substituents; r₁ ¹、R₁ ²、R₁ ³、R₁ ⁴Each independently preferably selected from a hydrogen atom, a halogen atom, C_1-20Hydrocarbyl/heterohydrocarbyl, substituted C_1-20A hydrocarbon group/heterohydrocarbon group, the substituent atom or substituent group being not particularly limited; r₁ ¹、R₁ ²、R₁ ³、R₁ ⁴Each independently more preferably from a hydrogen atom, a halogen atom, C_1-20Alkyl radical, C_1-20Aryl radical, C_1-20Heterohydrocarbyl radical, C_1-20Hydrocarbyloxyacyl group, C_1-20A substituent formed of a hydrocarbylthioacyl group and a combination of two or more of the above groups; r₁ ¹、R₁ ²、R₁ ³、 R₁ ⁴Each independently of the others is preferably selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl;

wherein Z is₂Is a divalent linking atom or a divalent linking group; when Z is₂When selected from divalent linking atoms, it is selected from S atoms; when Z is₂When the divalent linking group is selected, the divalent linking group contains a hetero atom or does not contain a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10; the structure thereof is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure or a cyclic structure; the cyclic structure is selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; in general terms, Z₂Selected from, but not limited to, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed by a hydrocarbyl/heterohydrocarbyl group and a combination of two or more of the above groups, wherein the substituent atom or substituent group is not particularly limited and is selected from any one or more of a halogen atom, a hydrocarbyl substituent group, and a heteroatom-containing substituent group; z₂More preferably divalent acrylic or methacrylic acid and the corresponding esters thereof, N-mers (N.gtoreq.2) of divalent styrene or methylstyrene such as trimers, tetramers;

when Z is₂Selected from divalent linking atoms, Z₁Is and C²A divalent linking group in which the atoms are directly linked; the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure of the divalent linking group is not particularly limited, and the divalent linking group includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, preferably an aromatic ring; in general terms, the divalent linking group is selected from, but not limited to, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z1 is more preferably selected from divalent C_1-20Alkyl, divalent C_1-20Aromatic hydrocarbon radical, divalent C_1-20Alkoxy, divalent C_1-20Aryloxy, divalent C_1-20Alkylthio, divalent C_1-20Arylthio, most preferably selected from divalent C_1-20An alkylthio group; in particular, Z₁Preferably from methylene, methylene sulfide, ethylene, propylene, butylene, pentylene, hexylene, divalent phenyl ether, divalent benzyl, divalent ethoxy, divalent butoxy, divalent hexyloxy, most preferably selected from methylene sulfide; when Z is₂Selected from said divalent linking groups, Z₁Is and C²A divalent linking group in which the atoms are directly linked; the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure of the divalent linking group is not particularly limited, and the divalent linking group includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, preferably an aromatic ring; in general terms, the divalent linking group is selected from, but not limited to: divalent heteroatom radical linking group, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z₁More preferably from divalent connecting group with electron-withdrawing effect, divalent connecting group substituted by electron-withdrawing effect substituent, so as to facilitate the homolytic cleavage of the force sensitive group and obtain more remarkable force-induced response effect; wherein, the divalent linking group with electron-withdrawing effect includes but is not limited to acyl, acyloxy, acylthio, phenylene; the divalent linking group substituted by the substituent having the electron-withdrawing effect includes, but is not limited to, acyl group, acyloxy group, acylthio group, phenylene group, nitro group, sulfonic acid group, aromatic hydrocarbon group, cyano group, halogen atom, and divalent C group substituted by trifluoromethyl group_1-20Hydrocarbyl/heterohydrocarbyl; by way of example, the divalent linking group substituted with an electron-withdrawing substituent includes, but is not limited to, an acyl group, an acyloxy group, an acylthio group, a phenylene group, a nitro group, a sulfonic acid group, an aromatic hydrocarbon group, a cyano group, a halogen atom, a trifluoromethyl-substituted phenylene group, a benzylidene group, a naphthylidene group, a pyrrolylidene group, a pyridylidene group;

wherein the content of the first and second substances,

A typical structure of the formula 1-S-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein n is the number of repeating units, can be a fixed value or an average value, and is an integer greater than or equal to 1;

In the invention, the covalent force sensitive group of the thio/seleno ester type homogeneous splitting mechanism is a force sensitive group containing thio/seleno ester force sensitive elements, and the structural general formula of the covalent force sensitive group includes but is not limited to the following types:

wherein, W₆Each independently selected from a sulfur atom or a selenium atom;

wherein Z is₃A divalent linking group containing or not containing a heteroatom, the number of carbon atoms of which is not particularly limited, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, the structure of which is not particularly limited, including but not limited to a linear structure, a branched structure, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; by way of example, Z₃Selected from, but not limited to, divalent heteroatom linkers, divalent heteroatom group linkers, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;

wherein Z4 is a divalent linking group containing or not containing a heteroatom, the number of carbon atoms thereof is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure thereof is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring and combinations thereof, preferably an aromatic ring; the divalent linking group is selected from but not limited to divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z₄More preferably C substituted by cyano, alkyl, aryl, ester groups_1-20Hydrocarbyl/heterohydrocarbyl;

wherein the content of the first and second substances,

Wherein the structure represented by formula 1-T-1 is preferably selected from at least a subset of the following general structures:

wherein, W₆、Z₄、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-T-1;

wherein Z is₅Selected from oxygen atom, sulfur atom, selenium atom, silicon atom, carbon atom, nitrogen atom; when Z is₅When it is an oxygen atom, a sulfur atom, or a selenium atom, R₁ ⁵、R₁ ⁶、R₁ ⁷Does not storeAt least one of the following steps; when Z is₅When it is a nitrogen atom, R₁ ⁵Exist, R₁ ⁶、R₁ ⁷Is absent; when Z is₅When it is a silicon atom or a carbon atom, R₁ ⁵、R₁ ⁶Exist, R₁ ⁷Is absent;

wherein R is₁ ⁵、R₁ ⁶、R₁ ⁷、R₁ ⁸Each independently selected from an atom (including a hydrogen atom), a substituent; r₁ ⁵、R₁ ⁶、R₁ ⁷、R₁ ⁸Each independently preferably selected from a hydrogen atom, a halogen atom, C_1-20Hydrocarbyl/heterohydrocarbyl, substituted C_1-20Hydrocarbyl/heterohydrocarbyl; r₁ ⁵、R₁ ⁶、R₁ ⁷、R₁ ⁸Each independently more preferably from a hydrogen atom, a halogen atom, C_1-20Alkyl radical, C_1-20Alkenyl radical, C_1-20Aryl radical, C_1-20Alkoxyacyl group, C_1-20Alkoxythioacyl, C_1-20Aryloxy acyl group, C_1-20Aryloxythioacyl, C_1-20Alkylthio acyl radical, C_1-20An arylthioacyl group;

wherein Z is₆Is a divalent linking group; the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, and the structure thereof is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, preferably an aromatic ring. The divalent linking group is selected from, but not limited to: divalent heteroatom radical linking group, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z₆Preferably selected from divalent linking groups having an electron-withdrawing effect, divalent linking groups substituted with electron-withdrawing substituents, to facilitate homolytic cleavage of said force-sensitive groups, to obtainMore remarkable force-induced response effect is obtained; wherein, the divalent linking group with electron-withdrawing effect includes but is not limited to acyl, acyloxy, acylthio, phenylene; the divalent linking group substituted by the substituent having the electron-withdrawing effect includes, but is not limited to, acyl group, acyloxy group, acylthio group, phenylene group, nitro group, sulfonic acid group, aromatic hydrocarbon group, cyano group, halogen atom, and divalent C group substituted by trifluoromethyl group_1-20Hydrocarbyl/heterohydrocarbyl. By way of example, the divalent linking group substituted with an electron-withdrawing substituent includes, but is not limited to, an acyl group, an acyloxy group, an acylthio group, a phenylene group, a nitro group, a sulfonic acid group, an aromatic hydrocarbon group, a cyano group, a halogen atom, a trifluoromethyl-substituted phenylene group, a benzylidene group, a naphthylidene group, a pyrrolylidene group, and a pyridylidene group.

A typical structure of the formula 1-T-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, covalent force sensitive groups based on the heterolytic mechanism include, but are not limited to, the following series: triaryl sulfur salt series, o-phthalaldehyde series, sulfonic acid series, and seleno/seleno-sulfur/seleno-nitrogen series.

In the invention, the covalent force-sensitive group of the triaryl sulfate series heterolysis mechanism refers to a force-sensitive group containing triaryl sulfate force-sensitive elements, and the structural general formula of the covalent force-sensitive group includes but is not limited to the following groups:

wherein the content of the first and second substances,

each independently of any suitable atom (including hydrogen atom)A), substituents, and substituted polymer chains with or without participation in force activation, wherein any two of the same ring structure are linked

With or without looping.

A typical structure of the formula 2-A-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent force-sensitive group of the ortho-phthalaldehyde series heterolysis mechanism is a force-sensitive group containing ortho-phthalaldehyde force-sensitive elements, and the structural general formula of the covalent force-sensitive group comprises but is not limited to the following groups:

wherein, the ring of M is aliphatic ring, ether ring or the combination of the aliphatic ring, the ether ring and the aromatic ring, the ring-forming atoms of the ring structure are respectively and independently carbon atoms, nitrogen atoms or other hetero atoms, and at least one ring-forming atom is oxygen atom; the hydrogen atoms attached to the ring-forming atoms may be substituted or unsubstituted with any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;

wherein the content of the first and second substances,

A typical structure of the formula 2-B-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the covalent force-sensitive group of the sulfonic acid group series heterolysis mechanism refers to a force-sensitive group containing sulfonic acid group force-sensitive elements therein, and the structural general formula thereof includes but is not limited to the following classes:

wherein the content of the first and second substances,

A typical structure of the formula 2-C-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent force-sensitive group of the seleno-oxo/seleno-thio/seleno-nitrogen series heterofission mechanism refers to a force-sensitive group containing seleno-oxo/seleno-thio/seleno-nitrogen force-sensitive elements, and the structural general formula includes but is not limited to the following types:

wherein each W is independently selected from oxygen atom and sulfur atomA seed; wherein the content of the first and second substances,

each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, to the same atom

With or without looping.

Wherein the structures represented by the general formulae 2-D-1 and 2-D-2 are preferably selected from at least a subset of the following general structures:

wherein W is as defined for formula 2-D-1; wherein the content of the first and second substances,

indicates that n is connected with

A nitrogen-containing aromatic ring of (a); the number of ring-forming atoms of the ring is not particularly limited, and is preferably from 5 to 8; except that at least one of the ring-forming atoms is a nitrogen atom and the ring and the selenium atom are connected through the nitrogen atom, the remaining ring-forming atoms are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms may be substituted or unsubstituted with any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; wherein the value of n is 0, 1 or an integer greater than 1; at different positions

Structure of (1)The same or different; said

The structure of (a) is preferably selected from pyridine rings and substituted forms thereof;

any two of which are each independently attached to the same atom, including a hydrogen atom, a substituent, and a substituted polymer chain, with or without participation in force activation

With or without rings, any two of the same ring structure

With or without looping.

Typical structures of the general formulae 2-D-1, 2-D-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein X is selected from but not limited to fluorine atom, chlorine atom, bromine atom, cyano group, and isothiocyanato group, preferably from chlorine atom and bromine atom; the definition, selection range and preferable range of W are the same as those of the general formula 2-D-1;

each independently and a substituted polymer chain involved in force activation.

In the present invention, covalent force-sensitive groups based on the reverse cyclization mechanism include, but are not limited to, the following series: cyclobutane series, monoepoxybutane series, dioxetane series, dinitrocyclobutane series, cyclobutene series, triazole ring series, DA series, hetero DA series, light-controlled DA series, and [4+4] cycloaddition series.

In the invention, the covalent force-sensitive group of the cyclobutane series reverse cyclization mechanism refers to a force-sensitive group containing a cyclobutane force-sensitive element, and the structural general formula of the covalent force-sensitive group includes but is not limited to the following groups:

wherein each Q is independently selected from an oxygen atom, a carbon atom; b represents the number of connections to Q, respectively; when each Q is independently selected from oxygen atoms, b ═ 0; when each Q is independently selected from carbon atoms, b ═ 2;

Wherein the structure represented by the general formula 3-A-1 is preferably selected from at least a subset of the following general structures:

wherein each J is independently selected from the group consisting of oxygen atoms, sulfur atoms, substituted versions of secondary amine groups; ar is independently selected from aryl, preferably phenyl; n represents the number of connections to Ar; x₀Each independently selected from a halogen atom, preferably from a fluorine atom, a chlorine atom, a bromine atom;

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-A-1.

Wherein the structure represented by the general formula 3-A-1-1 is further preferably selected from the following general structures:

wherein each J' is independently selected from an oxygen atom, a sulfur atom; j is defined, selected and preferred in the same range as in the general formula 3-A-1-3;

A typical structure of the formula 3-A-1-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein, R, R₁、R₂Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation; j is defined, selected and preferred in the same range as in the general formula 3-A-1-3; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;

Wherein the structure represented by the general formula 3-A-1-2 is further preferably selected from the following general structures:

wherein the definition, the selection range and the preferred range of J are the same as those of the general formula 3-A-1-3; definition of JThe selection range and the preferred range are the same as the general formula 3-A-1-1-6;

A typical structure of the formula 3-A-1-2 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by the general formula 3-A-1-3 is further preferably selected from the following general structures:

wherein the definition, the selection range and the preferred range of J are the same as those of the general formula 3-A-1-3;

Typical structures of the general formula 3-A-1-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein R is₁、R₂Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;

Wherein the structure represented by formula 3-A-1-4 is further preferably selected from the following general structures:

Typical structures of the general formula 3-A-1-4 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-A-1-5 is further preferably selected from the following general structures:

Typical structures of the general formula 3-A-1-5 can be exemplified as follows, but the present invention is not limited thereto:

wherein R is selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;

Wherein the structure represented by the general formula 3-A-1-6 is further preferably selected from the following general structures:

wherein the definition, the selection range and the preferred range of J are the same as those of the general formula 3-A-1-3; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;

definition, selection range, and advantages ofThe selection range is the same as that of the general formula 3-A-1.

Typical structures of the general formula 3-A-1-6 can be exemplified as follows, but the present invention is not limited thereto:

wherein, R, R₁、R₂、R₃Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;

Wherein the structure represented by the general formula 3-A-1-7 is further preferably selected from the following general structures:

Typical structures of the general formula 3-A-1-7 may be exemplified as follows, but the present invention is not limited thereto:

wherein, R, R₁、R₂、R₃、R₄Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;

Wherein the structure represented by the general formula 3-A-1-8 is further preferably selected from the following general structures:

Typical structures of the general formula 3-A-1-8 can be exemplified as follows, but the present invention is not limited thereto:

wherein, R, R₁、R₂Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;

Wherein the structure represented by formula 3-A-1-9 is further preferably selected from the following general structures:

Typical structures of the general formula 3-A-1-9 can be exemplified as follows, but the present invention is not limited thereto:

Typical structures of the general formula 3-A-1-10 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

are independent of each other and participate in forceThe activated substituted polymer chains are linked.

Typical structures of the general formula 3-A-1-11 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by formula 3-A-1-12 is further preferably selected from the following general structures:

wherein the content of the first and second substances,

Typical structures of the general formula 3-A-1-12 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In addition, the typical structure of the covalent force sensitive group of the cyclobutane series reverse cyclization mechanism can be exemplified as follows, but the present invention is not limited thereto:

wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;

A typical structure of the formula 3-A-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Typical structures of the general formula 3-A-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein R is₁、R₂Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;

Typical structures of the general formula 3-A-4 may be exemplified as follows, but the present invention is not limited thereto:

In the present invention, the covalent force-sensitive group of the reverse cyclization mechanism of the mono-heterocyclic butane series refers to a force-sensitive group containing a mono-heterocyclic butane force-sensitive element, and the structural general formula thereof includes but is not limited to the following types:

wherein Q is selected from oxygen atom and carbon atom; b represents the number of connections to Q; when Q is selected from oxygen atom, b ═ 0; when Q is selected from carbon atoms, b ═ 2; d is selected from oxygen atom, sulfur atom and nitrogen atom; a represents the number of connections to D; when D is selected from oxygen atom and sulfur atom, a is 0; when D is selected from a nitrogen atom, a ═ 1;

A typical structure of the formula 3-B-1 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by the general formula 3-B-2 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-B-2.

A typical structure of the formula 3-B-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;

In the present invention, the covalent force-sensitive group of the reverse cyclization mechanism of the dioxetane series refers to a force-sensitive group containing a dioxetane force-sensitive element, and the structural general formula thereof includes but is not limited to the following groups:

wherein J is selected from the group consisting of a direct bond, an oxygen atom, a sulfur atom, a substituted form of a secondary amine group, a methylene group, and substituted forms thereof; wherein Ar is selected from aromatic rings; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atomsAn atom, a sulfur atom, a boron atom, a phosphorus atom, a silicon atom, a hydrogen atom attached to a ring-forming atom may be substituted or unsubstituted with any suitable substituent atom, substituent group; among them, the substituent atom or the substituent is not particularly limited, and it is preferably selected from a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, C_1-20Alkyl radical, C_1-20Alkylsiloxy group, C_1-20Acyloxy, C_1-20Alkoxyacyl group, C_1-20Alkoxy radical, C_1-20Alkylthio radical, C_1-20An alkylamino group; suitable Ar's may be selected from the following structures by way of example, but the invention is not limited thereto:

wherein L is₁Is a divalent linking group selected from, but not limited to, an oxygen atom, a sulfur atom, substituted forms of secondary amine groups, methylene groups, and substituted forms thereof; l is₂Is a divalent linking group selected from, but not limited to, a direct bond, an oxygen atom, a sulfur atom, substituted forms of secondary amine groups, methylene and substituted forms thereof, carbonyl, thiocarbonyl; wherein the content of the first and second substances,

Typical structures of the formulae 3-C-1 to 3-C-7 may be exemplified as follows, but the present invention is not limited thereto:

In the present invention, the covalent force-sensitive group of the reverse cyclization mechanism of the diazocyclobutane series refers to a force-sensitive group containing a diazobutane force-sensitive element, and the structural general formula thereof includes but is not limited to the following groups:

Typical structures of the general formulae 3-D-1 and 3-D-2 are exemplified below, but the present invention is not limited thereto:

In the invention, the covalent force-sensitive group of the cyclobutene series reverse cyclization mechanism refers to a force-sensitive group containing cyclobutene force-sensitive elements, and the structural general formula of the covalent force-sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are independently selected from carbon atom, nitrogen atom or other hetero atoms, the ring structure is preferably 6-50 membered ring, more preferably 6-12 membered ring; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the ring structure is preferably a benzene ring, a naphthalene ring, an anthracene ring and substituted forms of the above ring structures; n represents the number of linkages to the ring-forming atoms of the cyclic structure; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;

Typical structures of the general formulae 3-E-1 to 3-E-7 may be exemplified as follows, but the present invention is not limited thereto:

each independently of ginsengLinked to a force activated substituted polymer chain.

In the invention, the covalent force sensitive groups of the cyclobutane series, the monoheterocyclic butane series, the dioxetane series, the dinitrocyclobutane series and the cyclobutene series can also be activated by other actions besides mechanical force, for example, the cyclobutane series covalent force sensitive groups can perform reverse cyclization reaction under the irradiation of ultraviolet light with certain frequency so as to dissociate the force sensitive groups; the covalent force sensitive groups of the dioxetane series can be subjected to a reverse cyclization reaction under one or more of the activation effects of chemistry, biology, heat and the like, so that the force sensitive groups are dissociated.

In the invention, the covalent force-sensitive group of the triazole ring series reverse cyclization mechanism is a force-sensitive group containing a triazole ring force-sensitive element, and the structural general formula of the covalent force-sensitive group comprises but is not limited to the following groups:

wherein the content of the first and second substances,

A typical structure of the formula 3-F-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent force-sensitive group of the DA series reverse cyclization mechanism refers to a force-sensitive group containing DA force-sensitive elements, and the structural general formula of the covalent force-sensitive group comprises but is not limited to the following classes:

wherein, each I is independently selected from an oxygen atom, a sulfur atom, a substitution form of a secondary amino group, a substitution form of an amido group, an ester group and a divalent small molecule hydrocarbon group, and is more preferably selected from an oxygen atom, a methylene group, a 1, 2-ethylene group, a 1, 1' -vinyl group, a substitution form of a secondary amino group, a substitution form of an amido group and an ester group;

the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are independently selected from carbon atom, nitrogen atom or other hetero atoms, the ring structure is preferably 6-50 rings, more preferably 6-12 rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the ring structure is preferably a benzene ring, a naphthalene ring, an anthracene ring and substituted forms of the above groups; n represents the number of linkages to the ring-forming atoms of the cyclic structure;

Wherein the structure represented by formula 3-G-1 is preferably selected from at least a subset of the following general structures:

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-1.

A typical structure of the formula 3-G-1 may be exemplified as follows, but the present invention is not limited thereto:

A typical structure of the formula 3-G-2 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-G-3 is preferably selected from at least a subset of the following general structures:

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-3.

Typical structures of the general formula 3-G-3 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-G-4 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-4.

Typical structures of the general formula 3-G-4 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-G-5 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-5.

Wherein the structure represented by the general formula 3-G-5-1 is further preferably selected from the following general structures:

A typical structure of the formula 3-G-5-1 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by the general formula 3-G-5-2 is further preferably selected from the following general structures:

A typical structure of the formula 3-G-5-2 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-G-5-3 is further preferably selected from the following general structures:

wherein R is₁Each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;

definition, selection range, and advantages ofThe selection range is the same as that of the general formula 3-G-5.

Typical structures of the general formula 3-G-5-3 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-G-6 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-6.

Typical structures of the general formula 3-G-6 can be exemplified as follows, but the present invention is not limited thereto:

wherein, R, R₁Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;

Wherein the structure represented by formula 3-G-7 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-7.

Wherein the structure represented by the general formula 3-G-7-1 is further preferably selected from the following general structures:

A typical structure of the formula 3-G-7-1 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by the general formula 3-G-7-2 is further preferably selected from the following general structures:

A typical structure of the formula 3-G-7-2 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-G-8 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-8.

Typical structures of the general formula 3-G-8 may be exemplified as follows, but the present invention is not limited thereto:

The typical structure of the covalent force-sensitive group of the DA series reverse cyclization mechanism can also be exemplified as follows, but the present invention is not limited thereto:

In the invention, the covalent force-sensitive group of the hetero DA series reverse cyclization mechanism refers to a force-sensitive group containing a hetero DA force-sensitive element, and the structural general formula of the covalent force-sensitive group includes but is not limited to the following groups:

wherein, P₁A substituted form selected from an oxygen atom, a sulfur atom, a nitrogen atom; p₂Substituted forms selected from carbon atoms, nitrogen atoms; c. C₁、c₂Respectively represent and P₁、P₂The number of connected connections; when P is present₁When selected from oxygen atom, sulfur atom, c₁0; when P is present₁、P₂When selected from nitrogen atoms, c₁、c₂1 is ═ 1; when P is present₂When selected from carbon atoms, c₂2; i is selected from the group consisting of an oxygen atom, a sulfur atom, a substituted form of a secondary amine group, a substituted form of an amide group, an ester group, a divalent small hydrocarbon group, more preferably from the group consisting of an oxygen atom, a methylene group, a 1, 2-ethylene group, a 1, 2-vinylidene group, a 1, 1' -vinyl group, a substituted form of a secondary amine group, a substituted form of an amide group, an ester group;

Wherein the structure represented by the general formula 3-H-1 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-H-1.

A typical structure of the formula 3-H-1 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by the general formula 3-H-2 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-H-2.

A typical structure of the formula 3-H-2 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-H-3 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-H-3.

A typical structure of the formula 3-H-3 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-H-4 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-H-4.

Typical structures of the general formula 3-H-4 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-H-5 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-H-5.

Typical structures of the general formula 3-H-5 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by the general formula 3-H-6 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-H-6.

Typical structures of the general formula 3-H-6 can be exemplified as follows, but the present invention is not limited thereto:

The typical structure of the covalent force-sensitive group of the heteroDA series reverse cyclization mechanism can also be exemplified as follows, but the present invention is not limited thereto:

In the invention, the covalent force-sensitive group of the light-controlled DA series reverse cyclization mechanism refers to a force-sensitive group which contains a light-controlled locking element and a DA element sensitive to mechanical force, wherein the DA element can be used as a part of the light-controlled locking element; the existence of the light-operated locking element enables the force-sensitive clusters to have different structures under different illumination conditions and show different response effects on mechanical force, thereby achieving the purpose of locking/unlocking the force-sensitive elements; under the condition of light-operated unlocking, the DA force-sensitive element can perform inverse DA chemical reaction under the action of mechanical force, so that the polymer directly and/or indirectly generates chemical signal change, specific response to mechanical force is achieved, and force-induced response performance/effect is obtained; when the force-sensitive element is locked, it cannot be activated by mechanical force to express the force-sensitive property, or is more difficult to be activated by mechanical force to express the force-sensitive property. By utilizing the characteristics, the mechanochemical performance of the material can be regulated and controlled by selecting specific illumination conditions, the locking/unlocking regulation effect is achieved, and the applicability and the functional responsiveness of the force sensitive group are improved. Wherein, ultraviolet light (generally, ultraviolet light with a wavelength range of 310-380 nm) is selected to lock the force sensitive groups, and visible light (generally, visible light with a wavelength range of more than 420 nm) is selected to unlock the force sensitive groups. The ultraviolet light and the visible light used as the light source in the present invention have various and unlimited sources, and may be ultraviolet light or visible light directly generated by a high pressure mercury lamp, a metal halogen lamp, a mercury lamp, a xenon lamp, an LED lamp, etc. with a desired wavelength, or ultraviolet light or visible light obtained by energy transfer (including up-conversion fluorescence or down-conversion fluorescence) of a fluorophore; the fluorophore may be selected from organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, inorganic fluorophores, organic-inorganic hybrid fluorophores, and the like.

In the invention, the light control locking element comprises the following structural units:

wherein the content of the first and second substances,

each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of which

With or without rings including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.

In the invention, the Diels-Alder force-sensitive element contains at least one of the following structural units:

wherein, K₀A substitution pattern selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, a₀Represents a group K₀The number of connected connections; when K is₀When selected from oxygen atom, sulfur atom, a₀0; when K is₀When selected from substituted forms of nitrogen atoms, a₀1 is ═ 1; when K is₀When selected from carbon atoms, a₀＝2；

In the invention, the covalent force sensitive group of the reverse cyclization mechanism of the optically controlled DA series has a structural general formula including but not limited to the following classes:

wherein, K₁、K₂、K₃、K₄、K₅、K₆Each independently selected from the group consisting of carbon, oxygen, sulfur, and nitrogen, and at K₁、K₂Or K₃K4, or K₅、K₆At least one of them is selected from carbon atoms; a is₁、a₂、a₃、a₄、a₅、a₆Respectively represent and K₁、K₂、 K₃、K₄、K₅、K₆The number of connected connections; when K is₁、K₂、K₃、K₄、K₅、K₆Each independently selected from an oxygen atom and a sulfur atom₁、 a₂、a₃、a₄、a₅、a₆0; when K is₁、K₂、K₃、K₄、K₅、K₆Each independently selected from the substituted forms of the nitrogen atom, a₁、a₂、a₃、a₄、 a₅、a₆1 is ═ 1; when K is₁、K₂、K₃、K₄、K₅、K₆Each independently selected from carbon atoms, a₁、a₂、a₃、a₄、a₅、a₆＝2；I₁、I₂、I₃Each independently absent or each independently selected from the group consisting of an oxygen atom, a 1, 1 '-carbonyl group, a methylene group and substituted forms thereof, a 1, 2-ethylene group and substituted forms thereof, a 1, 1' -vinyl group and substituted forms thereof; when I is₁、I₂、I₃Each independently absent, b ═ 2; when I is₁、I₂、I₃Each independently selected from the group consisting of an oxygen atom, 1 '-carbonyl, methylene and substituted forms thereof, 1, 2-ethylene and substituted forms thereof, 1' -vinyl and substituted forms thereof, b ═ 1; m is selected from the group consisting of oxygen atom, substituted form of nitrogen atom, divalent alkoxy chain

Substituted forms of oxygen atoms, nitrogen atoms are preferred; c represents the number of connections to M; when M is selected from an oxygen atom, a divalent alkoxy chain, c ═ 0; when M is selected from nitrogen atoms, c ═ 1; c₁、C₂、 C₃、C₄、C₅、C₆Represent carbon atoms in different positions;

each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, and preferably at K₁And K₂K to₃And K₄K to₅And K₆C to₁And C₂C to₃And C₄C to₅And C₆Forming a ring; the ring formed may be any number of rings, preferably five-membered rings and six-membered rings, which may be aliphatic rings, aromatic rings, ether rings, condensed rings and combinations thereof, the ring-forming atoms are each independently selected from the group consisting of carbon atoms, oxygen atoms, substituted forms of nitrogen atoms, sulfur atoms, silicon atoms, selenium atoms or other heteroatoms, and the hydrogen atoms on the ring-forming atoms may be substituted with any substituent or may not be substituted; wherein, K₁And K₂K to₃And K₄K to₅And K₆The ring formed between preferably has the following structure:

C₁and C₂C to₃And C₄The ring formed between preferably has the following structure:

C₅and C₆The ring formed between preferably has the following structure:

wherein the structure represented by the general formula 3-I-1 is preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain with or without participation in force activation, and R₁、R₂No ring is formed between the two;

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; e₁、E₂Each independently selected from any one of the following structures:

a typical structure of the formula 3-I-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula 3-I-2 is preferably selected from at least a subset of the following general structures:

wherein E is₁、E₂The definition, selection range and preferable range of the formula (I) are the same as those of the general formula 3-I-1-1;

A typical structure of the general formula 3-I-2 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula 3-I-3 is preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂、R₃、R₄Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, and which does not form a ring between each two; e is selected from any one of the following structures:

wherein the content of the first and second substances,

Typical structures of the general formula 3-I-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula 3-I-4 is preferably selected from at least a subset of the following general structures:

wherein the definition, the selection range and the preferred range of E are the same as those of the general formula 3-I-3-1;

Typical structures of the general formulae 3 to I-4 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula 3-I-5 is preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂、R₃、R₄、R₅、R₆Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, and which does not form a ring between each two;

Typical structures of the general formulae 3 to I-5 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula 3-I-6 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

Typical structures of the general formulae 3 to I-6 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula 3-I-7 is preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain with or without participation in force activation, and R₁、R₂No ring is formed between the two; the definition, the selection range and the preferred range of the E are the same as those of the general formula 3-I-3-1; f is selected from any one of the following structures:

Typical structures of the general formulae 3 to I-7 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula 3-I-8 is preferably selected from at least a subset of the following general structures:

wherein the definition, the selection range and the preferred range of E are the same as those of the general formula 3-I-3-1; the definition, the selection range and the preferred range of F are the same as those of the general formula 3-I-7-1;

Typical structures of the general formulae 3 to I-8 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula 3-I-9 is preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain with or without participation in force activation, and R₁、R₂Do not formA ring; g is selected from any one of the following structures:

Typical structures of the general formulae 3 to I-9 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula 3-I-10 is preferably selected from at least a subset of the following general structures:

wherein, the definition, the selection range and the preferred range of G are the same as those of the general formula 3-I-9-1;

Typical structures of the general formulae 3 to I-10 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula 3-I-11 is preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂、R₃、R₄Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, and which does not form a ring between each two; the definition, the selection range and the preferred range of F are the same as those of the general formula 3-I-7-1;

Typical structures of the general formulae 3 to I-11 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula 3-I-12 is preferably selected from at least a subset of the following general structures:

wherein, the definition, the selection range and the preferred range of F are the same as those of the general formula 3-I-7-1;

Typical structures of the general formulae 3 to I-12 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein, R in the typical structure example of the 3-I series is independently selected from any suitable atom (including hydrogen atom), substituent and substituted polymer chain which does not participate in force activation, preferably from hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl, amino, carboxyl, ester group, cyano, methyl, ethyl, propyl, vinyl, trifluoromethyl, phenyl, pyridyl, more preferably from hydrogen atom, fluorine atom, cyano, methyl, phenyl; r₁、 R₂、R₃、R₄、R₅、R₆Each independently selected from any suitable hydrogen atom, substituted alkyl group, and substituted polymer chain not involved in force activation; r₀Each independently selected from the group consisting of: -H, -CH₃、-F、-Cl、-Br、-COOH、-CN、

In the invention, the covalent force sensitive groups of DA series, hybrid DA series and light-operated DA series reverse cyclization mechanisms can also undergo reverse cyclization reaction through thermal activation so as to dissociate the force sensitive groups.

In the present invention, the covalent force-sensitive group of the [4+4] cycloaddition series reverse cyclization mechanism refers to a force-sensitive group containing a [4+4] cycloaddition force-sensitive element, and the structural general formula thereof includes but is not limited to the following classes:

wherein the content of the first and second substances,

the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are respectively and independently selected from carbon atoms, substitution forms of nitrogen atoms or other hetero atoms, the ring structure is preferably 6-50-membered ring, more preferably 6-12-membered ring; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the ring structure is preferably a benzene ring, a naphthalene ring, an anthracene ring, an aza-benzene, an aza-naphthalene, an aza-anthracene or a substituted form of the above groups; i is₆～I₁₄Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a substituted form of an amide group, an ester group, a substituted form of an imine group, and a divalent small hydrocarbon group, more preferably from the group consisting of an oxygen atom, a methylene group, a 1, 2-diethylene group, a 1, 2-vinylidene group, and a substituted form of an amide groupSubstitution forms, ester groups, substitution forms of imino groups;

Wherein the structure represented by the general formula 3-J-1 is preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂、R₃、R₄Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, and which does not form a ring between each two;

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-1.

A typical structure of the formula 3-J-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by formula 3-J-2 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

definition and selection range ofThe preferred range is the same as that of the general formula 3-J-2.

A typical structure of the formula 3-J-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by formula 3-J-3 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-3.

Typical structures of the general formula 3-J-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Among them, the force sensitive groups of formula 3-J-4, which are preferably selected from a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-4.

Typical structures of the general formula 3-J-4 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Among them, the force sensitive groups of formula 3-J-5, which are preferably selected from a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-5.

Typical structures of the general formula 3-J-5 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Among them, the force sensitive groups of formula 3-J-6, which are preferably selected from a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-6.

Typical structures of the general formulae 3-J-6 may be exemplified as follows, but the present invention is not limited thereto:

wherein R is₁Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;

Wherein the structure represented by formula 3-J-7 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-7.

Typical structures of the general formula 3-J-7 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by formula 3-J-8 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-8.

Typical structures of the general formula 3-J-8 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by formula 3-J-9 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-9.

Typical structures of the general formula 3-J-9 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by formula 3-J-10 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-10.

Typical structures of the general formula 3-J-10 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by formula 3-J-11 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-11.

Typical structures of the general formula 3-J-11 may be exemplified as follows, but the present invention is not limited thereto:

Among them, the force sensitive groups of formula 3-J-12, which are preferably selected from a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-12.

Typical structures of the general formula 3-J-12 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by formula 3-J-13 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-13.

Typical structures of the general formula 3-J-13 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-J-14 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-14.

Typical structures of the general formula 3-J-14 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-J-15 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-15.

Typical structures of the general formula 3-J-15 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-J-16 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-16.

Typical structures of the general formulae 3-J-16 may be exemplified as follows, but the present invention is not limited thereto:

Wherein the structure represented by formula 3-J-17 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-17.

Typical structures of the general formula 3-J-17 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

The typical structure of the covalent force sensitive group of the [4+4] cycloaddition series reverse cyclization mechanism can also be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent force-sensitive group of the [4+4] cycloaddition series reverse cyclization mechanism can also perform reverse cyclization reaction under the irradiation of ultraviolet light with certain frequency so as to dissociate the force-sensitive group.

In the present invention, covalent force-sensitive groups based on the mechanism of electrocyclization include, but are not limited to, the following series: six-membered ring series, five-membered ring series, three-membered ring series.

In the present invention, the covalent force-sensitive group of the electrical cyclization mechanism of the six-membered ring series refers to a force-sensitive group containing six-membered ring force-sensitive elements, and the structural general formula thereof includes but is not limited to the following classes:

wherein X is selected from oxygen atom, sulfur atom, selenium atom, tellurium atom, C-R, N-R, preferably oxygen atom; y is selected from C-R and nitrogen atom; each R is independently any suitable atom, substituent, substituted polymer chain; m is a metal atom selected from Be, Zn, Cu, Co, Hg, Pb, Pt, Fe, Cr, Ni, preferably Be, Zn, Cu, Co;

each independently of the other, to any suitable atom (including a hydrogen atom), substituent, substituted polymer chain, whether or not participating in force activation, different on the same atom

Can be linked to form a ring, on different atoms

Or can be connected into a ring. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.

The six-membered ring force-sensitive groups of the present invention comprising the general structural formula (4-A-1) are further preferably selected from, but not limited to, the following structures:

wherein, X₁Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, C-R, N-R, preferably from an oxygen atom; y is₁Each independently selected from C-R, nitrogen atom; z₁Is selected from C- (R)₂Nitrogen atom, sulfur atom, oxygen atom, tellurium atom, preferably C- (R)₂A nitrogen atom; z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂Nitrogen atom, preferably C- (R)₂A nitrogen atom; when Z is₁Or Z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂When connected to it

The number is 0;

an aromatic ring having an arbitrary number of elements; n is a total number of hydrogen atoms, substituent atoms, substituents, and substituent polymer chains bonded to the ring-constituting atoms, and is 0, 1 or an integer X, Y, R greater than 1,

The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.

wherein, X, X₁、Y、Y₁、R、Z₁、Z₂、

n、

wherein, X₂Each independently selected from carbon atom, oxygen atom, sulfur atom, N-R; x₃Each independently selected from the group consisting of an oxygen atom, a sulfur atom, N-R; x, X₁、Y、Y₁、R、Z₁、Z₂、

In the present invention, the six-membered ring force-sensitive group having the general structural formula (4-A-1) is exemplified by the following structures:

wherein, X, X₁、X₂、X₃、Y、Y₁The selection range of R is as described in the series of force-sensitive groups, and is not described in detail herein;

each independently linked to a polymer chain involved in force activation.

The six-membered ring force-sensitive groups of the present invention comprising the general structural formula (4-A-2) are further preferably selected from, but not limited to, the following structures:

wherein, X, R, Z₁、Z₂、

n、

wherein, X, Z₁、Z₂、

The selection range of the pressure-sensitive groups is as described in the series of the force-sensitive groups, and the detailed description is omitted;

represents an aromatic ring having an arbitrary number of elements.

wherein, X, R, Z₁、Z₂、

In the present invention, the six-membered ring force-sensitive group having the general structural formula (4-A-2) is exemplified by the following structures:

wherein the content of the first and second substances,

each independently linked to a polymer chain involved in force activation.

The six-membered ring force-sensitive groups of the present invention comprising the general structural formula (4-A-3) are further preferably selected from, but not limited to, the following structures:

wherein X, M,

The selection range of the pressure-sensitive groups is as described in the series of the force-sensitive groups, and the detailed description is omitted.

wherein X, M, n,

represents an aromatic ring having an arbitrary number of elements.

wherein M, R,

In the present invention, the six-membered ring force-sensitive group having the general structural formula (4-A-3) is exemplified by the following structures:

wherein the content of the first and second substances,

each independently linked to a polymer chain involved in force activation.

The six-membered ring force-sensitive groups of the present invention comprising the general structural formula (4-A-4) are further preferably selected from, but not limited to, the following structures:

wherein, X, Y, Z₁、Z₂、

n is selected from the group consisting of the anterior surfaces of force sensitive groups of the present seriesAs such, no further description is provided herein.

wherein, X, Y, Z₁、Z₂、

n、

wherein, X, Y, R, Z₁、Z₂、

In the present invention, the six-membered ring force-sensitive group having the general structural formula (4-A-4) is exemplified by the following structures:

wherein, the selection range of X, Y is as described in the series of force-sensitive groups, and is not described in detail herein;

each independently linked to a polymer chain involved in force activation.

The six-membered ring force-sensitive groups of the present invention comprising the general structural formula (4-A-5) are further preferably selected from, but not limited to, the following structures:

wherein the content of the first and second substances,

wherein the content of the first and second substances,

n、

wherein R is,

In the present invention, the six-membered ring force-sensitive group having the general structural formula (4-A-5) is exemplified by the following structures:

wherein the content of the first and second substances,

each independently linked to a polymer chain involved in force activation.

The six-membered ring force-sensitive groups of the present invention comprising the general structural formula (4-A-6) are further preferably selected from, but not limited to, the following structures:

wherein X, R,

n、

wherein X, R,

n、

wherein R is,

The selection range of the pressure-sensitive groups is as described in the series of the force-sensitive groups, and the detailed description is omitted; r_xEach independently is a substituent atom, substituent group, substituted polymer chain other than a hydrogen atom.

In the present invention, the six-membered ring force-sensitive group having the general structural formula (4-A-6) is exemplified by the following structures:

wherein, the selection range of X is as the previous description of the series of force-sensitive groups, and the description is omitted; r_xEach independently is a substituent atom, substituent group, substituted polymer chain other than a hydrogen atom;

each independently linked to a polymer chain involved in force activation.

The six-membered ring force-sensitive groups of the present invention comprising the general structural formula (4-A-7) are further preferably selected from, but not limited to, the following structures:

wherein, X, Z₂、

wherein, X, Z₂、

The selection range of n is as described above in the series of force-sensitive groups and will not be described in detail here.

wherein R is,

In the present invention, the six-membered ring force-sensitive group having the general structural formula (4-A-7) is exemplified by the following structures:

wherein the content of the first and second substances,

each independently linked to a polymer chain involved in force activation.

In the invention, the covalent force sensitive group of the five-membered ring series electrical cyclization mechanism is a force sensitive group containing five-membered ring force sensitive elements, and the structural general formula of the covalent force sensitive group comprises but is not limited to the following groups:

wherein A0 is selected from

A₁Is selected from

A₂Is selected from

Wherein the structure represented by the general formula 4-B-1 is preferably selected from at least a subset of the following general structures:

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation;

wherein, T₁Each independently of the other being a substituent group, preferably an electron-withdrawing group, and two T' s₁Can be connected to form a ring; by way of example, such electron-withdrawing groups include, but are not limited to, acyl groups, aldehyde groups, sulfonic acid groups, nitrile groups, quaternary amine groups, ester groups, halogenated alkyl groups, and the like; wherein, T₁Each independently is preferably acyl, ester group, nitrile group, fluoroalkyl group; specifically, T is exemplified₁Exemplary structures of (a) include, but are not limited to, the following:

wherein the content of the first and second substances,

is a conjugated ring structure or a heterocyclic ring structure containing double bonds; position 1 is attached to a force-activatable bond and position 2 is attached to another linking atom of the five-membered ring; n is

Is 0, 1 or an integer greater than 1, m is the number of R therein, which is 0, 1 or an integer greater than 1; wherein, the ring-forming atom at the 1-position side and

the ring-forming atoms on the side of the position 2 and the ring-forming atoms on the symmetry axis shown by the dotted line are connected with R; the ring structure is preferably

Because it is sensitive to light at the same time, it can realize double response of force and light.

A typical structure of the formula 4-B-1 may be exemplified as follows, but the present invention is not limited thereto:

specifically, the typical structure of the formula 4-B-1 can be further exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.

Wherein the structure of formula 4-B-2 is preferably selected from at least a subset of the following general structures:

wherein A is₀、

The definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-2;

wherein the content of the first and second substances,

is a conjugated ring structure or a heterocyclic structure with positive charge; n is

The total number of (a) is 0, 1 or an integer greater than 1; the ring structure is preferably

Wherein the content of the first and second substances,

is an aromatic ring structure; the aromatic ring can be any aromatic ring or aromatic heterocyclic ring, and the ring-forming atoms are respectively and independently carbon atoms or hetero atoms; wherein the content of the first and second substances,

to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; n is

The total number of (a) is 0, 1 or an integer greater than 1; by way of example only, the following may be mentioned,

exemplary structures of (a) include, but are not limited to, the following:

among them, the force sensitive group of the general formula 4-B-2 is further preferably selected from the following general structure:

wherein A is₀、

The definition and the selection range of the formula (I) are the same as those of the general formula 4-B-2;

the definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-2-1;

the definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-2-2;

wherein the content of the first and second substances,

is a conjugated ring structure or a heterocyclic ring structure with strong electron-withdrawing groups and/or heteroatoms, n is

The total number of (a) is 0, 1 or an integer greater than 1; the strong electron-withdrawing group is preferably nitro; the heteroatom is preferably a nitrogen atom; by way of example only, the following may be mentioned,

exemplary structures of (a) include, but are not limited to, the following:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-2-2; wherein the content of the first and second substances,

is a conjugated ring structure or a conjugated heterocyclic structure, n is

A typical structure of the formula 4-B-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

specifically, the typical structure of the formula 4-B-2 can be further exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structures represented by the general formulae 4-B-3 to 4-B-6 are preferably selected from at least a subset of the following general structures:

wherein A is₁The definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-3; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;

wherein, T₂Each independently a substituent group, preferably an electron-withdrawing group, and two T's in the general formulae 4-B-4-1, 4-B-6-1₂Can be connected to form a ring; by way of example, such electron-withdrawing groups include, but are not limited to, acyl groups, aldehyde groups, sulfonic acid groups, nitrile groups, quaternary ammonium groups, ester groups, haloalkyl groupsEtc.; wherein, T₂Each independently is preferably acyl, ester group, nitrile group, fluoroalkyl group; specifically, T is not connected to form a ring, for example₂Exemplary structures of (a) include, but are not limited to, the following: :

specifically, as an example, two T's in the general formulae 4-B-4-1 and 4-B-6-1, which are linked to form a ring₂Selected from, but not limited to:

wherein the content of the first and second substances,

is a heterocyclic ring containing at least one nitrogen atom, A_xIs a carbon atom or a nitrogen atom, and n is a ring member attached to a heterocyclic ring

The total number of (a) is 1 or an integer greater than 1; the heterocyclic ring containing at least one nitrogen atom is preferably an aromatic heterocyclic ring containing at least one nitrogen atom;

when A is_xIn the case of carbon atoms, suitable heterocyclic structures containing at least one nitrogen atom include, by way of example and not limitation, the following:

when A is_xIn the case of a nitrogen atom, suitable heterocyclic structures containing at least two nitrogen atoms include, by way of example and not limitation, the following:

wherein the content of the first and second substances,

is an aromatic ring structure, each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation; n is the total number of R numbers, and is 0, 1 or an integer more than 1; by way of example, the

Exemplary structures of (a) include, but are not limited to, the following:

among them, the structure represented by the general formulae 4-B-3 to 4-B-6 is more preferably:

wherein E is₁Each independently selected from one of two structures shown below:

wherein the content of the first and second substances,

each independently is an aromatic ring structure, n is the total number of atoms (including hydrogen atoms) bonded to atoms constituting the aromatic ring, substituents, and substituted polymer chains, and is 0, 1, or an integer greater than 1;

by way of example, E₁In (1),

exemplary structures of (a) include, but are not limited to, the following:

by way of example, E₁In (1),

including but not limited to the following:

wherein E is₂Are any suitable atoms (including hydrogen atoms), substituents, and substituted polymer chains, with or without participation in force activation, preferably E₁(ii) a In the same structure, when E₂Is selected in the range of E₁When E is greater₁And E₂Are independent of each other;

wherein the definition, the selection range and the preferable range of the other parameters are shown as the general formula 4-B-3-1 to 4-B-6-1.

Among them, the general formulae 4-B-3 to 4-B-6 are more preferably spiro structures represented by the following formulae:

wherein, the linking group E_xEach independently selected from a direct bond,

Wherein the group consisting of a linking group E_xThe ring structure to which it is attached being substituted E₁The ring structures contained in (1) may be the same or different; the definition, selection range and preferable range of the other parameters are shown as general formulas 4-B-3-1 to 4-B-6-1.

In one embodiment of the present invention, the general formula 4-B-3-1-1-1 is preferably that the force-sensitive element is connected with some specific structures so as to realize a structure responding to specific metal ions, so that the force-sensitive group has ion detection function besides force response. By way of example, typical structures that can achieve a response to a particular metal ion are listed below, but the invention is not limited thereto:

Cu²⁺：

Hg²⁺：

Fe³⁺：

wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;

In another embodiment of the present invention, the general formula 4-B-3-1-1-1 is preferably a structure capable of chelating with metal ions and achieving forced ion release, and typical structures capable of chelating with metal ions and achieving forced ion release are listed as follows by way of example, but the present invention is not limited thereto:

wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation,

In another embodiment of the present invention, the general formula 4-B-3-1-1-1 is preferably a structure which is linked to an energy receptor and can effect energy transfer upon force activation; by way of example, typical structures that can be attached to an energy receptor and that can effect energy transfer upon force activation are as follows, but the invention is not limited thereto:

wherein L is any suitable covalent linking group having a length of less than 10 nm; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;

Other typical structures shown in the general formula 4-B-3 are exemplified below, but the present invention is not limited thereto:

wherein A is₁The definition and selection range of (A) are the same as those of the general formula 4-B-3, preferably

Specifically, the typical structure shown by the general formula 4-B-3 is further exemplified as follows, but the present invention is not limited thereto:

wherein A is₁The definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-3;

The typical structure shown in the formula 4-B-4 is exemplified as follows, but the present invention is not limited thereto:

Specifically, the typical structure shown by the general formula 4-B-4 is further exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

The typical structure shown in the formula 4-B-5 is exemplified as follows, but the present invention is not limited thereto:

Specifically, the typical structure shown by the general formula 4-B-5 is further exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Typical structures shown by the general formula 4-B-6 are exemplified below, but the present invention is not limited thereto:

Specifically, the typical structure shown by the general formula 4-B-6 is further exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula 4-B-7 is preferably selected from at least a subset of the following general structures:

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; wherein E is₁、E₂The definition, selection range and preferable range of the formula (I) are the same as those of the general formula 4-B-3-1-1;

wherein the content of the first and second substances,

is an aromatic ring structure, is a linking position, wherein position 1 is linked to a carbon atom and position 2 is linked to an oxy-genConnecting the son; wherein the ring-forming atom at the 1-position side and the ring-forming atom on the axis of symmetry indicated by the dotted line are bonded to R, and the ring-forming atom at the 2-position side and

connecting; n is the total number of R's bonded to the atoms constituting the aromatic ring, and m is

The total number of the number; by way of example, such ring structures include, but are not limited to, the following:

wherein, T₃Each independently selected from one of two structures shown below:

two T in the same type₃When selected from the same structure, T₃The specific structures of the components can be the same or different; wherein the content of the first and second substances,

by way of example, T₃In (1),

exemplary structures of (a) include, but are not limited to, the following:

by way of example, T₃In (1),

exemplary structures of (a) include, but are not limited to, the following:

typical structures of the general formula 4-B-7 are exemplified below, but the present invention is not limited thereto:

Specifically, the typical structure of the formula 4-B-7 is further exemplified below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the covalent force-sensitive group of the electrical cyclization mechanism of the three-membered ring series refers to a force-sensitive group containing three-membered ring (including three-membered ring and four-membered/five-membered ring) force-sensitive element, and the structural general formula includes but is not limited to the following groups:

wherein the content of the first and second substances,

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; a is selected from-O-, -S-),

Wherein, each E is independently selected from hydrogen atom, halogen atom, alkyl and alkoxy.

Wherein the structure represented by the general formula 4-C-1 is preferably selected from at least a subset of the following general structures:

wherein E is_xEach independently selected from a halogen atom, preferably a fluorine atom, a bromine atom, a chlorine atom; e_yEach independently selected from hydrogen atom, alkyl and alkoxy; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;

Wherein, the structure represented by the general formula 4-C-1-1 is further preferably selected from the following general structures:

wherein E is_XEach independently selected from a halogen atom, preferably a fluorine atom, a bromine atom, a chlorine atom; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;

wherein, E in the general formula 4-C-1-1-1_xIn the case of bromine atom, the bromine atom is preferably used because it can react with carboxyl group in the system after being activated by force to achieve the special effect of enhancing crosslinking by force, and the structure represented by the general formula 4-C-1-1-2 can release hydrogen halide after being activated by force to achieve the change of pH value by force.

A typical structure of the formula 4-C-1-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein, the structure represented by the general formula 4-C-1-2 is further preferably selected from the following general structures:

A typical structure of the formula 4-C-1-2 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein, the structure represented by the general formula 4-C-1-3 is further preferably selected from the following general structures:

wherein E is_xEach independently selected from a halogen atom, preferably a fluorine atom, a bromine atom, a chlorine atom;

wherein, the five-membered ring at the center can form furyl after the force activation of the general formula 4-C-1-3-1, and can react with other proper groups in the system to realize the special effect of strengthening the force-induced crosslinking.

Typical structures of the general formula 4-C-1-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein, the structure represented by the general formula 4-C-1-4 is further preferably selected from the following general structures:

among them, the force sensitive groups shown in the general formula 4-C-1-4-2 can react with carboxyl in the system after being activated by force to realize the special effect of force-induced enhancement, and the force sensitive groups shown in the general formula 4-C-1-4-3 can change color after being activated by force to realize the special effect of force-induced color change, so that the method is more preferable.

A typical structure of the formula 4-C-1-4 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Typical structures of the general formula 4-C-1-5 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, covalent force sensitive groups based on the bending activation mechanism include, but are not limited to, the following series: alkyne-furan adduct series, anthracene-triazoline-dione adduct series, and alkynyl series.

In the present invention, the covalent force-sensitive group of the bending activation mechanism of the alkyne-furan adduct series refers to a force-sensitive group containing alkyne-furan adduct force-sensitive elements, and the structural general formula thereof includes but is not limited to the following types:

A typical structure of the formula 5-A-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the covalent force-sensitive group of the bending activation mechanism of the anthracene-triazoline-dione adduct series refers to a force-sensitive group containing anthracene-triazoline-dione adduct force-sensitive units, and the structural general formula of the covalent force-sensitive group includes but is not limited to the following types:

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; the anthracene group generated after the force-sensitive group is activated by force has a fluorescence effect, can realize special effects including but not limited to force-induced fluorescence and the like, and is preferably connected with other functional groups with a fluorescence enhancement effect, so that the force-induced fluorescence effect is more remarkable; the triazolinedione group generated after the force-sensitive group is activated by force can be subjected to addition reaction with groups such as diene group and the like, and when R is a substituted polymer chain which does not participate in the force activation or is connected with the triazolinedione group in another force-sensitive group and the system simultaneously contains the groups such as diene group and the like, special effects including but not limited to force-induced chemical reaction, force-induced crosslinking enhancement and the like can be realized, so that the triazolinedione group is also preferable.

A typical structure of the formula 5-B-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent force-sensitive group of the alkynyl series bending activation mechanism refers to a force-sensitive group containing alkynyl force-sensitive elements, and the structural general formula of the covalent force-sensitive group includes but is not limited to the following:

wherein the content of the first and second substances,

each independently linked to a substituted polymer chain participating in force activation; after being bent and activated, the series of force sensitive groups can generate azide-alkyne click reaction without catalysts with azide groups, and special effects including but not limited to force-induced crosslinking and the like are realized.

A typical structure of the formula 5-C-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, covalent force-sensitive groups based on other mechanisms include, but are not limited to, the following series: a double nitrite series, a 1, 1' -linked condensed ring series and a bisthiomaleimide series.

In the invention, the covalent force-sensitive group of the other mechanism of the double-nitrite series refers to a force-sensitive group containing a double-nitrite force-sensitive element, and the structural general formula of the covalent force-sensitive group includes but is not limited to the following groups:

wherein X is selected from oxygen atom, sulfur atom, preferably oxygen atom;

Can be linked to form a ring, on different atoms

In the present invention, the structure of the covalent force-sensitive group of the other mechanism of the double nitrite series can be exemplified as follows:

wherein the content of the first and second substances,

In the present invention, the covalent force-sensitive group of other mechanism of the 1, 1 '-linked condensed ring series refers to a force-sensitive group containing a 1, 1' -linked condensed ring force-sensitive element, and the structural general formula thereof includes but is not limited to the following classes:

wherein each R is independently any suitable atom, substituent, substituted polymer chain;

represents an aromatic ring having an arbitrary number of elements.

In the present invention, the structure of the covalent force sensitive group of the other mechanism of the 1, 1' -linked condensed ring series can be exemplified as follows:

wherein the content of the first and second substances,

In the present invention, the covalent force-sensitive group of the dithiomaleimide series with other mechanisms refers to a force-sensitive group containing a dithiomaleimide force-sensitive element, and the structural general formula includes but is not limited to the following groups:

wherein the content of the first and second substances,

an aromatic ring having an arbitrary number of elements;

In the present invention, the covalent force-sensitive group of the bis-thiolylimide series has other mechanisms, and the structure thereof can be exemplified as follows:

wherein the content of the first and second substances,

In the present invention, the division is performed in a non-covalent complexing manner, and the non-covalent force sensitive groups include, but are not limited to, the following groups: non-covalent force sensitive groups based on supramolecular complexes, non-covalent force sensitive groups based on supramolecular assemblies, non-covalent force sensitive groups based on compositions, non-covalent force sensitive groups based on aggregates. The non-covalent force sensitive groups are capable of specifically responding to mechanical forces and produce significant specific force-induced response properties/effects, such as catalytic, optical, spectroscopic, etc. supramolecular interactions.

In the present invention, the non-covalent force-sensitive groups based on supramolecular complexes include, but are not limited to, the following series: coordination bond series, host-guest interaction series, hydrogen bond interaction series and pi-pi stacking interaction series.

In the present invention, non-covalent force-sensitive groups based on coordination bonds include, but are not limited to, the following sub-series: complexation of unsaturated carbon-carbon bonds with transition metals, carbene-metal coordination bonds, boron-nitrogen coordination bonds, platinum-phosphorus coordination bonds, metallocene coordination bonds, and ligand-lanthanide metal ion complexation.

In the present invention, the non-covalent force-sensitive group of the complexation of the unsaturated carbon-carbon bond and the transition metal refers to a force-sensitive group containing a complexation force-sensitive element of the unsaturated carbon-carbon bond and the transition metal, and the structural general formula thereof includes but is not limited to the following types:

wherein the content of the first and second substances,

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; each R is independently any suitable atom, substituent, substituted polymer chain; in different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.

The unsaturated carbon-carbon bond of the present invention is further preferably selected from, but not limited to, the following structures:

wherein the content of the first and second substances,

an aromatic ring having an arbitrary number of elements; n is the total number of hydrogen atoms, substituent atoms, substituents, and substituent polymer chains bonded to the atoms constituting the ring, and is 0, 1, or an integer greater than 1;

The complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-1) according to the present invention is further preferably selected from, but not limited to, the following structures:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-1) and the transition metal of the present invention is exemplified by the following:

the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-2) according to the present invention is further preferably selected from, but not limited to, the following structures:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-2) and the transition metal of the present invention is exemplified by the following:

the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-3) according to the present invention is further preferably selected from, but not limited to, the following structures:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-3) and the transition metal of the present invention is exemplified by the following:

the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-4) according to the present invention is further preferably selected from, but not limited to, the following structures:

the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-5) according to the present invention is further preferably selected from, but not limited to, the following structures:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-5) and the transition metal of the present invention is exemplified by the following:

the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-6) according to the present invention is further preferably selected from, but not limited to, the following structures:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-6) and the transition metal of the present invention is exemplified by the following:

the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-7) according to the present invention is further preferably selected from, but not limited to, the following structures:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-7) and the transition metal of the present invention is exemplified by the following:

the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-8) according to the present invention is further preferably selected from, but not limited to, the following structures:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-8) and the transition metal of the present invention is exemplified by the following:

the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-9) according to the present invention is further preferably selected from, but not limited to, the following structures:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-9) and the transition metal of the present invention is exemplified by the following:

the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-10) according to the present invention is further preferably selected from, but not limited to, the following structures:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-10) and the transition metal of the present invention is exemplified by the following:

the structure of the complex of the unsaturated carbon-carbon bond having the general structural formula (A-11) and the transition metal of the present invention is exemplified by the following:

in the invention, the non-covalent force-sensitive group of the carbene-metal coordination bond refers to a force-sensitive group containing a force-sensitive element of the carbene-metal coordination bond, and the structural general formula of the non-covalent force-sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

In the present invention, the carbene-metal coordination bond, carbene ligand, is further preferably selected from, but not limited to, the following structures:

wherein, X₄Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, C- (R)₂Preferably from an oxygen atom;

the selection range of R is as described above in the series of force-sensitive groups and will not be described in detail herein.

In the invention, the non-covalent force-sensitive group of the carbene-metal coordination bond refers to a force-sensitive group containing a force-sensitive element of the carbene-metal coordination bond, wherein the structural general formula of the carbene includes but is not limited to the following classes:

wherein the content of the first and second substances,

wherein, X₄、

In the present invention, the carbene-metal coordination bond having the general structural formulas (B-1), (B-2), (B-3) and (B-4) can be selected from, but not limited to, the following structures:

wherein, X₄、

The selection range of the pressure-sensitive groups is as described in the series of the force-sensitive groups, and the detailed description is omitted; m is a metal center, which may be any suitable ionic form, compound/chelate form, and combinations thereof, of any one of the transition metals; .

In the present invention, the carbene-metal coordination bond having the general structural formulae (B-1), (B-2), (B-3) and (B-4) has the following structure:

wherein, X₄、M、

In the present invention, the non-covalent force-sensitive group of boron-nitrogen coordination bond refers to a force-sensitive group containing a force-sensitive element of boron-nitrogen coordination bond, and the structural formula thereof includes but is not limited to the following classes:

wherein the content of the first and second substances,

The boron-nitrogen coordination bond of the present invention, formula (C-1), may further preferably be selected from, but not limited to, at least one of the following structures:

wherein the content of the first and second substances,

r, n, the ranges of choice are as previously described in the series of force-sensitive clusters and will not be further described herein;

represents any number of nitrogen heterocycles, including but not limited to aliphatic nitrogen heterocycles, aromatic nitrogen heterocycles, and combinations thereof.

In the present invention, said boron-nitrogen coordination bond having the general structural formula (C-1) is further preferably selected from, but not limited to, the following structures:

in the present invention, the boron-nitrogen coordination bond having the general structural formula (C-1) is exemplified by the following structures:

in the present invention, the non-covalent force-sensitive group of platinum-phosphorus coordination bond refers to a force-sensitive group containing platinum-phosphorus coordination bond force-sensitive elements therein, and the structural formula thereof includes but is not limited to the following classes:

wherein, X₅Each independently selected from a chlorine atom, a bromine atom, an iodine atom, preferably from a chlorine atom;

In the present invention, said platinum-phosphorus coordination bond having the general structural formula (D-1) is further preferably selected from, but not limited to, the following subclasses:

wherein, X₅、

In the present invention, said platinum-phosphorus coordination bond having the general structural formula (D-1) is further preferably selected from, but not limited to, the following structures:

wherein, X₅、

In the present invention, the structure of the platinum-phosphorus coordination bond having the general structural formula (D-1) is exemplified as follows:

in the present invention, the non-covalent force-sensitive group of the metallocene coordination bond refers to a force-sensitive group containing a force-sensitive moiety of the metallocene coordination bond, and the structural general formula thereof includes but is not limited to the following groups:

wherein, M is a metal center,

is a ligand of cyclopentadiene and a ligand of cyclopentadiene,

the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted. The metal centers are preferably metals of the first to seventh subgroups and of the eighth group. The first mentionedMetals from subgroups one through seventh and eighth also include the lanthanide metals (i.e., La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and the actinide metals (i.e., Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr). The metal center is more preferably a metal of the first subgroup (Cu, Ag, Au), a metal of the second subgroup (Zn, Cd), a metal of the eighth group (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), a metal of the lanthanide series (La, Eu, Tb, Ho, Tm, Lu), a metal of the actinide series (Th). More preferably, Cu, Zn, Fe, Co, Ni, Pd, Ag, Pt, Au, La, Ce, Eu, Tb or Th, and still more preferably Fe, Co or Ni.

In the present invention, the metallocene coordination bond having the general structural formula (E-1) is exemplified by the following structures:

wherein the content of the first and second substances,

In the invention, the non-covalent force-sensitive group of ligand-lanthanide metal ion complexation refers to a force-sensitive group containing a ligand-lanthanide metal ion complexation force-sensitive element, and the non-covalent force-sensitive group can change the position of the ligand group more easily when being stressed, thereby showing obvious stress response properties including changes of fluorescence, color and the like.

In embodiments of the present invention, suitable ligand groups may be exemplified by, but are not limited to:

in an embodiment of the invention, the lanthanide metal includes La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; preferably lanthanide series Ce, Eu, Tb, Ho, Tm, Lu; more preferably Ce, Eu, Tb, to obtain more remarkable stress responsiveness.

In the embodiment of the present invention, the combination of the ligand group and the metal center is not particularly limited as long as the ligand can form a suitable metal-ligand interaction with the metal center. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

in the present invention, the non-covalent force-sensitive group for host-guest action refers to a force-sensitive group containing a force-sensitive element for host-guest action, the host (represented by H) in the host-guest action is a compound (macromolecule or inorganic organic ionic skeleton) having a cavity capable of achieving molecular recognition, and the guest (represented by G) is a compound (small molecule or ionic group) capable of being recognized by the host and inserted into the cavity of the host, one host molecule can recognize a plurality of guest molecules, and in the present invention, it is preferable that one host molecule recognizes at most two guest molecules, and the host molecules include, but are not limited to, ethers (including crown ether, cryptether, sphenol, hemispherical ether, pod ether, lasso ether, benzocrown ether, heteropentary ether, heterocryptate ether, mixed cryptate ether), cyclodextrin, cyclophane, cucurbituril, calixarene, pillararene and suitable inorganic organic ionic skeletons, preferably spiro crown ether, β -cyclodextrin, calixarene, pillared aromatic hydrocarbon, and compound having a long-ring structure capable of stabilizing the host molecule structure under the conditions that the compound can form a long-ring structure, a long-bridged chain-bridged aromatic hydrocarbon structure, a compound, a long-bridged compound, a compound capable of achieving a suitable strength under the action under the condition that is moderate, and a compound, a compound capable of achieving the compound under the effect under the normal condition that can be a compound, a compound can form a long-chain-bridged ring structure under the compound, a long-fused ring structure under the compound, a.

Suitable host groups may be exemplified by, but are not limited to:

Ni(PDC)(H₂O)₂skeleton, Zn₃(PTC)₂(H₂O)₈·4H₂An O skeleton;

suitable guest groups may be exemplified by, but are not limited to:

in the embodiment of the present invention, the combination of the host group and the guest group is not particularly limited as long as the host can form a suitable host-guest interaction with the guest. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

in the present invention, the hydrogen-bonding non-covalent force sensitive group is any suitable supramolecular interaction established by hydrogen bonding, and is generally a hydrogen bond link between Z and Y through a hydrogen atom covalently connected with an atom Z with large electronegativity and an atom Y with large electronegativity and small radius, wherein the hydrogen bond link is formed in a form of Z-h. The hydrogen bond function can exist as supramolecular polymerization and/or crosslinking and/or intrachain cyclization, namely the hydrogen bond can only play a role of connecting two or more chain segment units to increase the size of a polymer chain but not play a role of supramolecular crosslinking, or the hydrogen bond only plays a role of interchain supramolecular crosslinking, or only plays a role of intrachain cyclization, or the combination of any two or more of the three. The present invention also does not exclude that the hydrogen bonds play a grafting role.

In embodiments of the present invention, the hydrogen bonds may be any number of teeth. Wherein the number of teeth refers to the number of hydrogen bonds formed by a donor (H, i.e., a hydrogen atom) and an acceptor (Y, i.e., an electronegative atom that accepts a hydrogen atom) of hydrogen bonding groups, each H. In the following formula, the hydrogen bonding of monodentate, bidentate and tridentate hydrogen bonding groups is schematically illustrated, respectively.

The bonding of the monodentate, bidentate and tridentate hydrogen bonds can be specifically exemplified as follows:

the more the number of teeth of the hydrogen bond, the greater the synergistic effect and the greater the strength of the hydrogen bond. In the embodiment of the present invention, the number of teeth of the hydrogen bond is not limited. If the number of teeth of the hydrogen bond is large, the strength is high, the effects of promoting the force-induced response polymer to keep a balanced structure and improving the mechanical properties (modulus and strength) can be achieved, and the toughening effect can be achieved after the force activation. If the number of teeth of the hydrogen bond is small, the strength is low, and the force-induced response effect is weak. In embodiments of the present invention, two or more teeth are preferred for hydrogen bonding to facilitate a significant force-induced response.

In embodiments of the invention, the hydrogen bonding may be effected by the presence of non-covalent interactions between any suitable hydrogen bonding groups. Wherein, the hydrogen bond group can only contain a hydrogen bond donor, only contain a hydrogen bond acceptor, or contain both the hydrogen bond donor and the hydrogen bond acceptor, preferably contain both the hydrogen bond donor and the hydrogen bond acceptor. Wherein, the hydrogen bonding group preferably comprises the following structural components:

more preferably at least one of the following structural components:

further preferably at least one of the following structural components:

wherein the content of the first and second substances,

refers to a linkage to a polymer chain, cross-link, or any other suitable group/atom, including a hydrogen atom. In the embodiments of the present invention, the hydrogen bonding group is preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, thiourea groups, pyrazolyl groups, imidazolyl groups, imidazolinyl groups, triazolyl groups, purine groups, porphyrin groups, derivatives thereof, and the like.

In the present invention, said hydrogen bonding groups may be present only on the polymer chain backbone (including side chains/branches/bifurcations), referred to as backbone hydrogen bonding groups; or may be present only in pendant groups (also including multilevel structures of pendant groups), referred to as pendant hydrogen bonding groups; or may be present only on the polymer chain/small molecule end group, referred to as an end hydrogen bonding group; or may be present in at least two of the polymer chain backbone, the polymer chain pendant group, the polymer chain/small molecule end group. When present on at least two of the polymer chain backbone, the polymer chain pendant groups, and the polymer chain/small molecule end groups at the same time, hydrogen bonds may be formed between hydrogen bonding groups in different positions, in particular instances, for example, the backbone hydrogen bonding groups may form hydrogen bonds with the pendant hydrogen bonding groups.

Among these, suitable backbone hydrogen bonding groups are exemplified by (but the invention is not limited to):

among these, suitable pendant hydrogen bonding groups/terminal hydrogen bonding groups may have the above-mentioned skeleton hydrogen bonding group structure, and are exemplified by (but the invention is not limited to) the following:

wherein m and n are the number of repeating units, and may be fixed values or average values, and are preferably less than 20, and more preferably less than 5.

In the invention, the noncovalent force sensitive group with pi-pi stacking effect refers to a force sensitive group which can provide a pi-bond electron cloud structure and form pi-pi stacking effect force sensitive elements by mutual overlapping of the pi-bond electron clouds, and the position of a ligand group is easier to change when the force is applied, so that obvious stress response properties including changes of fluorescence, color and the like are shown.

Structures of compounds capable of providing a pi-bonded electron cloud, including but not limited to most condensed cyclic compounds and some heterocyclic compounds with pi-pi conjugation, suitable groups may be exemplified by, but not limited to, the following:

preference is given to

The pi-pi stacking effect has simple forming mode, can stably exist in the polymer, is less influenced by the external environment, and can be conveniently regulated and controlled by changing the conjugated compound and the content.

In the embodiment of the present invention, the combination of the compounds providing the pi-bonded electron cloud is not particularly limited as long as a suitable pi-pi stacking effect is formed between the compounds. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

in the present invention, the non-covalent force sensitive groups based on supramolecular assemblies include, but are not limited to, the following series: the non-covalent force sensitive group comprises a donor-acceptor series, a diketopyrrolopyrrole series, a conjugated series, a platinum coordination series, a gold coordination series, a beryllium coordination series, a copper coordination series, an iridium coordination series, a boron coordination series, a phenothiazine series, a dioxaborolane series and a dye molecule series.

In the present invention, the non-covalent force-sensitive group of the donor-acceptor series refers to a force-sensitive group containing a self-assembly aggregate force-sensitive element formed by a donor-acceptor self-assembly element, and the structural general formula thereof includes but is not limited to the following classes:

wherein, W⁴Is an atom or group having an electron withdrawing effect; wherein, the atom with electron-withdrawing effect is selected from but not limited to oxygen atom or sulfur atom, preferably oxygen atom; the group with electron-withdrawing effect is selected from but not limited to:

wherein Ar is⁷、Ar⁸Each independently selected from aromatic rings having an electron donating effect; wherein the aromatic ring structure is a polycyclic structure or a fused ring structure; by way of example, suitable Ar' s⁷、Ar⁸Selected from, but not limited to:

wherein the content of the first and second substances,

A typical structure of the formula F-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

A typical structure of the formula F-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

A typical structure of the formula F-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the non-covalent force-sensitive group of diketopyrrolopyrrole series refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by diketopyrrolopyrrole self-assembly elements, and the structural general formula of the non-covalent force-sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

A typical structure of the formula G-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the conjugated series non-covalent force-sensitive groups refer to force-sensitive groups containing self-assembly aggregate force-sensitive elements formed by conjugated self-assembly elements; wherein, the conjugated self-assembly motif includes but is not limited to the following subseries: polydiacetylene series, polydiphenylacetylene series, polythiophene series, polypyrrole series, anthraquinone series, polyfluorene series, oligomeric p-phenylene vinylene series, bis (benzoxazole) stilbene series, and aza-condensed ring sub-series self-assembly motif.

Wherein, the structural general formula of the polydiacetylene subunit self-assembly unit includes but not limited to the following types:

wherein n is the number of the repeating units, and the value range of n is an integer greater than 2, preferably an integer greater than or equal to 5, and more preferably an integer greater than or equal to 10;

A typical structure of the formula H-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein n and p are the number of the repeating units, and the value ranges thereof are respectively independent integers more than 2, preferably more than or equal to 5, and more preferably more than or equal to 10;

Wherein, the structural general formula of the polydiphenylacetylene self-assembly motif comprises but is not limited to the following types:

wherein n is,

The definition, selection range and preferable range of (A) are the same as those of the general formula H-1.

A typical structure of the formula H-2 can be exemplified as follows, but the present invention is not limited thereto:

wherein n, n₁、n₂The number of the repeating units is an integer which is greater than 2, preferably greater than or equal to 5, and more preferably greater than or equal to 10;

independently of one another and participating in force-activated substitutionThe polymer chains are linked.

Wherein, the structural general formula of the sub-series self-assembly motif of the polythiophene comprises but is not limited to the following classes:

wherein n is the number of the repeating units and the value range of n is an integer larger than 5;

A typical structure of the formula H-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein n, n₁、n₂The number of repeating units is an integer in the range of greater than 5.

Wherein, the structural general formula of the self-assembly motif of the polypyrrolidine series includes but is not limited to the following classes:

wherein n is,

The definition, selection range and preferable range of (A) are the same as those of the general formula H-3.

A typical structure of the formula H-4 can be exemplified as follows, but the present invention is not limited thereto:

wherein n, n₁、n₂Is the number of repeating units, and has a value in the range of more than5 is an integer;

Wherein, the structural general formula of the self-assembly motif of the anthraquinone sub-series includes but is not limited to the following classes:

wherein n is,

A typical structure of the formula H-5 can be exemplified as follows, but the present invention is not limited thereto:

wherein the definition, the selection range and the preferred range of n are the same as those of the general formula H-5;

Wherein, the structural general formula of the polyfluorenesub-series self-assembly motif includes but is not limited to the following classes:

wherein n is,

A typical structure of the formula H-6 can be exemplified as follows, but the present invention is not limited thereto:

wherein n, n₁、n₂The number of the repeating units is defined, and the value ranges of the repeating units are respectively independent integers more than 5;

Wherein, the structural general formula of the self-assembly unit of the oligomeric p-phenylene vinylene subunit includes but is not limited to the following types:

wherein n is,

A typical structure of the formula H-7 can be exemplified as follows, but the present invention is not limited thereto:

wherein the definition, the selection range and the preferred range of n are the same as those of the general formula H-7;

Wherein, the structural general formula of the bis (benzoxazole) stilbene sublines self-assembly motif includes but is not limited to the following classes:

wherein the content of the first and second substances,

selected from, but not limited to, at least one of the following structures:

A typical structure of the formula H-8 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein, the structural general formula of the self-assembly motif of the aza-condensed ring sub-series includes but is not limited to the following types:

wherein the content of the first and second substances,

A typical structure of the formula H-9 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the platinum coordination series non-covalent force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by platinum coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:

wherein each V is independently selected from a carbon atom or a nitrogen atom;

wherein Lg is₁Is a monodentate ligand coordinated to the platinum atom; wherein the monodentate ligand is selected from, but not limited to: a halogen atom,

Wherein Lg is₂Is a monodentate ligand coordinated to the platinum atom; each Lg₂Are the same or different; wherein the monodentate ligand is selected from, but not limited to:

wherein the content of the first and second substances,

is a bidentate ligand with V and nitrogen atoms as coordinating atoms; by way of example, the bidentate ligand is selected from, but not limited to:

wherein the content of the first and second substances,

is a tridentate ligand with V and nitrogen atoms as coordination atoms; by way of example, the tridentate ligand is selected from, but not limited to:

wherein the content of the first and second substances,

is a tetradentate ligand taking V and nitrogen atoms as coordination atoms; by way of example, the tetradentate ligand is selected from, but not limited to:

wherein the content of the first and second substances,

Typical structures of the formulae I-1 to I-4 may be illustrated below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the gold coordination series non-covalent force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by gold coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:

wherein Lg is₃Is a monodentate ligand coordinated to a gold atom; each Lg₃Are the same or different; wherein the monodentate ligand is selected from, but not limited to:

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure and a condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited and is selected from, but not limited to, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a boron atom, a phosphorus atom, a silicon atom; the hydrogen atoms on the ring-forming atoms may be substituted with any suitable substituent atom or substituent; wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. By way of example, those that are suitable

wherein the content of the first and second substances,

the definition, selection range and preferable range of the formula (I) are the same as those of the general formula (I-2);

wherein the content of the first and second substances,

is a bidentate ligand with a sulfur atom and a nitrogen atom as coordination atoms; by way of example, those that are suitable

wherein the content of the first and second substances,

is a bidentate ligand taking a phosphorus atom as a coordination atom, wherein, the metal atoms coordinated with phosphine can be the same gold atom or different gold atoms; by way of example, those that are suitable

wherein the content of the first and second substances,

Typical structures of formulae J-1 to J-7 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the beryllium coordinated series non-covalent force-sensitive group refers to a force-sensitive group containing self-assembled aggregate force-sensitive elements formed by beryllium coordinated self-assembled elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

A typical structure of the formula K-1 can be illustrated as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the copper coordination series non-covalent force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by copper coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

A typical structure of the formula L-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the iridium coordination series non-covalent force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by iridium coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

is a bidentate ligand with carbon atoms and nitrogen atoms as coordination atoms; by way of example, those that are suitable

wherein the content of the first and second substances,

is a bidentate ligand with nitrogen atoms as coordination atoms; by way of example, those that are suitable

wherein the content of the first and second substances,

A typical structure of the formula M-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the boron coordination series non-covalent force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by boron coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:

wherein, R is respectively and independently selected from halogen atom, cyano-group and C_1-10Hydrocarbyl/heterohydrocarbyl, substituted C_1-10Hydrocarbyl/heterohydrocarbyl; r is preferably selected from halogen atoms, phenyl, pentafluorophenyl; v, V' are each independently selected from an oxygen atom or a nitrogen atom;

each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, of any two of the same general formula

With or without looping.

Wherein the structures represented by the general formulae N-1 to N-5 are preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

is an aromatic ring; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure and a condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; wherein the content of the first and second substances,

to connect n

The ring-forming atoms of the ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms; wherein the content of the first and second substances,

to connect n

At least one of the ring-forming atoms of the nitrogen-containing aromatic heterocyclic ring is a nitrogen atom, the nitrogen-containing aromatic heterocyclic ring forms a coordinate bond with a boron atom through the nitrogen atom, and the rest ring-forming atoms are selected from but not limited to carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms; wherein the content of the first and second substances,

to connect n

At least two of the ring-forming atoms of (1) are carbon atoms, and the remaining ring-forming atoms are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms; wherein the content of the first and second substances,

to connect n

At least two of the ring-forming atoms of the nitrogen-containing aromatic heterocycle are nitrogen atoms, one of the nitrogen atoms and the boron atom form a coordination bond, and the rest ring-forming atoms are selected from but not limited to carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms;

wherein R, V, V

The definitions, selection ranges and preferred ranges of the general formulas N-1 to N-5 are the same.

Typical structures of the formulae N-1 to N-5 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the phenothiazine series non-covalent force-sensitive group refers to a force-sensitive group containing a self-assembly aggregate force-sensitive element formed by phenothiazine self-assembly elements; wherein, the phenothiazine self-assembly motif comprises but is not limited to the following classes:

wherein each R is independently selected from the group consisting of atoms (including hydrogen atoms), substituents, and substituted polymer chains that may or may not participate in force activation; wherein said substituent atoms are selected from, but not limited to: fluorine atom, chlorine atom, bromine atom, iodine atom; the substituent is preferably selected from substituents with electron-withdrawing effect, so that the intermolecular stacking effect is enhanced, and more remarkable force-induced responsiveness is obtained; wherein said substituents having electron withdrawing effect include but are not limited to: trifluoromethyl, trichloromethyl, nitro, cyano, sulfonic group, aldehyde group, alkyl acyl, alkoxy acyl, carboxyl, amide group;

wherein n is the total number of substituent atoms, substituents, and substituted polymer chains linked to the atoms constituting the ring structure, and is 0, 1, or an integer greater than 1; when n is more than 1, the structures of the R can be the same or different;

wherein the content of the first and second substances,

Typical structures of the general formulae O-1, O-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the dioxaborolane series non-covalent force-sensitive group refers to a force-sensitive group containing a self-assembly aggregate force-sensitive element formed by a dioxaborolane self-assembly element, and the structural general formula of the force-sensitive group comprises but is not limited to the following types:

wherein Ar is⁹Is an aromatic ring having an electron donating effect; wherein the aromatic ring is a polycyclic structure selected from the group consisting ofNot only are there:

wherein the content of the first and second substances,

A typical structure of the formula P-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the non-covalent force-sensitive groups of the dye molecule series refer to force-sensitive groups containing self-assembly aggregate force-sensitive elements formed by dye molecule self-assembly elements; wherein, the dye molecule self-assembly motif is selected from one of the following structural formulas:

wherein the hydrogen atoms on the dye molecules may be substituted or unsubstituted by any suitable atom, substituent, polymer chain; and the dye molecules are linked to the polymer by suitable means.

By way of example, the structure of a typical self-assembly motif of a dye molecule is shown below, but the invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, non-covalent aggregate-based force sensitive groups include, but are not limited to, the following series: divinylanthracene series, tetraarylethylene series, cyanoethylene series, berberine series, maleimide series, 4-hydropyran series non-covalent force-sensitive groups.

In the present invention, the divinylanthracene series non-covalent force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive units formed by divinylanthracene aggregation-induced emission units, and the general structural formula thereof includes but is not limited to the following groups:

wherein Ar is¹、Ar²Each independently selected from aromatic rings, the ring structure of which is selected from monocyclic structure, polycyclic structure and condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;

Typical structures of the formulae Q-1 to Q-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the non-covalent force-sensitive group of the tetraarylethylene series refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive element formed by a tetraarylethylene aggregation-induced emission element, and the structural general formula includes but is not limited to the following classes:

wherein, W¹Is a divalent linking group, each of which is independently selected from a direct bond, a,

Wherein Ar is³Each independently selected from aromatic rings, the structure of which is selected from monocyclic structure, polycyclic structure, spiro structure and condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted with any suitable substituent atom, substituent group, or substituted polymer chain; wherein the substituted atom, the substituent, the substituted polymer chain are not particularly limited; in order to increase steric hindrance and aggregation-induced emission of the luminescent moiety in a non-planar conformation, and to form loosely-packed aggregates, so as to obtain a more significant force-induced response effect, the ring structure of the aromatic ring is preferably a polycyclic structure or a fused ring structure; by reasonably selecting the polycyclic structure and the condensed ring structure, the spectral property of the formed force sensitive group can be regulated and controlled in a large range, so that the color change and the fluorescence/phosphorescence emission wavelength which can be adjusted in a large range can be obtained, and the use requirements of various application scenes can be met; in order to increase the intramolecular charge transfer property and obtain a more significant force-induced response effect, particularly a force-induced response effect with a significant change in fluorescence wavelength shift and a high force-induced color contrast, it is more preferable that the substituent on the aromatic ring structure is a substituent containingSubstituents with strong electron donating or electron withdrawing effects;

wherein the content of the first and second substances,

Typical structures of the formulae R-1 to R-7 may be illustrated below, but the invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the cyanoethylene series non-covalent force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by cyanoethylene aggregation-induced emission elements, and the structural general formula of the group includes but is not limited to the following classes:

wherein Ar is⁴Each independently selected from aromatic rings, the structure of which is selected from monocyclic structure, polycyclic structure, spiro structure and condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted with any suitable substituent atom, substituent group, or substituted polymer chain; the substituent atom, substituent group, and substituted polymer chain are not particularly limited. To increase steric hindrance and to concentrate non-planarity of the induced luminophoreConformation, forming loosely packed aggregates to obtain a more pronounced force-induced response effect, preferably the ring structure of the aromatic ring is a polycyclic, fused ring structure; by reasonably selecting the polycyclic structure and the condensed ring structure, the spectral property of the formed force sensitive group can be regulated and controlled in a large range, so that the color change and the fluorescence/phosphorescence emission wavelength which can be regulated in a large range can be obtained, and the application requirements of various application scenes can be met; in order to obtain more significant force-responsive effects, especially force-responsive effects with significant shift in fluorescence wavelength and high color contrast of force-induced discoloration, it is preferred that a portion of the hydrogen atoms on the aromatic ring be substituted with a heteroatom, a hydrocarbyl substituent, or a heteroatom substituent, by way of example, suitable heteroatoms, hydrocarbyl substituents, heteroatom substituents are selected from, but not limited to: fluorine atom, chlorine atom, bromine atom, iodine atom, trifluoromethyl group, pentafluorothio group, nitro group, cyano group, C_1-20Alkyl radical, C_1-20Aryl radical, C_1-20Alkoxy radical, C_1-20Alkylthio radical, C_1-20Alkylamino radical, C_1-20Aryloxy radical, C_1-20Arylthio radical, C_1-20An arylamine group. Ar is⁴Preferably at least one of the following structures, but the invention is not limited thereto:

by way of example, typical Ar⁴Including but not limited to one or more of the following structures:

wherein Ar is⁵Is a divalent aromatic ring, the structure of which is selected from a monocyclic structure, a polycyclic structure, a spiro structure and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted with any suitable substituent atom, substituent group, or substituted polymer chain; wherein, theThe substituent atom is preferably selected from fluorine atom, chlorine atom, bromine atom and iodine atom, and the substituent group is preferably selected from C_1-20Alkyl radical, C_1-20Aryl radical, C_1-20Alkoxy radical, C_1-20Alkylthio radical, C_1-20Alkylamino radical, C_1-20Aryloxy radical, C_1-20Arylthio radical, C_1-20An arylamine group. Ar is⁵Preferably at least one of the following structures, but the invention is not limited thereto:

by way of example, typical Ar⁵Including but not limited to one or more of the following structures:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula S-1 is further preferably selected from the following general structures:

wherein Ar is⁴、

The definition, selection range and preferable range of (A) are the same as those of the general formula S-1.

Typical structures of the formulae S-1 to S-4 may be illustrated below, but the invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the berberine series non-covalent force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by berberine aggregation-induced emission elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:

wherein a is an integer of 1-5, preferably 1 or 2;

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula; wherein the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or the substituent group is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent group and heteroatom-containing substituent group, preferably from substituent group with electron-donating effect;

wherein the content of the first and second substances,¹r is selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; when in use¹When R is selected from an atom or a substituent, it is preferably selected from an atom or a substituent having an electron-withdrawing effect;

wherein the content of the first and second substances,

A typical structure of the formula T-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the maleimide series non-covalent force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive element formed by maleimide aggregation-induced emission element, and its structural general formula includes but is not limited to the following classes:

wherein the content of the first and second substances,²r is selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; when in use²When R is selected from an atom or a substituent, it is preferably selected from an atom or a substituent having an electron-withdrawing effect; by way of example, said atoms or substituents having an electron-withdrawing effect are selected from, but not limited to: halogen atom, nitro group, pentafluorothio group, trifluoromethyl group, 4-trifluoromethyl-phenyl group;

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula;

wherein the content of the first and second substances,

indicates that n is connected with

wherein the content of the first and second substances,

Typical structures of the general formulae U-1, U-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the 4-hydropyran series non-covalent force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by 4-H pyran aggregation-induced emission elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:

wherein, W²Each of which isIndependently is a divalent linking group, each independently selected from

Wherein, W³Each independently an atom or group having an electron withdrawing effect, preferably from an oxygen atom or a sulfur atom, more preferably from an oxygen atom; the group with electron-withdrawing effect is selected from but not limited to:

wherein Ar is⁶Each independently selected from aromatic rings having an electron donating effect; wherein the aromatic ring structure is a monocyclic structure, a polycyclic structure or a condensed ring structure; by way of example, suitable Ar' s⁶Selected from, but not limited to:

wherein the content of the first and second substances,

each independently attached to any suitable hydrogen atom, substituent group, and substituted polymer chain that may or may not participate in force activation.

Typical structures of the formulae V-1 to V-3 may be illustrated below, but the invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the non-covalent force-sensitive group based on the energy transfer composition refers to a non-covalent force-responsive element formed by combining a non-mechanical force-responsive energy donor and a non-mechanical force-responsive energy acceptor which can transfer energy with each other, wherein the energy donor and the energy acceptor are respectively not responded by mechanical force, and when mechanical force is acted, the change of the distance, the arrangement form and the like between the energy donor and the energy acceptor is caused, so that the energy transfer process between the energy donor and the energy acceptor is weakened/inhibited or enhanced/promoted, and the change of fluorescence wavelength shift, fluorescence intensity enhancement or weakening, fluorescence lifetime extension or shortening and the like caused by the change shows specific force-induced response.

In the present invention, the "energy transfer" refers specifically to the transfer of photon energy from an energy donor to an energy acceptor; in one case, when an energy donor absorbs a photon of a certain frequency, it is excited to a higher energy state of an electron, and energy transfer to an adjacent energy acceptor is achieved by dipole resonance interaction between the energy donor and the energy acceptor before the electron returns to the ground state; in another case, when the energy donor emits light, energy transfer to the adjacent energy acceptor is achieved through dipole resonance interaction between the energy donor and the energy acceptor. In order to achieve energy transfer between the energy donor and the energy acceptor to achieve the desired force-induced response effect, the following conditions must be satisfied: 1) the emission spectrum of the energy donor and the absorption spectrum of the energy acceptor are partially overlapped; 2) the energy donor and the energy acceptor need to be close enough together, preferably at a distance of no more than 10 nm; 3) The energy donor and the energy acceptor must also be aligned in a suitable manner, with the transfer dipole orientation preferably being approximately parallel.

In the present invention, the energy donor in the non-covalent force sensitive moiety of the energy transfer composition may be selected from non-mechanical force responsive fluorophores and/or luminophores, and the energy acceptor may be selected from non-mechanical force responsive fluorophores and/or quenchers.

In the present invention, the energy donor and the energy acceptor contained in the non-covalent force-sensitive group of the energy transfer-based composition may be selected from the group consisting of, but not limited to, pre-existing, photo-activated, thermal-activated, electro-activated, chemical-activated, bio-activated, magnetic-activated moieties, and does not include force-activated moieties. In the present invention, when multiple energy donors and multiple energy acceptors are contained in the same polymer, each of the energy donors and energy acceptors can have more than one source. In a preferred embodiment of the present invention, all energy donors and energy acceptors are pre-existing, which facilitates force-induced activation by controlling mechanical force action alone, resulting in rapid and stable force-induced response; in another preferred embodiment of the invention, the part of the energy donor or energy donor is pre-existing, and the other part of the energy donor and energy acceptor is selected from the group consisting of those generated by photoactivation, those generated by thermal activation, those generated by electrical activation, those generated by chemical activation, those generated by biological activation, those generated by magnetic activation, and thus facilitates the achievement of a force-induced response effect by light control, thermal control, electrical control, chemical stimulation, biological stimulation and mechanical force in a dual or multiple coordinated control; in another preferred embodiment of the present invention, the energy donor and the energy acceptor are selected from one or more of photoactivated, thermoactivated, electroactive, chemically activated, biologically activated and magnetically activated, which is advantageous for obtaining abundant non-mechanical force response and achieving multiple coordinated force-induced response effects with mechanical force control of the composition to meet the needs of various special application scenarios.

In the present invention, the energy donor and the energy acceptor in the non-covalent force-sensitive group of the energy transfer composition may be on the same polymer chain, on different polymer chains, or one of them may be on the polymer chain; wherein the energy donor and the energy acceptor may be covalently linked to the polymer chain. In an embodiment of the invention, it is preferred that the distance between the energy donor and the energy acceptor does not exceed 10 nm.

In the invention, the energy transfer can be organically regulated and controlled by designing, selecting and adjusting the type, the quantity and the combination of the energy donor/the energy donor, so that excellent diversified and cooperatively controlled energy transfer performance and wide application are obtained.

In the present invention, the energy donor and the energy acceptor in the non-covalent force sensitive group based on the energy transfer composition may be different or identical, preferably different. When the energy donor and acceptor are the same, at least one of the donor and acceptor must have multiple excitation and/or emission wavelengths.

In the present invention, the energy transfer in the non-covalent force-sensitive groups based on the energy transfer composition may be of only one stage or may be of multiple stages. When the polymer contains a plurality of fluorophores/luminophores (or precursors thereof), under appropriate energy transfer conditions, multi-stage energy transfer can be formed, namely, the fluorescence/cold luminescence wavelength emitted by the first-stage energy donor is taken as the fluorescence excitation wavelength of the first-stage energy acceptor, the fluorescence wavelength emitted by the first-stage energy acceptor after being excited is taken as the fluorescence excitation wavelength of the second-stage energy acceptor, the fluorescence wavelength emitted by the second-stage energy acceptor after being excited is taken as the fluorescence excitation wavelength of the third-stage energy acceptor, and the like, so that the phenomenon of multi-stage energy transfer is realized. Where only the first transfer is present, the energy transfer may be fluorescence quenching; in multiple transfer stages, the energy transfer of the last stage may be fluorescence quenching.

In the invention, the fluorescence refers to a photoluminescence cold luminescence phenomenon that when a fluorophore is irradiated by incident light with a certain wavelength, the fluorophore enters an excited state after absorbing light energy, and is immediately de-excited to emit emergent light with a wavelength longer or shorter than that of the incident light; the wavelength of the incident light is called the excitation wavelength and the wavelength of the outgoing light is called the emission wavelength. When the emission wavelength is longer than the excitation wavelength, it is called down-conversion fluorescence; when the emission wavelength is longer than the excitation wavelength, it is called up-conversion fluorescence. In addition to photoluminescence, the fluorescence excitation wavelength that can be an energy acceptor or the cold luminescence that can be quenched by an energy acceptor can be any other suitable light that is not emitted by heat generation by a substance, including but not limited to chemiluminescence of a luminophore, bioluminescence of a luminophore. The fluorescence quenching refers to a phenomenon that the fluorescence intensity and fluorescence lifetime of a fluorescent/luminescent substance are reduced due to the presence of a quencher or a change in the fluorescence environment, and includes static quenching, dynamic quenching, and aggregate fluorescence quenching. The static quenching refers to a phenomenon that a complex is generated between a ground state fluorophore/luminophore and a quencher through weak combination, and the complex quenches fluorescence/luminescence; the dynamic quenching refers to that an excited state fluorophore/luminophore collides with a quenching group to quench the fluorescence/luminescence of the excited state fluorophore/luminophore; the fluorescence quenching refers to the property that some fluorophores/luminophores are aggregated to generate fluorescence quenching, and the self-quenching phenomenon is generated when the concentration of the fluorophores/luminophores is too large.

In the present invention, the fluorophore may be selected from the group consisting of organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, inorganic fluorophores, which may be selected from the group consisting of, but not limited to, covalent groups and non-covalent complexes, self-assemblies, compositions, aggregates and combinations thereof. The fluorophore may be selected from the group including, but not limited to, pre-existing, chemically activated, biologically activated, photoactivated, thermally activated, electroactive, and magnetically activated.

In the present invention, the pre-existing fluorophore refers to a substance that can absorb light energy and enter an excited state without any activation or intervention under the irradiation of incident light with a certain wavelength, and immediately de-excite and emit emergent light with a wavelength shorter or longer than that of the incident light, and includes, but is not limited to, organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, organic up-conversion fluorophores, inorganic up-conversion fluorophores, which may be selected from the group consisting of, but is not limited to, covalent structures and non-covalent complexes, self-assemblies, compositions, aggregates and combinations thereof.

Among these, the covalent organic fluorophores can be exemplified as follows, but the present invention is not limited thereto:

among them, the following are examples of the aggregation-induced emission organic fluorophore, but the present invention is not limited thereto:

the organic fluorophores of the other non-covalent complexes, self-assemblies, aggregates, compositions and various combinations thereof may be selected from any suitable structure. Wherein the composition organic fluorophore may itself be a donor and acceptor composition having energy transfer properties.

Among them, the organometallic fluorophore may be exemplified as follows, but the present invention is not limited thereto:

among them, the organic element fluorophore may be exemplified as follows, but the present invention is not limited thereto:

among them, the biological fluorophore can be exemplified as follows, but the present invention is not limited thereto:

GFP、EGFP、GFP-S65T、BFP、CFP、YFP、EBFP、Azurite、EBFP2、mTagBFP、TagRFP、EYFP、ECFP、Cerulean、mTFP、mTurquoise、mCitrine、mVenus、CyPet、YPet、phiYFP、DsRed、mBanana、 mOrange、dTomato、mTangerine、mStrawberry、mCherry、mKO、GFP-Phe66、Sirius、mPlum、mKate、 mKate2、Katushka、mNeptune、TagRFP657、IFP1.4、T-Sapphire、mAmetrine、mKeima、mLSS-Kate1、 mLSS-Kate2；

the inorganic fluorophores include but are not limited to sulfide fluorophores, aluminate fluorophores, silicate fluorophores, nitride fluorophores, oxide fluorophores, oxynitride fluorophores, rare earth fluorophores, and inorganic non-metal quantum dots, wherein part of the inorganic fluorophores are mainly composed of a substrate: activator composition, inorganic fluorophores may be exemplified as follows, but the invention is not limited thereto:

CaS:Eu、SrS:Ce、SrGa₂S₄:Eu、SrAl₂O₄:Ce、CaAl₂O₄:Eu、BaAl₂O₄:Ce、Lu₃Al₅O₁₂:Eu、Y₃Al₅O₁₂:Ce、 Tb₃Al₅O₁₂:Ce、Gd₃Al₅O₁₂:Eu、Ba₂SiO₄:Eu、Sr₂SiO₄:Eu、BaSi₂O₃:Eu、BaSiO₃:Eu、Ba₃SiO₅:Eu、Ba₂Si₃O₈:Eu、 Ba₃Si₅O₁₃:Eu、Ba₉Sc₂Si₆O₂₄:Eu、Ca₃Mg₂Si₃O₁₂:Ce、Ca₃Sc₂Si₃O₁₂:Ce、Ca₂Si₂O₇:Eu、SrLi₂SiO₄:Eu、CaLi₂SiO₄:Eu、 Ca₂Si₅N₈:Eu、Sr₂Si₅N₈:Eu、CaAlSiN₃:Eu、ZnO:Eu、ZnO:Li、SrSi₂N₂O₂:Eu、CaSi₂N₂O₂eu, CdS/ZnS quantum dot, ZnSe/ZnS quantum dot, InP/ZnS quantum dot, CdSe/ZnS quantum dot, carbon quantum dot, PbS quantum dot with emission wavelength in near infrared region, ZnS: Cu series long afterglow material, CaS: Bi series long afterglow material, SrAl₂O₄:Eu，Dy series long afterglow material, CaAl₂O₄Eu, Nd series long afterglow material, Sr₄Al₁₄O₂₅Eu, Dy series long afterglow material, Zn₂SiO₄Mn, As series long afterglow material, Sr2MgSi₂O₇Eu, Dy series long afterglow material, Ca₂MgSi₂O₇Eu, Dy series long afterglow material, MgSiO₃Mn, Eu, Dy series long afterglow material, CaTiO₃Pr, Al series long afterglow material, Ca₈Zn(SiO₄)₄Cl₂Eu series long afterglow material, Ca₂Si₅N₈Eu series long afterglow materials;

inorganic up-converting phosphors typically consist of a host, an activator and a sensitizer, usually doped into nanoparticles or glass by rare earth ions, to absorb long-wavelength radiation and emit short-wavelength fluorescence. Among them, rare earth ions can be exemplified as follows, but the present invention is not limited thereto: scandium ion, yttrium ion, lanthanum ion, cerium ion, neodymium ion, praseodymium ion, promethium ion, europium ion, samarium ion, terbium ion, gadolinium ion, dysprosium ion, holmium ion, erbium ion, thulium ion, lutetium ion, ytterbium ion;

among these, inorganic up-converting fluorophores can be exemplified as follows, but the present invention is not limited thereto:

NaYF₄:Er、CaF₂:Er、Gd₂(MoO₄)₃:Er、Y₂O₃:Er、Gd₂O₂S:Er、BaY₂F₈:Er、LiNbO₃:Er，Yb，Ln、Gd₂O₂:Er，Yb、 Y₃Al₅O₁₂:Er，Yb、TiO₂:Er，Yb、YF₃:Er，Yb、Lu₂O₃:Yb，Tm、NaYF₄:Er，Yb、LaCl₃:Pr、NaGdF₄:Yb，Tm@NaGdF₄core-shell nanostructure of Ln, NaYF₄:Yb，Tm、Y2BaZnO₅:Yb，Ho、NaYF₄:Yb，Er@NaYF₄Core-shell nanostructures of Yb, Tm, NaYF₄:Yb，Tm(@NaGdF₄Core-shell nanostructures of Yb.

The organic up-converting fluorophore is preferably an organic composition which achieves up-conversion effect by triplet-triplet annihilation based, said organic composition mainly consisting of a sensitizer and an organic up-converting energy acceptor.

Among them, the following sensitizers can be exemplified, but the present invention is not limited thereto:

among them, the organic up-conversion energy acceptor can be exemplified as follows, but the present invention is not limited thereto:

in the present invention, fluorophores such as organic fluorophores, organic metal fluorophores, organic element fluorophores, biological fluorophores, organic upconversion fluorophores, inorganic fluorophores, and inorganic upconversion fluorophores can also form various noncovalent complexes, self-assemblies, aggregates, and combinations thereof, which can be the same or different.

In the present invention, the fluorophore generated by chemical activation refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed by a structural change due to a chemical reaction. Suitable structures that can be chemically activated to generate fluorophores can be obtained by suitable structural modification and derivatization of suitable fluorophores as described above, although the invention is not limited thereto. The force-sensitive moieties/groups of the invention having force-sensitive properties can also be chemically activated under suitable conditions without a force-sensitive response to generate a fluorophore.

In the present invention, the fluorescence generated by biological activation refers to a structure having fluorescence in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed in structure by a biological reaction. Suitable bioactivatable fluorophore generating structures may be obtained by suitable structural modification and derivatization of the above-mentioned suitable fluorophores, although the invention is not limited thereto. The various force-sensitive moieties/groups of the invention having force-sensitive properties can also be biologically activated under suitable conditions without a force-sensitive response to generate a fluorophore.

In the present invention, the photo-activation generated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed by a structural change due to a photoreaction. Suitable photoactivatable fluorophore-generating structures can be obtained by suitable structural modification and derivatization of the above-mentioned suitable fluorophores. The following may be exemplified, but the invention is not limited thereto:

PA-GFP (trade Mark), PA-mCherryl (trade Mark), Kaede (trade Mark), PS-CFP2 (trade Mark), mEosFP (trade Mark), Dendra2 (trade Mark), Dronpa (trade Mark), rsFasLime (trade Mark), Pandon (trade Mark), bsDronpa (trade Mark), Kindling (trade Mark).

The force-sensitive moieties/groups of the present invention having force-sensitive properties can also be photoactivated under suitable conditions without a force-sensitive response to generate a fluorophore.

In the present invention, the thermally activated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor of the fluorophore is changed by a structural change due to a thermal reaction. Suitable structures for the heat-activatable fluorophores can be obtained by suitable structural modification and derivatization of the suitable fluorophores mentioned above, but the invention is not limited thereto. The various force-sensitive moieties/groups of the present invention having force-sensitive properties can also be thermally activated under suitable conditions without a force-sensitive response to generate a fluorophore.

In the present invention, the electrically activated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by structural change of its precursor under the action of an electric stress is changed. Suitable structures that can be electroactive to generate fluorophores may be obtained by suitable structural modification and derivatization of suitable fluorophores as described above, although the invention is not limited thereto. The various force-sensitive moieties/groups of the present invention having force-sensitive properties can also be electroactive under suitable conditions without a force-sensitive response to generate a fluorophore.

In the present invention, the magnetically activated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed by a structural change due to a magnetic reaction. Suitable structures which can be magnetically activated to generate fluorophores may be obtained by suitable structural modification and derivatization of suitable fluorophores as described above, although the invention is not limited thereto. The force-sensitive moieties/groups of the invention having force-sensitive properties can also be magnetically activated under suitable conditions without a force-sensitive response to generate a fluorophore.

In the present invention, the fluorophore-generating precursor, which may also be a covalent and/or non-covalent complex of a suitable fluorescent moiety and a quencher moiety, is in a quenched state before the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., and is activated by the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., to generate fluorescence from the fluorescent moiety, which may be any suitable entity as described above that can generate fluorescence upon excitation with light of a suitable wavelength.

In the present invention, the fluorophore may function as an energy donor under suitable conditions and may function as an energy acceptor under otherwise suitable conditions. By rational utilization of the fluorophores, a desirable combination of energy donors and acceptors can be obtained, resulting in excellent energy transfer properties.

In the present invention, the luminophore may be selected from, but not limited to, chemical activation generated, biological activation generated, photoactivation generated/photoluminescent, thermoactivation generated/thermoluminescable, electroactive generated/electroluminescent, magnetic activation generated/magnetoluminesceable.

In the present invention, the precursor of the luminophore generated by the chemical activation is called a chemiluminescent group, which refers to a chemical group capable of generating a luminescence phenomenon by a structural change after a chemical reaction, and includes, but is not limited to, a suitable dioxetane chemiluminescent system, a luminol chemiluminescent system, an oxalate peroxide chemiluminescent system, an acidic potassium permanganate chemiluminescent system, a tetravalent cerium chemiluminescent system, an acridinium ester chemiluminescent system, and a fluorescein chemiluminescent system.

Wherein the suitable dioxetane chemiluminescent system is comprised of a suitable dioxetane compound and a fluorescer, wherein the suitable dioxetane compound may be exemplified by, but is not limited to:

among them, the fluorescent agent may be exemplified as follows, but the present invention is not limited thereto:

5, 12-bis (phenylethynyl) naphthalene, 9, 10-diphenylanthracene, 1-chloro-9, 10-diphenylanthracene, 1-methoxy-9, 10-diphenylanthracene, 1, 5-dichloro-9, 10-diphenylanthracene, 1, 8-dimethoxy-9, 10-diphenylanthracene, pyrene, 9, 10-bis (phenylethynyl) anthracene, 1-chloro-9, 10-bis (phenylethynyl) anthracene, 1-methoxy-9, 10-bis (phenylethynyl) anthracene, rubrene, 5, 12-bis (phenylethynyl) tetracene, 2-chloro-bis (phenylethynyl) tetracene, rhodamine B, 6-chloro-bis (phenylethynyl) tetracene, 16, 17-dideoxy violanthrone;

the luminol chemiluminescence system can be exemplified as follows, but the invention is not limited thereto:

the oxalate peroxide chemiluminescence system comprises an oxalate compound, a fluorescent agent and hydrogen peroxide, wherein the oxalate compound can be exemplified as follows, but the invention is not limited to the following:

the chemiluminescence system of the acidic potassium permanganate consists of acidic potassium permanganate and a substance to be detected, and some adaptive compounds can be added to enhance the chemiluminescence intensity of the acidic potassium permanganate₄Test substance or acidic KMnO₄- (luminescence enhancer) -analyte, which may be exemplified as follows, but the present invention is not limited thereto:

acidic KMnO₄Oxalate, acidic KMnO₄Luminol, acidic KMnO₄- (divalent lead ion) -luminol, acidic KMnO₄-SO₂Acidic KMnO₄Sulfite, acidic KMnO₄Glutamic acid, acidic KMnO₄Aspartic acid, acidic KMnO₄- (Formaldehyde) -L-Tryptophan, acidic KMnO₄- (Formaldehyde) -methotrexate, acidic KMnO₄- (Formaldehyde) -Dichloromethabenzuron, acidic KMnO₄- (Formaldehyde) -Aminopyrine, acidic KMnO₄- (Formaldehyde) -iodine, acidic KMnO₄- (Formaldehyde) -tyrosine, acidic KMnO₄- (glyoxal) -imipramine, acidic KMnO₄- (glyoxal) -dipyridamole, acidic KMnO₄- (glyoxal) -reserpine, acidic KMnO₄- (sodium dithionite) -riboflavin, acidic KMnO₄- (sodium dithionite) -tetrahydropalmatine, acidic KMnO₄- (sodium dithionite) -vitamin B₆Acidic KMnO₄- (sodium dithionite) -pipemidic acid, acidSex KMnO₄Morphine, acidic KMnO₄-buprenorphine, acidic KMnO₄-para-aminobenzoate, acidic KMnO₄Codeine, acidic KMnO₄Tryptophan, acidic KMnO₄Dopamine, acidic KMnO₄Levodopa, acidic KMnO₄Adrenaline, acidic KMnO₄-methoxybenzylaminopyridine, acidic KMnO₄-DL-malic acid;

the tetravalent cerium chemiluminescence system is composed of tetravalent cerium and a test object, and some adaptive compounds can be added to enhance the chemiluminescence intensity, and in the invention, the tetravalent cerium chemiluminescence system is expressed as a tetravalent cerium-test object or a tetravalent cerium- (luminescence enhancer) -test object, which can be exemplified as follows, but the invention is not limited thereto:

tetravalent cerium-paracetamol, tetravalent cerium-naproxen, tetravalent cerium-phenacetin, tetravalent cerium-biphenyltriphenol, tetravalent cerium-sulfite, tetravalent cerium- (quinine) -penicillamine, tetravalent cerium- (quinine) -2-mercaptoethane sulfonate, tetravalent cerium- (quinine) -cysteine, tetravalent cerium- (quinine) -thiazole Schiff base, tetravalent cerium- (quinine) -sulfite, tetravalent cerium- (cinchonine) -sulfite, tetravalent cerium- (ciprofloxacin) -sulfite, tetravalent cerium- (oxfloxacin) -sulfite, tetravalent cerium- (norfloxacin) -sulfite, pentavalent cerium-and-bismuth-containing compound, and mixtures thereof, Tetravalent cerium- (sipafloxacin) -sulfite, tetravalent cerium- (roxofloxacin) -sulfite, tetravalent cerium- (Tb)³⁺+ enoxacin) -sulfite, tetravalent cerium- (Tb)³⁺+ fleroxacin) -sulfite, tetravalent cerium- (Tb)³⁺+ gatifloxacin) -sulfite, tetravalent cerium- (N-tetrahydrobenzothiazole imine schiff base) -sulfite, tetravalent cerium-rhodamine 5G, tetravalent cerium- (rhodamine B) -folic acid, tetravalent cerium- (rhodamine B) -ascorbic acid;

among them, the acridinium ester chemiluminescence system can be exemplified as follows, but the invention is not limited thereto:

4- (2-succinimidylcarbonyl) phenyl-10-carbaldehydeAcridine-9-carboxylate fluorosulfonate;

the fluorescein chemiluminescence system can be exemplified as follows, but the invention is not limited to the following:

in the present invention, the biologically-activated luminophore, a precursor thereof, is referred to as a biologically-activatable luminophore, which refers to a chemical or biological group that is capable of undergoing a structural change by a biological reaction (e.g., catalysis by a biological enzyme) to produce a luminescence phenomenon. The bioactivated luminescence may be exemplified as follows, but the present invention is not limited thereto: marine animal luminescence, bacterial luminescence, firefly luminescence; wherein the marine animals are luminous, including but not limited to luminous marine animals such as noctiluca, dinoflagellate, radioworms, jellyfish, sea feathers, ctenopharyngodon idellus, multicastoma, krill, cerasus, cephalopods, echinoderm, tunicates, fish, clamworm, sea bamboo shoot, sea worm, copepods, schizothorax, Phillips longifolus, columna gigas and the like; the bacteria emit light, and the bacteria include but are not limited to luminescent heterobrevibacterium, luminous bacillus leiognathi, Shewanella villosa, alteromonas haiensis, Vibrio harveyi, Vibrio livialis biotype I, Vibrio fischeri, Vibrio paradoxus, Vibrio orientalis, Vibrio mediterranei, Vibrio arctica, Vibrio cholerae, Vibrio qinghai and the like; the firefly luminescence includes but is not limited to fluorescein bioluminescence and dioxetane bioluminescence.

In the present invention, the photo-activation generated/photo-luminescent luminophore and its precursor are called photo-activation luminophores, which refer to chemical groups that can undergo a structural change after a photo-reaction, thereby generating a luminescence phenomenon.

In the present invention, the thermally activated/thermoluminescable luminophore precursor thereof is referred to as a thermoactivatable luminophore, which refers to a chemical group that is capable of undergoing a structural change upon thermal reaction, thereby generating a luminescence phenomenon.

In the present invention, the electroactive produced/electroluminescent luminophore and its precursor are referred to as an electroactive luminophore, which means a chemical group that can generate a luminescence phenomenon by a structural change or charge/hole combination or electrical excitation after an electrochemical reaction. Examples thereof may be as follows, but the present invention is not limited thereto:

in the present invention, the electrically activatable luminophores further comprise organic light emitting diodes and inorganic light emitting diodes. Wherein, the organic light emitting diode includes, but not limited to, an organic small molecule light emitting diode and an organic polymer light emitting diode; wherein the electron transport layer material in the organic small molecule light emitting diode can be selected from fluorescent dye compounds such as Alq, Znq, Gaq, Bebq, Balq, DPVBi, ZnSPB, PBD, OXD, BBOT, etc.; the material of the hole transport layer is selected from, but not limited to, aromatic amine fluorescent compounds, such as organic materials like TPD, TDATA, etc. Organic polymer light emitting diodes include, but are not limited to: organic electroluminescent materials such as poly (p-phenylenes), poly (acetylenes), poly (carbazoles), polyfluorenes, and polythiophenes. Wherein, the inorganic light emitting diode material includes but not limited to: gallium arsenide light emitting diodes, gallium phosphide light emitting diodes, silicon carbide light emitting diodes, gallium nitride light emitting diodes, zinc selenide light emitting diodes, gallium phosphide light emitting diodes, aluminum arsenide light emitting diodes.

In the present invention, the magnetically activated/magnetoluminesceable luminophore and its precursor are referred to as magnetically activated luminophores, which refer to chemical groups capable of undergoing a structural change after a magnetic reaction, thereby generating a luminescence phenomenon.

In the present invention, the luminophore-generating precursor, which may also be a covalent and/or non-covalent complex of a suitable luminophore and a quencher, is in a quenched state before the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., and is activated by the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., to produce luminescence from the luminophore, which may be any suitable entity as described above that can produce luminescence upon excitation with light of a suitable wavelength.

It is noted that the same luminophore can exist simultaneously with one or more activated luminescence processes, such as dioxetane luminescence, oxalate peroxide luminescence, fluorescein luminescence, both chemically activated luminescence and biologically activated luminescence.

In the context of the present invention, the quencher refers to a non-fluorescent energy acceptor, which may also be selected from pre-existing or activated. Groups that can act as pre-existing quencher energy acceptors include, but are not limited to: quenching dyes having a basic skeleton such as NPI, NBD, DABCYL, BHQ, ATTO, Eclipse, MGB, QXL, QSY, Cy, Lowa Black, and IRDYE, and quenching dye derivatives thereof include, specifically, the following:

ATT0540Q (trade name), ATT0580Q (trade name), ATT0612Q (trade name), Eclipse (trade name), MGB (trade name), QXL490 (trade name), QXL520 (trade name), QXL570 (trade name), QXL610 (trade name), QXL670 (trade name), QXL680 (trade name), Cy5Q (trade name), Cy7Q (trade name), Lowa Black FQ (trade name), Lowa Black RQ (trade name), IRDYE QC-1 (trade name).

In the present invention, the fluorophore having an aggregate fluorescence quenching property includes, but is not limited to, triphenylamine-based fluorophore, fused ring-based fluorophore, rylimide-based fluorophore, rubrene-based fluorophore, porphyrin-based fluorophore, phthalocyanine-based fluorophore, and the like, and specifically, the following may be cited:

in the invention, the quenching group can also be selected from a structure with fluorescence quenching performance generated by activating a part of force-sensitive elements/force-sensitive groups with force-sensitive characteristics under other actions besides the mechanical force action.

In the present invention, suitable activatable fluorophores, luminophores, quenchers, which may have two or more activation methods, may be used independently, simultaneously or sequentially, and the different activation methods may even produce different activation effects.

In the present invention, the force-sensitive moiety/group having force-sensitive property capable of generating a fluorophore and/or a quencher by an activation action of one or more of chemical, biological, photothermal, thermal, electrical, magnetic, etc. other than mechanical force is mainly selected from a radical type structure, a five-membered ring structure, a six-membered ring structure, a cyclobutane structure, a monoacyclocyclobutane structure, a dioxetane structure, a cyclobutene structure, a DA structure, a hetero DA structure, a light-operated DA structure, a [4+4] cycloaddition structure, a metal-ligand structure. The force-sensitive element/group with force-sensitive property capable of generating a luminophore by other than mechanical force, such as activation by one or more of chemical, biological, photothermal, thermal, electrical, magnetic, etc., is selected from dioxetane structures. The structure can be connected to a polymer chain in a small molecule form, a single-chain connection form or a multi-chain connection form which cannot bear force of a basic unit structure, so that the structure cannot be stressed and activated; or even if it can be activated by a force, it cannot be activated by regulating the magnitude of the force so that the mechanical force is smaller than its activation force. Those skilled in the art may implement the present invention with reasonable benefit from the logic and concepts disclosed herein. These rich selectivities also represent advantages of the present invention.

In the present invention, in order to obtain the desired force-responsive properties, the non-covalent force-sensitive groups of the energy transfer-based composition must be aligned in a suitable manner, preferably with nearly parallel transfer dipole orientation, in addition to satisfying the partial overlap of the emission spectrum of the energy donor and the absorption spectrum of the energy acceptor and the need for close enough proximity of the energy donor and the energy acceptor.

In an embodiment of the present invention, in the crosslinked polymer, the force-sensitive group may be located on the crosslinked polymer network backbone, a side chain backbone, preferably on the crosslinked network backbone. In the present invention, it is also not excluded that the force-sensitive groups may be located in side groups and end groups of the polymer chain, but that they do not achieve a force-induced response, since no force is applied in the side groups and end groups, but may be responsive in other suitable ways.

In the invention, the polymer crosslinked network contains polymer chain segments, including a polymer crosslinked network skeleton chain segment and a polymer crosslinked network side chain segment. The segment preferably has a molecular weight of not less than 1000. The different types of chemical structures refer to chemical structure types including but not limited to carbon chain structures, carbon-hetero chain structures, element-organic chain structures, carbon element chain structures, element-organic hetero chain structures, and carbon-hetero element chain structures. In an embodiment of the invention, the segment does not include a force-sensitive moiety on the segment, nor a small molecule linker for linking the force-sensitive moiety and the segment.

In the present invention, the carbon chain structure refers to a polymer chain in which the main chain of the segment is mainly composed of carbon atoms, which may be selected from any one of the following groups, any unsaturated form, any substituted form, and combinations thereof: polyolefin-based chains such as polyethylene chains, polypropylene chains, polyisobutylene chains, polystyrene chains, polyvinyl chloride chains, polyvinylidene chloride chains, polyvinyl fluoride chains, polytetrafluoroethylene chains, polytrifluorochloroethylene chains, polyvinyl acetate chains, polyvinyl alkyl ether chains, polybutadiene chains, polyisoprene chains, polychloroprene chains, polynorbornene chains, and the like; polyacrylic acid chains such as polymethyl acrylate chains, polymethyl methacrylate chains, and the like; polyacrylonitrile-based chains such as polyacrylonitrile chains and the like; preferred are polyethylene chains, polypropylene chains, polystyrene chains, polyvinyl chloride chains, polybutadiene chains, polyisoprene chains, polymethyl acrylate chains, and polyacrylonitrile chains.

In the present invention, the carbon hetero chain structure refers to a polymer chain in which the main chain of the chain segment is mainly composed of carbon atoms and heteroatoms such as nitrogen, oxygen, sulfur, and the like, and may be selected from any one of the following groups, any unsaturated form, any substituted form, any hybridized form, and combinations thereof: polyether chains such as polyethylene oxide chains, polypropylene oxide chains, polytetrahydrofuran chains, polyphenylene ether chains, and the like; polyester-based chains such as polycaprolactone chains, polypentalactone chains, polylactide chains, polyethylene terephthalate chains, unsaturated polyester chains, alkyd chains, polycarbonate chains, bio-polyester chains, and the like; polysulfone chains, polyphenylene sulfide chains, polyimide chains, etc.; polyethylene oxide chains, polytetrahydrofuran chains, polycaprolactone chains, polylactide chains are preferred.

In the present invention, the carbon element chain structure means that the chain segment main chain contains element atoms besides carbon atoms, wherein the element atoms include but are not limited to P, Si, Se, Ni, Co, Pt, Ru, Ti, Al, Ir.

In the present invention, the carbon-heteroatom chain structure means that the chain main chain contains heteroatoms besides carbon atoms, wherein the heteroatoms include, but are not limited to, oxygen, nitrogen and sulfur.

In the present invention, the term "elemental organic chain structure" refers to a polymer in which the main chain of the chain segment does not contain carbon atoms, and is mainly composed of silicon, boron, aluminum, oxygen, nitrogen, phosphorus, sulfur and other atoms, but has an organic group in a side group. Such as polyorganosiloxanes, whose main chain is a siloxane chain and whose pendant groups are methyl, ethyl, etc. Preferred polyorganosiloxanes include, but are not limited to, for example, polyorganosiloxane chains, polymethylethylorganosiloxane chains, polydiethylalkylorganosiloxane chains, polymethylphenylorganosiloxane chains, polydiphenylorganosiloxane chains, hydrogenpolyorganosiloxane chains, polyorganosiloxane nitrogen chains, polyorganosiloxane sulfur chains, polyorganophosiloxane chains, polyorganopolysiloxane chains. Further, there are organoboron polymer chain residues such as organoborane chain residues, polyorganoborazine chain residues, polyorganoborasulfane chain residues, polyorganoboraphosphoalkane chain residues, etc.; an organophosphorus-based polymer chain residue; an organolead-based polymer chain residue; an organotin-based polymer chain residue; an organic arsenic-based polymer chain residue; an organic antimony-based polymer chain residue.

In the present invention, the element organic hetero chain structure means that the chain segment main chain contains only element atoms and hetero atoms.

In an embodiment of the present invention, it is preferred that the segments of the at least two different types of chemical structures are selected from the group consisting of carbon chain and carbon hetero chain combinations, carbon chain and element organic chain combinations, carbon hetero chain and element organic chain combinations, carbon chain and carbon hetero element chain combinations, carbon hetero chain and carbon hetero element chain combinations.

In the present invention, for the force-responsive crosslinked polymer having the above-described crosslinked network chemical structure, it preferably has the following structure, but the invention is not limited thereto.

In a preferred embodiment of the invention (first network structure), the force-responsive crosslinked polymer comprises a homolytic force-sensitive group, wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the embodiment, the cross-linking structure improves the mechanical property of the polymer to a certain extent, and the homolytic force sensitive groups generate free radicals or change color after being activated by force, thereby being beneficial to realizing force-induced cross-linking and force-induced color change.

In another preferred embodiment of the present invention (second network structure), the force-responsive cross-linked polymer comprises a reversible free-radical type force-sensitive group, wherein the degree of cross-linking of the common covalent cross-links is above its gel point and the degree of cross-linking of the force-sensitive group cross-links is above its gel point. In this embodiment, the reversible free radical type force-sensitive group is a force-sensitive group having dynamic covalent properties, which can provide self-repairability to the polymer in addition to providing force-responsive properties to the polymer.

In another preferred embodiment of the present invention (third network structure), the force-responsive crosslinked polymer comprises a bisaryl cyclic ketone force-sensitive group, wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the embodiment, the biaryl cyclic ketone force sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after the force is activated.

In another preferred embodiment of the present invention (fourth network structure), the force-responsive crosslinked polymer comprises a bisaryl cyclopentenedione force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the embodiment, the diaryl cyclopentenedione force sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after force activation.

In another preferred embodiment of the present invention (fifth network structure), the force-responsive crosslinked polymer comprises a bisaryl chromene force sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force sensitive group crosslinks is above its gel point. In the embodiment, the biaryl chromene force sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after force activation.

In another preferred embodiment of the present invention (sixth network structure), the force-responsive crosslinked polymer comprises a dicyanotetrarylethane force-sensitive moiety wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive moiety crosslinks is above its gel point. In the embodiment, the dicyano tetraarylethane force sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after the force is activated.

In another preferred embodiment of the present invention (seventh network structure), the force-responsive crosslinked polymer comprises a bisarylfuranone force sensitive group, wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force sensitive group crosslinks is above its gel point. In the embodiment, the biaryl furanone force sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after force activation.

In another preferred embodiment of the present invention (eighth network structure), the force-responsive crosslinked polymer comprises an aryl pinacol force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the embodiment, the aryl pinacol force sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after force activation.

In another preferred embodiment of the present invention (ninth network structure), the force-responsive crosslinked polymer comprises a tetracyanoethane force-sensitive moiety wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive moiety crosslinks is above its gel point. In the embodiment, the tetracyanoethane force-sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after force activation.

In another preferred embodiment of the present invention (tenth network structure), the force-responsive crosslinked polymer comprises a bifluorene force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the embodiment, the bifluorene is convenient to prepare and has strong stress sensitivity, and the color can be obviously changed after force activation.

In another preferred embodiment of the present invention (eleventh network structure), the force-responsive crosslinked polymer comprises a heterolytic force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the embodiment, the cross-linking structure enables the mechanical property of the polymer to be improved to a certain extent, and the heterolytic force sensitive groups are easy to initiate reaction after being activated by force, thereby being beneficial to realizing force-induced cross-linking.

In another preferred embodiment of the present invention (twelfth network structure), the force-responsive crosslinked polymer comprises a triarylsulfonium salt series of force-sensitive groups, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive groups crosslinks is above its gel point. In the embodiment, the triaryl sulfonium salt series force sensitive groups are convenient to prepare and strong in stress sensitivity, and can recover the stress sensitivity under certain conditions after force activation and be reused.

In another preferred embodiment of the present invention (thirteenth network structure), the force-responsive crosslinked polymer comprises a reverse cyclization force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the embodiment, the cross-linking structure enables the mechanical property of the polymer to be improved to a certain extent, and the reaction condition of the reverse cyclization force sensitive group is simple and convenient to prepare; unsaturated bonds are generated after the force sensitive groups are activated, and the method is convenient for realizing force-induced crosslinking.

In another preferred embodiment of the present invention (fourteenth network structure), the force-responsive crosslinked polymer comprises a cyclobutane reverse cyclization force-sensitive groups, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive groups crosslinks is above its gel point. In the embodiment, the cyclobutane reverse cyclization force sensitive groups are various in types, simple to prepare and strong in force sensitivity, and crosslinking can be conveniently realized by utilizing double bonds generated after the force sensitive groups are activated.

In another preferred embodiment of the present invention (fifteenth network structure), the force-responsive crosslinked polymer comprises a dioxetane reverse cyclization force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the embodiment, the dioxetane reverse cyclization force-sensitive groups are various in types and adjustable in structure, and the force-induced luminescence property is conveniently realized.

In another preferred embodiment of the present invention (sixteenth network structure), the force-responsive crosslinked polymer comprises a DA series reverse cyclization force-sensitive groups wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive groups crosslinks is above its gel point. In the embodiment, the DA series reverse cyclization force sensitive groups are various in types, simple to prepare and strong in force sensitivity, double bonds generated after the force sensitive groups are activated are utilized to conveniently realize crosslinking, and the DA series reverse cyclization force sensitive groups can have the change of fluorescence wavelength by selecting a proper structure.

In another preferred embodiment of the present invention (seventeenth network), the force-responsive crosslinked polymer comprises a hetero DA-series reverse cyclization force-sensitive group, wherein the degree of ordinary covalent crosslinking is above its gel point and the degree of force-sensitive group crosslinking is above its gel point. In the embodiment, the hetero DA series reverse cyclization force sensitive groups are various in types, simple to prepare and strong in force sensitivity, double bonds generated after the force sensitive groups are activated are utilized to conveniently realize crosslinking, and the hetero DA series reverse cyclization force sensitive groups can have the change of fluorescence wavelength by selecting a proper structure.

In another preferred embodiment of the present invention (eighteenth network structure), the force-responsive crosslinked polymer comprises a [4+4] cycloaddition reverse cyclization force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the present embodiment, the structure of the [4+4] cycloaddition reverse cyclization force-sensitive group generated after force activation is likely to change in fluorescence wavelength.

In another preferred embodiment of the present invention (nineteenth network structure), the force-responsive crosslinked polymer comprises an electrocyclic force-sensitive group, wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the embodiment, the cross-linked structure enables the mechanical property of the polymer to be improved to a certain extent, the response of the electrocyclic force sensitive group under the action of stress is generally accompanied with the change of color, and the electrocyclic force sensitive group is more conveniently used for preparing the warning indication material.

In another preferred embodiment of the present invention (twentieth network structure), the force-responsive crosslinked polymer comprises a six-membered ring series of force-sensitive groups, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive groups crosslinks is above its gel point. In the present embodiment, six-membered ring series force sensitive groups are various in kind and strong in force sensitivity, and different six-membered ring force sensitive groups have different force activation effects and can be selected and used as needed.

In another preferred embodiment of the present invention (twenty first network structure), the force-responsive crosslinked polymer comprises a spiropyran force-sensitive group wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the present embodiment, the spiropyran force-sensitive groups have strong force sensitivity, and can be selectively used as needed by controlling the kind and number of substituents to have different force-activating effects.

In another preferred embodiment of the present invention (twenty-second network structure), the force-responsive crosslinked polymer comprises a spirothiopyran force-sensitive group wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the embodiment, the spirothiopyran force-sensitive groups have strong force sensitivity, and can have different force activation effects by controlling the types and the number of the substituent groups, and can be selected and used according to requirements; and the sulfydryl generated after the force sensitive groups are activated is easy to react, so that the force-induced crosslinking is conveniently realized.

In another preferred embodiment of the present invention (twenty-third network structure), the force-responsive crosslinked polymer comprises a spirooxazine force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the present embodiment, the spirooxazine force sensitive group has strong force sensitivity, and can have different force activation effects by controlling the type and number of the substituents, and can be selectively used as required.

In another preferred embodiment of the present invention (twenty-fourth network structure), the force-responsive crosslinked polymer comprises a five-membered ring series of force-sensitive groups, wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive groups crosslinks is above its gel point. In the embodiment, the five-membered ring series force sensitive groups are various in types and strong in force sensitivity, and different five-membered ring force sensitive groups have different force activation effects and can be selected for use according to requirements.

In another preferred embodiment of the present invention (twenty-fifth network structure), the force-responsive crosslinked polymer contains a rhodamine force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the present embodiment, the rhodamine group has strong force sensitivity, and can have different force activation effects by controlling the type and number of the substituents, and can be selectively used as needed.

In another preferred embodiment of the present invention (twenty-sixth network structure), the force-responsive crosslinked polymer comprises a bend-activating force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the embodiment, the cross-linked structure improves the mechanical property of the polymer to a certain extent, and the bending activation force sensitive group can release small molecules and change of fluorescence wavelength under the action of stress, so that the polymer material is convenient to be used as a polymer material for special application.

In another preferred embodiment of the present invention (twenty-seventh network structure), the force-responsive crosslinked polymer comprises a force-sensitive group of an adduct series of anthracene and a Triazolinedione (TAD), wherein the degree of crosslinking of conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the embodiment, the adduct series force-sensitive groups of anthracene and triazoline diketone (TAD) can release small molecules and change the fluorescence wavelength under the action of stress, and are convenient to be used as polymer materials for special applications.

In another preferred embodiment of the present invention (twenty-eighth network structure), the force-responsive crosslinked polymer comprises a bisthiomaleimide-series force-sensitive groups, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive groups is above its gel point. In the embodiment, the cross-linked structure enables the mechanical property of the polymer to be improved to a certain extent, and the dithiomaleimide series force sensitive groups can realize the effects of fluorescence change, color change and the like under the action of stress, so that the dithiomaleimide series force sensitive groups can be conveniently used as polymer materials for special applications.

In another preferred embodiment of the present invention (twenty-ninth network structure), the force-responsive cross-linked polymer comprises a force-sensitive group of the dinitroso series, wherein the degree of cross-linking of conventional covalent cross-linking is above its gel point and the degree of cross-linking of the force-sensitive group is above its gel point. In the embodiment, the cross-linked structure enables the mechanical property of the polymer to be improved to a certain extent, and the force sensitive groups in the dinitroso series can realize the stress response effect of releasing small molecules under the stress action, so that the polymer material can be conveniently used as a polymer material for special application.

In another preferred embodiment of the present invention (thirtieth network structure), the force-responsive crosslinked polymer is a non-covalent force-sensitive group, wherein the degree of crosslinking of ordinary covalent crosslinks is above its gel point and the degree of crosslinking of force-sensitive groups crosslinks is above its gel point. In the embodiment, the cross-linked structure improves the mechanical property of the polymer to a certain extent, the non-covalent force sensitive groups are various in types, and the polymer material with force-induced fluorescence change and force-induced catalysis is easy to prepare.

In another preferred embodiment of the present invention (thirty-one network structure), the force-responsive cross-linked polymer is a supramolecular complex force-sensitive group, wherein the degree of cross-linking of the common covalent cross-links is above its gel point and the degree of cross-linking of the force-sensitive group cross-links is above its gel point. In this embodiment, the supramolecular complex force sensitive groups are of various types and have high stress sensitivity, and can be recovered under a certain condition after force activation, thereby achieving the effect of repeated activation.

In another preferred embodiment of the present invention (thirty-second network structure), the force-responsive cross-linked polymer is a carbene-metal coordination bond force-sensitive group, wherein the degree of cross-linking is above its gel point for conventional covalent cross-linking and above its gel point for force-sensitive group cross-linking. In the embodiment, the force-sensitive group of the carbene-metal coordination bond can generate carbene with catalytic action after force activation, and is convenient for realizing the effect of force-induced catalysis.

In another preferred embodiment of the present invention (thirty-third network structure), the force-responsive crosslinked polymer comprises a ligand-lanthanide metal ion complexing force-sensitive group, wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is above its gel point. In the embodiment, the ligand-lanthanide metal ion complexing force sensitive group is convenient to prepare, and by combining different ligand structures and lanthanide metals, the fluorescence color of the force sensitive group can be regulated, so that the polymer material with fluorescence change caused by force can be easily prepared.

In another preferred embodiment of the present invention (thirty-fourth network structure), the force-responsive cross-linked polymer comprises a hydrogen-bonding force-sensitive group, wherein the degree of cross-linking of ordinary covalent cross-linking is above its gel point and the degree of cross-linking of the force-sensitive group cross-linking is above its gel point. In the embodiment, the hydrogen bond acting force sensitive groups are various in types, and the effect of toughening caused by the polymer material is conveniently realized by adopting the hydrogen bond acting force sensitive groups.

In another preferred embodiment of the present invention (thirty-fifth network structure), the force-responsive crosslinked polymer comprises a homolytic force-sensitive group, wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the embodiment, the common covalent crosslinking action improves the mechanical property of the polymer, plays a certain role in protecting the force sensitive groups, and the homolytic force sensitive groups generate free radicals or change color after being activated by force, thereby being beneficial to realizing the force-induced crosslinking and the force-induced color change.

In another preferred embodiment of the present invention (thirty-sixth network structure), the force-responsive crosslinked polymer comprises a reversible free radical type force-sensitive group, wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the embodiment, the reversible free radical type force-sensitive group is a force-sensitive group with dynamic covalent property, which can provide the polymer with force-induced response performance, and the crosslinking degree of the force-sensitive group crosslinking is below the gel point thereof, so that the chain segment motion after the activation of the force-sensitive group is facilitated, and the stress response performance of the polymer can be recovered more quickly.

In another preferred embodiment of the present invention (thirty-seventh network structure), the force-responsive crosslinked polymer comprises a bisaryl cyclic ketone force-sensitive group, wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the embodiment, the biaryl cyclic ketone force sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after the force is activated.

In another preferred embodiment of the present invention (thirty-eighth network structure), the force-responsive crosslinked polymer comprises a bisaryl cyclopentenedione force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the embodiment, the diaryl cyclopentenedione force sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after force activation.

In another preferred embodiment of the present invention (thirty-ninth network structure), the force-responsive crosslinked polymer comprises a bisaryl chromene force sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force sensitive group crosslinks is below its gel point. In the embodiment, the biaryl chromene force sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after force activation.

In another preferred embodiment of the present invention (fortieth network structure), the force-responsive crosslinked polymer comprises a dicyanotetrarylethane force-sensitive moiety wherein the degree of crosslinking of conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive moiety crosslinks is below its gel point. In the embodiment, the dicyano tetraarylethane force sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after the force is activated.

In another preferred embodiment of the present invention (forty-first network structure), the force-responsive crosslinked polymer comprises a bisarylfuranone force-sensitive moiety, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive moiety crosslinks is below its gel point. In the embodiment, the biaryl furanone force sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after force activation.

In another preferred embodiment of the present invention (forty-second network structure), the force-responsive crosslinked polymer comprises an aryl pinacol force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the embodiment, the aryl pinacol force sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after force activation.

In another preferred embodiment of the present invention (the forty-third network structure), the force-responsive crosslinked polymer comprises a tetracyanoethane force-sensitive moiety wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive moiety crosslinks is below its gel point. In the embodiment, the tetracyanoethane force-sensitive group is convenient to prepare and strong in stress sensitivity, and the color can be obviously changed after force activation.

In another preferred embodiment of the present invention (forty-fourth network structure), the force-responsive crosslinked polymer contains a bifluorene force-sensitive group, wherein the degree of crosslinking of ordinary covalent crosslinks is above its gel point and the degree of crosslinking of force-sensitive group crosslinks is below its gel point. In the embodiment, the bifluorene is convenient to prepare and has strong stress sensitivity, and the color can be obviously changed after force activation.

In another preferred embodiment of the present invention (forty-fifth network structure), the force-responsive crosslinked polymer comprises a heterolytic force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the embodiment, the common covalent crosslinking action improves the mechanical property of the polymer, plays a certain role in protecting the force sensitive groups, and the heterolytic force sensitive groups are easy to initiate reaction after being activated by force, thereby being beneficial to realizing the force-induced crosslinking.

In another preferred embodiment of the present invention (forty-sixth network structure), the force-responsive crosslinked polymer comprises a triarylsulfonium salt series of force-sensitive groups, wherein the degree of crosslinking of conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive groups crosslinks is below its gel point. In the embodiment, the nitrogen oxide/nitrogen sulfur series force sensitive groups are convenient to prepare and strong in stress sensitivity, can generate free radicals with catalytic action after force activation, and can initiate double bond polymerization to form crosslinking.

In another preferred embodiment of the present invention (forty-seventh network structure), the force-responsive crosslinked polymer comprises a reverse cyclized force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the embodiment, the common covalent crosslinking action improves the mechanical property of the polymer, plays a certain role in protecting the force sensitive groups, and has simple reaction conditions and convenient preparation of the reverse cyclization force sensitive groups; unsaturated bonds are generated after the force sensitive groups are activated, and the method is convenient for realizing force-induced crosslinking.

In another preferred embodiment of the present invention (forty-eight network structures), the force-responsive crosslinked polymer comprises a cyclobutane reverse cyclization force-sensitive groups, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive groups crosslinks is below its gel point. In the embodiment, the cyclobutane reverse cyclization force sensitive groups are various in types, simple to prepare and strong in force sensitivity, and crosslinking can be conveniently realized by utilizing double bonds generated after the force sensitive groups are activated.

In another preferred embodiment of the present invention (forty-ninth network structure), the force-responsive crosslinked polymer comprises a dioxetane reverse cyclization force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the embodiment, the dioxetane reverse cyclization force-sensitive groups are various in types and adjustable in structure, and the force-induced luminescence property is conveniently realized.

In another preferred embodiment of the present invention (fifty-th network structure), the force-responsive crosslinked polymer comprises a DA-series reverse cyclization force-sensitive groups, wherein the degree of ordinary covalent crosslinking is above its gel point and the degree of force-sensitive group crosslinking is below its gel point. In the embodiment, the DA series reverse cyclization force sensitive groups are various in types, simple to prepare and strong in force sensitivity, double bonds generated after the force sensitive groups are activated are utilized to conveniently realize crosslinking, and the DA series reverse cyclization force sensitive groups can have the change of fluorescence wavelength by selecting a proper structure.

In another preferred embodiment of the present invention (fifty-first network structure), the force-responsive crosslinked polymer comprises a hetero DA series reverse cyclization force-sensitive group, wherein the degree of ordinary covalent crosslinking is above its gel point and the degree of force-sensitive group crosslinking is below its gel point. In the embodiment, the hetero DA series reverse cyclization force sensitive groups are various in types, simple to prepare and strong in force sensitivity, double bonds generated after the force sensitive groups are activated are utilized to conveniently realize crosslinking, and the hetero DA series reverse cyclization force sensitive groups can have the change of fluorescence wavelength by selecting a proper structure.

In another preferred embodiment of the present invention (fifty-second network structure), the force-responsive crosslinked polymer comprises a [4+4] cycloaddition reverse cyclization force-sensitive group, wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the present embodiment, the structure of the [4+4] cycloaddition reverse cyclization force-sensitive group generated after force activation is likely to change in fluorescence wavelength.

In another preferred embodiment of the present invention (fifty-third network structure), the force-responsive crosslinked polymer comprises an electrocyclic force-sensitive group, wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the embodiment, the common covalent crosslinking action improves the mechanical property of the polymer and plays a certain role in protecting the force sensitive groups, and the response of the electrocyclic force sensitive groups under the action of stress is generally accompanied with the change of color, so that the electrocyclic force sensitive groups can be conveniently used for preparing warning and indicating materials.

In another preferred embodiment of the present invention (fifty-fourth network structure), the force-responsive crosslinked polymer comprises a six-membered ring series of force-sensitive groups, wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive groups crosslinks is below its gel point. In the present embodiment, six-membered ring series force sensitive groups are various in kind and strong in force sensitivity, and different six-membered ring force sensitive groups have different force activation effects and can be selected and used as needed.

In another preferred embodiment of the present invention (fifty-fifth network structure), the force-responsive crosslinked polymer comprises a spiropyran force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the present embodiment, the spiropyran force-sensitive groups have strong force sensitivity, and can be selectively used as needed by controlling the kind and number of substituents to have different force-activating effects.

In another preferred embodiment of the present invention (fifty-sixth network structure), the force-responsive crosslinked polymer comprises a spirothiopyran force-sensitive group wherein the degree of ordinary covalent crosslinking is above its gel point and the degree of force-sensitive group crosslinking is below its gel point. In the embodiment, the spirothiopyran force-sensitive groups have strong force sensitivity, and can have different force activation effects by controlling the types and the number of the substituent groups, and can be selected and used according to requirements; and the sulfydryl generated after the force sensitive groups are activated is easy to react, so that the force-induced crosslinking is conveniently realized.

In another preferred embodiment of the present invention (fifty-seventh network structure), the force-responsive crosslinked polymer comprises a spirooxazine force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the present embodiment, the spirooxazine force sensitive group has strong force sensitivity, and can have different force activation effects by controlling the type and number of the substituents, and can be selectively used as required.

In another preferred embodiment of the present invention (fifty-eighth network structure), the force-responsive crosslinked polymer comprises a five-membered ring series of force-sensitive groups, wherein the degree of crosslinking of the common covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive groups crosslinks is below its gel point. In the embodiment, the five-membered ring series force sensitive groups are various in types and strong in force sensitivity, and different five-membered ring force sensitive groups have different force activation effects and can be selected for use according to requirements.

In another preferred embodiment of the present invention (fifty-ninth network structure), the force-responsive crosslinked polymer contains a rhodamine force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the present embodiment, the rhodamine group has strong force sensitivity, and can have different force activation effects by controlling the type and number of the substituents, and can be selectively used as needed.

In another preferred embodiment of the present invention (sixty network structures), the force-responsive crosslinked polymer contains a bend-activating force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the embodiment, the common covalent crosslinking action improves the mechanical property of the polymer and plays a certain role in protecting the force sensitive groups, and the bending activation force sensitive groups can release small molecules and change the fluorescence wavelength under the action of stress, so that the polymer material is convenient to be used as a polymer material for special application.

In another preferred embodiment of the present invention (sixty-first network structure), the force-responsive crosslinked polymer comprises a force-sensitive group of an adduct series of anthracene and a Triazolinedione (TAD), wherein the degree of crosslinking of conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the embodiment, the adduct series force-sensitive groups of anthracene and triazoline diketone (TAD) can release small molecules and change the fluorescence wavelength under the action of stress, and are convenient to be used as polymer materials for special applications.

In another preferred embodiment of the present invention (sixty-second network structure), the force-responsive cross-linked polymer contains a force-sensitive group of the dinitroso series wherein the degree of cross-linking for ordinary covalent cross-linking is above its gel point and the degree of cross-linking for the force-sensitive group cross-linking is below its gel point. In the embodiment, the cross-linked structure enables the mechanical property of the polymer to be improved to a certain extent, and the force sensitive groups in the dinitroso series can realize the stress response effect of releasing small molecules under the stress action, so that the polymer material can be conveniently used as a polymer material for special application.

In another preferred embodiment of the present invention (sixty-third network structure), the force-responsive cross-linked polymer is a non-covalent force-sensitive group, wherein the degree of cross-linking of ordinary covalent cross-linking is above its gel point and the degree of cross-linking of the force-sensitive group cross-linking is below its gel point. In the embodiment, the common covalent crosslinking action improves the mechanical property of the polymer and plays a certain role in protecting the force sensitive groups, the non-covalent force sensitive groups are various in types, and the polymer material with force-induced fluorescence change and force-induced catalysis is easy to prepare.

In another preferred embodiment of the present invention (sixty-four network structure), the force-responsive cross-linked polymer is a supramolecular complex force-sensitive group, wherein the degree of cross-linking of ordinary covalent cross-linking is above its gel point and the degree of cross-linking of the force-sensitive group cross-linking is below its gel point. In this embodiment, the supramolecular complex force sensitive groups are of various types and have high stress sensitivity, and can be recovered under a certain condition after force activation, thereby achieving the effect of repeated activation.

In another preferred embodiment of the present invention (sixty-five network structures), the force-responsive crosslinked polymer is a carbene-metal coordination bond force-sensitive group, wherein the degree of crosslinking is above its gel point for conventional covalent crosslinking and below its gel point for force-sensitive group crosslinking. In the embodiment, the force-sensitive group of the carbene-metal coordination bond can generate carbene with catalytic action after force activation, and is convenient for realizing the effect of force-induced catalysis.

In another preferred embodiment of the present invention (sixty-sixth network structure), the force-responsive crosslinked polymer comprises a ligand-lanthanide metal ion complexing force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the embodiment, the ligand-lanthanide metal ion complexing force sensitive group is convenient to prepare, and by combining different ligand structures and lanthanide metals, the fluorescence color of the force sensitive group can be regulated, so that the polymer material with fluorescence change caused by force can be easily prepared.

In another preferred embodiment of the present invention (sixty-seventh network structure), the force-responsive crosslinked polymer comprises a hydrogen bonding force-sensitive group, wherein the degree of crosslinking of the conventional covalent crosslinks is above its gel point and the degree of crosslinking of the force-sensitive group crosslinks is below its gel point. In the embodiment, the hydrogen bond acting force sensitive groups are various in types, and the effect of toughening caused by the polymer material is conveniently realized by adopting the hydrogen bond acting force sensitive groups.

Can be linked to form a ring, on different atoms

Can be linked to form a ring, on different atoms

Can be linked to form a ring, on different atoms

Can be linked to form a ring, on different atoms

wherein X is selected from thiogenA sulfur atom, a selenium atom, a tellurium atom, C-R, N-R, preferably from a sulfur atom; y is C-R; each R is independently any suitable atom, substituent, substituted polymer chain;

Can be linked to form a ring, on different atoms

wherein X is selected from the group consisting of a sulfur atom, a selenium atom, a tellurium atom, C-R, N-R, preferably from a sulfur atom; y is C-R; each R is independently any suitable atom, substituent,A substituted polymer chain;

Can be linked to form a ring, on different atoms

wherein, X, X₁Selected from oxygen atoms; y is C-R; y is₁Selected from C-R, nitrogen atom; each R is independently any suitable atom, substituent, substituted polymer chain; z₁Is selected from C- (R)₂Nitrogen atom, sulfur atom, oxygen atom, tellurium atom, preferably C- (R)₂A nitrogen atom; z₂Selected from sulfur atom, oxygen atom, selenium atom,Tellurium atom, C- (R)₂Nitrogen atom, preferably C- (R)₂A nitrogen atom; when Z is₁Or Z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂When connected to it

The number is 0;

Can be linked to form a ring, on different atoms

The number is 0;

an aromatic ring having an arbitrary number of elements; n is the total number of hydrogen atoms, substituent atoms, substituents, and substituent polymer chains bonded to the atoms constituting the ring, and is 0, 1, or an integer greater than 1; the aromatic ring can be any aromatic ring or aromatic heterocyclic ring, and the ring-forming atoms are respectively and independently carbon atoms or hetero atoms; the heteroatom can be selected from nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom and boron atom; hydrogen atoms of aromatic rings forming ring atomsThe substituents may be substituted or unsubstituted; it can be a single ring structure, a multi-ring structure, a spiro structure, a fused ring structure, a bridged ring structure, or a nested ring structure.

Can be linked to form a ring, on different atoms

wherein, X, X₁Is selected fromAn oxygen atom; y is C-R; each R is independently any suitable atom, substituent, substituted polymer chain; z₁Is selected from C- (R)₂Nitrogen atom, sulfur atom, oxygen atom, tellurium atom, preferably C- (R)₂A nitrogen atom; z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂Nitrogen atom, preferably C- (R)₂A nitrogen atom; when Z is₁Or Z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂When connected to it

The number is 0;

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. In the same structural formulaIn the same position, groups or structures having the same symbols are independent of each other, and may be the same or different.

The number is 0;

an aromatic ring having an arbitrary number of elements; n is the total number of hydrogen atoms, substituent atoms, substituents, and substituent polymer chains bonded to the atoms constituting the ring, and is 0, 1, or an integer greater than 1; said aromatic compoundA ring which can be any aromatic ring or aromatic heterocyclic ring, and ring-forming atoms are each independently a carbon atom or a heteroatom; the heteroatom can be selected from nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom and boron atom; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; it can be a single ring structure, a multi-ring structure, a spiro structure, a fused ring structure, a bridged ring structure, or a nested ring structure.

Can be linked to form a ring, on different atoms

The present invention may be implemented in other embodiments, and those skilled in the art can reasonably realize the present invention based on the logic and context thereof. Different chemical structures of the cross-linked network chain segments have different mechanical properties, heat resistance, cold resistance, weather resistance, hydrolytic stability and the like, for example, carbon chains and carbon hybrid chains have good mechanical properties, and the glass transition temperature is adjustable in a large range; the polyorganosiloxane has excellent heat resistance, cold resistance and weather resistance, but has weaker mechanical property; different topological structures have different mechanical properties, and different force sensitive groups have different force responsiveness; the crosslinked networks constructed from polymer segments of at least two different types of chemical structures are versatile in structure and performance, and the crosslinked networks constructed from polymer segments of a single chemical structure have particular applicability, and thus can be made to achieve desirable structures and performance in accordance with the teachings of the present invention.

In the invention, the effects of stress induction, damage warning and the like can be directly performed except for the effects of mechanochromism, mechanochromatism change, mechanoluminescence and the like, and the effects of ion release, mechanocatalysis, polymerization initiated by a force-induced free radical, force-induced crosslinking, force-induced self-repairing, force-induced grafting and the like can also be realized. For example, when a force-sensitive element/group containing dynamic covalent features and/or supramolecular action is used, the activated force not only has certain self-repairing performance, but also has the functions or effects of shape memory, plasticity, formation of new cross-linking and the like, and has abundant performance and application; after force activation, the force sensitive group containing the spirothiopyran structure can be subjected to grafting, crosslinking and other reactions with a reactive group contained on a polymer or a reactive group generated by a precursor of the spirothiopyran structure under a specific condition, such as maleimide or a precursor of the spirothiopyran structure, such as a pyrolytic DA structure, so that the spirothiopyran structure has functions of functionalization, self-repairing by force, crosslinking enhancement by force and the like; the specific structure of the force sensitive group through the homolytic mechanism can initiate free radical polymerization or crosslinking after being activated, so that the structure of a polymer system is changed; the supermolecular complex structure, particularly a coordination structure, can be activated to generate a catalyst, catalyze reactions such as organic reaction, polymerization or crosslinking, enhance fluorescence, provide self-repairing effect, generate force-induced enhancement and the like, for example, force-induced generation of Grubb's catalyst, and catalyze olefin metathesis reaction to generate polymerization or crosslinking; after force-induced activation, force-sensitive groups of various cyclobutane structures can generate photoinduced ring closing reaction, free radical polymerization/crosslinking reaction, click chemical reaction and the like, so that the functions of self-repairing, force-induced enhancement and the like are achieved; the specific force sensitive group containing epoxy group structure is activated to generate a ylide structure, and then reacts with cyano group to be functionalized, grafted or crosslinked, so as to achieve the effect of modification or crosslinking. The properties obtainable by the present invention are far more than these, and the properties obtainable are well understood by the skilled person on the basis of the force sensitive groups and polymer structures proposed by the present invention.

In embodiments of the present invention, the small molecule and/or polymer segment used to link the force sensitive group may have any suitable topology, including but not limited to linear structures, branched structures (including but not limited to star, H, dendritic, comb, hyperbranched), cyclic structures (including but not limited to monocyclic, polycyclic, bridged, nested, annulated, grommet), two-dimensional/three-dimensional cluster structures, and combinations of two or any of the foregoing, preferably linear and branched structures.

In the embodiment of the present invention, the polymer chain segment and/or the small molecule linker for linking the force-sensitive group can be directly selected from commercial raw materials, or can be synthesized by any suitable chemical reaction or polymerization method.

In the present invention, when the polymer is prepared, according to the actual requirements of the preparation process, the forming process, the use performance requirements and the like, the additives, the fillers and the swelling agents can be selectively added or used as the formulation components of the polymer, which can improve the material processing performance, improve the product quality and yield, reduce the product cost or endow the product with certain specific application performance, but the additives or the used substances are not necessary.

Wherein, the auxiliary agent can include but is not limited to one or a combination of several of the following, such as synthesis auxiliary agents, including catalysts and initiators; stabilizing aids including antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants; the auxiliary agent for improving the mechanical property comprises a toughening agent and a coupling agent; the auxiliary agents for improving the processing performance comprise a solvent, a lubricant, a release agent, a plasticizer, a thickening agent, a thixotropic agent and a flatting agent; the color light changing auxiliary agent comprises a coloring agent, a fluorescent whitening agent and a delustering agent; other auxiliary agents include antistatic agents, sterilization and mildew proofing agents, foaming agents, foam stabilizers, nucleating agents, rheological agents and the like.

In the present invention, the filler includes, but is not limited to, inorganic non-metallic fillers, organic fillers, and organometallic compound fillers.

The inorganic non-metal filler includes, but is not limited to, any one or more of the following: calcium carbonate, china clay, barium sulfate, calcium sulfate and calcium sulfite, talc, white carbon, quartz, mica powder, clay, asbestos fiber, orthoclase, chalk, limestone, barite powder, gypsum, silica, graphite, calcium sulfate and calcium sulfite, calcium carbonate, calcium sulfate, talc, silica, graphite, calcium carbonate, calcium sulfate,Carbon black, graphene oxide, fullerene, carbon nano tube, black phosphorus nanosheet, molybdenum disulfide, diatomite, red mud, wollastonite, silicon-aluminum carbon black, aluminum hydroxide, magnesium hydroxide and nano Fe₃O₄Particulate, nano gamma-Fe₂O₃Particulate, nano MgFe₂O₄Particulate, nano-MnFe₂O₄Granular, nano CoFe₂O₄Particles, quantum dots (including but not limited to silicon quantum dots, germanium quantum dots, cadmium sulfide quantum dots, cadmium selenide quantum dots, cadmium telluride quantum dots, zinc selenide quantum dots, lead sulfide quantum dots, lead selenide quantum dots, indium phosphide quantum dots, and indium arsenide quantum dots), upconversion crystal particles (including but not limited to NaYF)₄:Er、CaF₂:Er、Gd₂(MoO₄)₃:Er、Y₂O₃:Er、Gd₂O₂S:Er、 BaY₂F₈:Er、LiNbO₃:Er，Yb，Ln、Gd₂O₂:Er，Yb、Y₃Al₅O₁₂:Er，Yb、TiO₂:Er，Yb、YF₃:Er，Yb、Lu₂O₃:Yb，Tm、 NaYF₄:Er，Yb、LaCl₃:Pr、NaGdF₄:Yb，Tm@NaGdF₄Core-shell nanostructure of Ln, NaYF₄:Yb，Tm、Y2BaZnO₅:Yb，Ho、NaYF₄:Yb，Er@NaYF₄Core-shell nanostructures of Yb, Tm, NaYF₄:Yb，Tm@NaGdF₄Core-shell nanostructure of Yb), oil shale powder, expanded perlite powder, aluminum nitride powder, boron nitride powder, vermiculite, iron mud, white mud, alkali mud, boron mud, glass beads, resin beads, glass powder, glass fibers, carbon fibers, quartz fibers, carbon-core boron fibers, titanium diboride fibers, calcium titanate fibers, silicon carbide fibers, ceramic fibers, whiskers and the like. In one embodiment of the present invention, inorganic non-metallic fillers having electrical conductivity, including but not limited to graphite, carbon black, graphene, carbon nanotubes, carbon fibers, are preferred, which facilitate obtaining a composite material having electrical conductivity and/or electrothermal function. In another embodiment of the present invention, it is preferable to use a non-metallic filler having a heat generating function by infrared and/or near infrared lightIncluding but not limited to graphene, graphene oxide, carbon nanotubes, black phosphorus nanoplatelets, nano-Fe₃O₄The composite material which can be heated by infrared and/or near infrared light is conveniently obtained. In another embodiment of the present invention, inorganic non-metallic fillers with thermal conductivity, including but not limited to graphite, graphene, carbon nanotubes, aluminum nitride, boron nitride, silicon carbide, are preferred, which facilitate obtaining composite materials with thermal conductivity.

The metal filler includes metal compounds, including but not limited to any one or any several of the following: metal powders, fibers including but not limited to powders, fibers of copper, silver, nickel, iron, gold, and the like, and alloys thereof; nano-metal particles including, but not limited to, nano-gold particles, nano-silver particles, nano-palladium particles, nano-iron particles, nano-cobalt particles, nano-nickel particles, nano-CoPt₃Particles, nano FePt particles, nano FePd particles, nickel-iron bimetal magnetic nanoparticles and other nano metal particles capable of heating under at least one of infrared, near infrared, ultraviolet and electromagnetic action; liquid metals including, but not limited to, mercury, gallium indium liquid alloys, gallium indium tin liquid alloys, other gallium based liquid metal alloys. In one embodiment of the present invention, fillers that can be heated electromagnetically and/or near-infrared, including but not limited to nanogold, nanosilver, and nanopalladium, are preferred for remote heating. In another embodiment of the present invention, liquid metal fillers are preferred, which can enhance the thermal and electrical conductivity of the flexible substrate while maintaining the flexibility and ductility of the substrate.

The organic filler comprises any one or more of ① natural organic filler, ② synthetic resin filler, ③ synthetic rubber filler, ④ synthetic fiber filler, ⑤ foamable polymer particles, ⑥ conjugated polymer and ⑦ organic functional dye/pigment, and the organic filler with the properties of ultraviolet absorption, fluorescence, luminescence, photo-thermal property and the like has important significance to the invention and can fully utilize the properties to obtain multifunctionality.

The organic metal compound filler contains a metal organic complex component, wherein a metal atom is directly connected with a carbon atom to form a bond (including a coordination bond, a sigma bond and the like), and the metal organic complex component can be a small molecule or a large molecule and can be in an amorphous or crystal structure. Metal organic compounds tend to have excellent properties including uv absorption, fluorescence, luminescence, magnetism, catalysis, photo-thermal, electromagnetic heat, and the like.

Wherein, the type of the filler is not limited, and is mainly determined according to the required material performance, and calcium carbonate, clay, carbon black, graphene, (hollow) glass microsphere and nano Fe are preferred₃O₄Particles, nano-silica, quantum dots, up-conversion metal particles, foamed microspheres, foamable particles, glass fibers, carbon fibers, metal powder, nano-metal particles, synthetic rubber, synthetic fibers, synthetic resin, resin microbeads, organometallic compounds, organic materials having photo-thermal properties. The amount of the filler used is not particularly limited, but is generally 1 to 30% by weight. In the embodiment of the invention, the filler can be selectively modified and then dispersed and compounded or directly connected into a polymer chain, so that the dispersibility, the compatibility, the filling amount and the like can be effectively improved, and the filler has important significance particularly on the action of photo-thermal, electromagnetic heat and the like.

Wherein, the swelling agent can include but is not limited to water, organic solvent, ionic liquid, oligomer and plasticizer. The oligomers can also be regarded as plasticizers.

Wherein the ionic liquid in the swelling agent is generally composed of an organic cation and an inorganic anion, and the cation is selected from, by way of example, but not limited to, alkyl quaternary ammonium ions, alkyl quaternary phosphine ions, 1, 3-dialkyl-substituted imidazolium ions, N-alkyl-substituted pyridinium ions, and the like; the anion is selected from the group including but not limited to halogen, tetrafluoroborate, hexafluorophosphate, and also CF₃SO₃ ^-、(CF3SO₂)₂N^-、C₃F₇COO^-、 C₄F₉SO₃ ^-、CF₃COO^-、(CF₃SO₂)₃C^-、(C₂F₅SO₂)₃C^-、(C₂F₅SO₂)₂N^-、SbF₆ ^-、AsF₆ ^-And the like. In the ionic liquid used in the present invention, the cation is preferably an imidazolium cation, and the anion is preferably a hexafluorophosphate ion or a tetrafluoroborate ion.

In the embodiment of the invention, the form of the force-responsive polymer can be common solid, gel (including hydrogel, organogel, oligomer swelling gel, plasticizer swelling gel and ionic liquid swelling gel), elastomer, foam material and the like, wherein the content of soluble small molecular weight components in the common solid and the foam material is generally not higher than 10 wt%, and the content of small molecular weight components in the gel is generally not lower than 50 wt%. The shape and volume of the common solid are fixed, the common solid has better mechanical strength and can not be restrained by an organic swelling agent or water. Elastomers have the general properties of ordinary solids, but at the same time have better elasticity and are softer. The gel is generally higher in softness and lower in solid content, and the swelling agent has the functions of conduction, conveying and the like and has outstanding advantages. The foam material has the advantages of low density, lightness and high specific strength, can overcome the problems of brittleness of part of common solids and low mechanical strength of organogel, and has good elasticity and soft and comfortable characteristics. Materials of different morphologies may have suitable uses in different fields.

In an embodiment of the present invention, the polymer gel may be obtained by crosslinking in a swelling agent (including one or a combination of water, an organic solvent, an oligomer, a plasticizer, and an ionic liquid), or may be obtained by swelling with a swelling agent after the polymer is prepared. Of course, the present invention is not limited to this, and those skilled in the art can implement the present invention reasonably and effectively according to the logic and context of the present invention.

In the preparation process of the polymer, three methods, namely a mechanical foaming method, a physical foaming method and a chemical foaming method, are mainly adopted for foaming.

The mechanical foaming method is that a large amount of air or other gases are introduced into emulsion, suspension or solution of polymer by means of strong stirring in the preparation process of the polymer to form uniform foam, and then the uniform foam is formed into foam material through physical or chemical change. Air can be introduced and an emulsifier or surfactant can be added to shorten the molding cycle.

Wherein, the physical foaming method is to realize the foaming of the polymer by using the physical principle in the preparation process of the polymer, and the method comprises the following steps: (1) inert gas foaming, i.e. by pressing inert gas into molten polymer or pasty material under pressure, then raising the temperature under reduced pressure to expand the dissolved gas and foam; (2) evaporating, gasifying and foaming low-boiling-point liquid, namely pressing the low-boiling-point liquid into the polymer or dissolving the liquid into the polymer (particles) under certain pressure and temperature conditions, heating and softening the polymer, and evaporating and gasifying the liquid to foam; (3) dissolving out method, i.e. soaking liquid medium into polymer to dissolve out solid matter added in advance to make polymer have lots of pores and be foamed, for example, mixing soluble matter salt with polymer, etc. first, after forming into product, placing the product in water to make repeated treatment, dissolving out soluble matter to obtain open-cell foamed product; (4) the hollow microsphere method is that hollow microspheres are added into the material and then compounded to form closed cell foamed polymer; (5) a filling expandable particle method of mixing filling expandable particles and expanding the expandable particles during molding or mixing to actively foam the polymer material; among them, it is preferable to carry out foaming by a method of dissolving an inert gas and a low boiling point liquid in the polymer. The physical foaming method has the advantages of low toxicity in operation, low cost of foaming raw materials, no residue of foaming agent and the like. In addition, the preparation method can also adopt a freeze drying method.

The chemical foaming method is a method for generating gas and foaming along with chemical reaction in the process of foaming polymer, and includes, but is not limited to, the following two methods: (1) the thermal decomposition type foaming method is a method of foaming by using a gas released by decomposition of a chemical foaming agent after heating. And (2) a foaming method in which the polymer components interact with each other to generate a gas, that is, a chemical reaction between two or more components in a foaming system is used to generate an inert gas (such as carbon dioxide or nitrogen) to expand the polymer and thus foam the polymer. In order to control the polymerization reaction and the foaming reaction to be carried out in balance in the foaming process and ensure that the product has better quality, a small amount of catalyst and foam stabilizer (or surfactant) are generally added. Among these, foaming is preferably performed by a method of adding a chemical foaming agent to a polymer.

In the preparation process of the polymer, a person skilled in the art can select a proper foaming method and a foam material forming method to prepare the foam material according to the actual preparation situation and the target polymer performance.

In an embodiment of the present invention, the structure of the polymer foam material relates to three structures of an open-cell structure, a closed-cell structure, and a half-open and half-closed structure. In the open pore structure, the cells are communicated with each other or completely communicated with each other, gas or liquid can pass through the single dimension or the three dimensions, and the cell diameter is different from 0.01 to 3 mm. The closed cell structure has an independent cell structure, the inner cells are separated from each other by a wall membrane, most of the inner cells are not communicated with each other, and the cell diameters are different from 0.01 mm to 3 mm. The contained cells have a structure which is not communicated with each other, and the structure is a semi-open cell structure. For a foam structure which has been formed into closed cells, it can also be made into an open cell structure by mechanical pressing or chemical methods, and the skilled person can select them according to the actual needs.

In embodiments of the present invention, polymer foams are classified by their hardness into three categories, soft, hard and semi-hard: (1) a flexible foam having a modulus of elasticity of less than 70MPa at 23 ℃ and 50% relative humidity; (2) a rigid foam having an elastic modulus greater than 700MPa at 23 ℃ and 50% relative humidity; (3) semi-rigid (or semi-flexible) foams, foams between the two above categories, having a modulus of elasticity between 70MPa and 700 MPa.

In embodiments of the present invention, the polymer foam materials may be further classified by their density into low-foaming, medium-foaming and high-foaming. Low-foaming foams having a density of more than 0.4g/cm³The foaming multiplying power is less than 1.5; the medium-foamed foam material has a density of 0.1-0.4 g/cm³The foaming ratio is 1.5-9; and a high-foaming foam material having a density of less than 0.1g/cm³The expansion ratio is greater than 9.

Those skilled in the art can select suitable foaming method and forming method to prepare the polymer foam product according to actual conditions and requirements.

The force-induced response cross-linked polymer in the invention contains a force sensitive group which can be selected abundantly, and can obtain different stress responsiveness; through proper force sensitive group selection and network structure design, the obtained polymer material can be widely applied to the fields of ion detection materials, stress detection materials, sensor materials, biological analysis materials, toy materials, elastic materials, energy storage device materials and the like.

For example, the adhesive with a damage warning function can be prepared by utilizing the force-induced color change of the force sensitive groups, and the adhesive is applied to various occasions and has the functions of reducing damage and prolonging the service life of an adhesive material, so that the use safety is improved; the material can also be used for preparing polymer plugging glue with excellent mechanical properties, sealing plugs, sealing rings and other sealing elements, is widely applied to the aspects of electronic appliances, pipeline sealing and the like, reflects the current stress condition of the material through the change of the color of the material, and plays a role in early warning; based on the stress response of the force sensitive groups, a scratch-resistant coating with a force-induced enhancement function can be designed and prepared, the scratched part can be displayed when the coating is scratched, the coating can be repaired and/or force-induced crosslinking enhancement is generated before damage, the maintenance is convenient, the service life of the coating is prolonged, and the long-acting anticorrosion protection of a matrix material is realized; through proper component selection and formula design, a polymer gasket or a polymer plate with a force-induced response function can be prepared, and a force-induced response material can accurately reflect a damaged area, is convenient for human participation in a repair process, enables the repair of the material to be more perfect, and also enables the material to show great application potential in the fields of military industry, aerospace, electronics, bionics and the like.

For another example, by introducing a suitable force-sensitive group, the polymer material can exhibit a suitable force-induced response effect under the action of an external force, so that a polymer film, a fiber or a plate with excellent performance can be obtained; the response condition of the polymer material can be greatly widened through the force-induced responsiveness of the force sensitive group, so that the application range and the field of the polymer material are wider; the polymer material can also be made into toys and fitness materials with stress enhancement and stress discoloration.

The force-responsive crosslinked polymers of the present invention are further described below in connection with certain embodiments. The specific examples are intended to illustrate the present invention in further detail, and are not intended to limit the scope of the present invention.

Example 1

0.3 molar equivalent of the compound (a), 0.3 molar equivalent of pentaerythritol, 2 molar equivalent of carboxyl terminated polytetrahydrofuran having a molecular weight of 5000, methylene chloride as a solvent, 0.01 molar equivalent of N, N-diisopropylcarbodiimide and 0.01 molar equivalent of diphenyl-4-phenylthiophenylthiophenylsulfonium salt were added, the reaction system was stirred at room temperature for 24 hours, the solvent was removed, the reaction product was poured into a specific mold, and cooled to obtain a polymer film. In the embodiment, the polymer film prepared in the method changes the non-fluorescence of the polymer under the ultraviolet light into the blue fluorescence under the action of the tensile force, and the property can be used as a stress warning material.

Example 2

Weighing 0.3 molar equivalent of the compound (a), 0.1 molar equivalent of the aluminum-containing catalyst compound (c) and 1 molar equivalent of racemic lactide, putting the mixture into a reactor, taking toluene as a solvent, heating to 70 ℃ under a nitrogen atmosphere, stirring for reaction for 4 hours, then cooling in ice water for 10 minutes, then cooling in ice for 10 minutes, then adding 0.3 molar equivalent of glycerol, heating at 70 ℃ for 120 hours again, precipitating the obtained polymer in cold petroleum ether, and swelling the filtered product in an ethanol solvent for 24 hours to prepare the polymer organogel. The force sensitive groups of the polymer can open rings under the action of stress, so that the toughness of the organogel is improved, the organogel can be self-degraded under certain conditions, and the organogel can be used as a drug wrapping material.

Example 3

Dissolving 50 molar equivalent polyacrylic acid (molecular weight is 3000) in a reactor in sufficient acetone, bubbling for deoxygenation, adding 5 molar equivalent compound (a) and 5 molar equivalent polytetrahydrofuran (molecular weight is 500) after uniformly stirring, adding 5 molar equivalent N-hydroxysuccinimide and 5 molar equivalent N, N' -dicyclohexylcarbodiimide after uniformly dissolving and mixing, then continuing stirring for 24 hours at room temperature, removing the solvent, and swelling the polymer in an aqueous solution containing litmus reagent to prepare the polymer hydrogel. In the process of stretching or compressing the polymer, the color of the polymer gradually changes from blue to red, because sulfonic acid molecules are formed after the force sensitive groups are stressed to react with litmus reagents, the litmus reagents turn red, and the polymer hydrogel can be used as a stress detection material by utilizing the stress discoloration property.

Example 4

Taking 1 molar equivalent of modified polynorbornene (a) (taking N-allyl maleimide and cyclopentadiene as raw materials, preparing maleimide modified norbornene through Diels-Alder reaction, preparing carboxyl modified norbornene through Diels-Alder reaction of 1-butenoic acid and cyclopentadiene, preparing final products through addition polymerization reaction of the maleimide modified norbornene, the carboxyl modified norbornene and the norbornene with metallocene catalyst/methylaluminoxane as a catalytic system), 0.3 molar equivalent of compound (b) and 0.3 molar equivalent of polyethylene glycol (molecular weight 200) in a reactor, taking methylene dichloride as a solvent, adding 5 molar equivalent of N-hydroxysuccinimide, 5 molar equivalent of N, N' -dicyclohexylcarbodiimide and 2 wt% of ferroferric oxide nanoparticles after dissolving uniformly, then stirring is continued for 24 hours at room temperature, and finally the polymer elastomer is obtained, and the sample has good elasticity and toughness and can be extended in a larger range. The polymer is stretched and kept under stress for a period of time, the shape of the polymer is fixed, the stress is released after heating or continuous stretching, the polymer can recover the original shape, and the shape memory effect is realized; and the material has the effect of a magnetic field, and the shape of the material can be controlled by the magnetic field. The polymer can be used as a magnetically induced shape memory material.

Example 5

N-hydroxyethyl maleimide and polyacrylic acid (molecular weight 2000) are used as raw materials to prepare the maleimide modified polyacrylic acid. 1 molar equivalent of benzocyclobutene compound (a), 10 molar equivalent of maleimide modified polyacrylic acid and 1 molar equivalent of polyethylene glycol (molecular weight 300), toluene is used as a solvent, 0.05 molar equivalent of N, N-isopropyl carbodiimide and 0.05 molar equivalent of diphenyl-4-thiophenyl phenyl sulfonium salt are added, 1 wt% of talcum powder and 1 wt% of nano silver are added, and after ultrasonic dispersion, the reaction system is stirred and reacts for 24 hours at normal temperature to prepare the colloidal polymer. The polymer has certain adhesiveness, and the viscosity of the polymer gradually rises along with the extension of stirring time during stirring, so that the ring-opened cyclobutene and the maleimide generate cyclization reaction to generate a phenomenon of force-induced crosslinking. The polymer can be used as a bonding agent, and the bonding effect is better under the action of severe shear stress.

Example 6

0.3 molar equivalent of the force sensitive compound (a), 1 molar equivalent of the carboxyl modified polyether ketone compound (b) and 0.3 molar equivalent of polytetrahydrofuran (molecular weight 300) are weighed, DMF is taken as a solvent, after uniform stirring, 0.01 molar equivalent of N, N-isopropyl carbodiimide and 0.01 molar equivalent of diphenyl-4-thiophenyl phenyl sulfonium salt are added, and stirring reaction is carried out at room temperature for 24 hours. After the reaction is finished, the solvent is removed, and a polymer solid powder is prepared. When the polymer powder is ground, the fluorescence of the polymer powder under ultraviolet light is gradually obvious, blue fluorescence is emitted, and the polymer powder can be used as an anti-counterfeiting verification material.

Example 7

Weighing 1 molar equivalent of polymer (b) (with the molecular weight of 5000) in a dry clean flask, heating to 100 ℃, introducing nitrogen to remove water and remove oxygen for 1h, adding 0.01 molar equivalent of platinum dichloride, then adding 0.4 molar equivalent of polyethylene glycol (with the molecular weight of 500), 0.4 molar equivalent of spiropyran compound (a), 0.2 molar equivalent of olefin double-ended polyethylene glycol, 5 wt% of plant fiber, 5 wt% of barium sulfate and 5 wt% of talcum powder, continuing to react for 1h, after the reaction is finished, putting a polymer sample in a proper mold, drying for 24h in a vacuum oven, and then cooling to room temperature to finally obtain the high-elasticity polysiloxane-polyethylene glycol elastomer. Compared with the traditional polysiloxane material, the polymer prepared by the embodiment has the advantages that in the stretching process, the color is changed from transparent to purple along with the increase of the elongation, the larger the stress is, the darker the color is, the stress condition of the material can be reflected through the change of the color depth, and the management and the maintenance are convenient; after the stress is released, the color of the polymer is recovered to the original state and can be repeatedly used; and the product is stable to ultraviolet light and is not easy to change color under illumination.

Example 8

The ester group-terminated polymer (a) is prepared by using polyethylene glycol (molecular weight 1000), 2- ((allyloxy) methyl) oxirane, N-hydroxy maleimide and acetyl chloride as raw materials and potassium naphthalene as a catalyst.

Taking 5 molar equivalents of polymer (a), 1 molar equivalent of compound (b), 1 molar equivalent of ethanedithiol, 2 wt% of antioxidant 1010 and 0.1 molar equivalent of catalyst 2, 2-dimethoxy-2-phenylacetophenone (DMPA), putting the mixture into a reactor, using methanol/water solution as a solvent, carrying out bubbling deoxygenation by using nitrogen, putting the mixture under an ultraviolet lamp of 365nm for irradiation for 3 hours, and cooling after the reaction is finished to prepare the polymer hydrogel. In this example, the color of the prepared polymer hydrogel changes to orange yellow under the action of stress, and the color is darker as the stress is larger; meanwhile, when the polymer is stretched, the stress-strain curve fluctuates after the color of the polymer changes, because the mercapto group formed by ring opening of the spiropyran reacts with the maleimide in the polymer to form crosslinking, the effect of force-induced crosslinking is achieved, and the mechanical property of the polymer is improved. The polymer can be used as a stress protection auxiliary material, the stress can be fed back, the mechanical property of the polymer can be automatically enhanced when the stress is overlarge, and the safety is improved.

Example 9

1 molar equivalent of thiophene spirooxazine force-sensitive group compound (a), 5 molar equivalent of polyvinyl alcohol with molecular weight of 3000 and 1 molar equivalent of 1, 10-sebacic acid are added into dichloromethane which is used as a solvent, 0.05 molar equivalent of N, N-isopropyl carbodiimide and 0.05 molar equivalent of diphenyl-4-thiophenyl phenyl sulfonium salt are added, a reaction system is stirred and reacted for 24 hours at normal temperature, and the solvent is removed, so that a powdery polymer is prepared. In this example, the obtained polymer powder, which gradually changed its fluorescent color under ultraviolet light to green when ground, was used as an information storage material.

Example 9

50 molar equivalents of poly (acrylic acid-methyl acrylate) (molecular weight 2000) is dissolved in sufficient acetone in a reactor, the mixture is bubbled for deoxygenation, after the mixture is uniformly stirred, 5 molar equivalents of the compound (a), 5 molar equivalents of polytetrahydrofuran (molecular weight 300) and 1 molar equivalent of trifluoroacetic acid are added, after the mixture is uniformly dissolved and mixed, 5 molar equivalents of N-hydroxysuccinimide, 5 molar equivalents of N, N' -dicyclohexylcarbodiimide and 1 wt% of nano silver particles are added, then the mixture is continuously stirred for 24 hours at room temperature, and after the solvent is removed, the polymer elastomer is prepared. In the process of stretching the polymer, the color of the polymer gradually changes to orange red along with the increase of the elongation, and the polymer can be used as a stress warning material.

Example 10

1 mol equivalent of the compound (a), 20 mol equivalent of the compound (b), 1 mol equivalent of polyethylene glycol (molecular weight 300) and 0.5 wt% of nano Fe₃O₄The particles were put in a reactor, stirred uniformly with methylene chloride as a solvent, added with 0.1 molar equivalent of N, N-diisopropylcarbodiimide and 0.1 molar equivalent of diphenyl-4-phenylthiophenylthiophenylsulfonium salt, and stirred at room temperature for 24 hours. After the reaction is finished, adding 0.01 molar equivalent of bis (acetylacetone) di-n-butyltin and 0.5 molar equivalent of dimethyl siloxane into a reactor, stirring uniformly, continuing to react for 12 hours at 50 ℃, pouring the reaction liquid into a mold, and removing the solvent to obtain the polysiloxane elastomer. The polymer is made into a test sample strip, a tensile testing machine is utilized to carry out tensile test, the tensile strength of the sample is 3.24 +/-0.43 MPa, the elongation at break is 134.24 +/-24.34%, in the process of stretching, the stretching area of the polymer gradually turns red, the color change is obvious, the force-induced response is sensitive, the color depth is in direct proportion to the force, and the polymer can be used as a stress measurement material.

Example 11

50 molar equivalents of poly (acrylic acid-ethyl acrylate) (molecular weight 5000) is dissolved in sufficient acetone in a reactor, the mixture is bubbled for deoxygenation, after the mixture is uniformly stirred, 5 molar equivalents of the compound (a) and 5 molar equivalents of polyethylene glycol (molecular weight 200) are added, after the mixture is uniformly dissolved and mixed, 5 molar equivalents of N-hydroxysuccinimide and 5 molar equivalents of N, N' -dicyclohexylcarbodiimide are added, then the mixture is continuously stirred for 24 hours at room temperature, after the solvent is removed, the polymer is swelled in an aqueous solution containing litmus reagent, and a polymer hydrogel is prepared. During the process of stretching or compressing the polymer, the color of the polymer gradually changes from blue to red, which is caused by the fact that the litmus reagent turns red due to the action of hydrochloric acid molecules released after the force sensitive groups are stressed and the litmus reagent; meanwhile, after the ring is opened by stress, an anthracene ring structure is formed, so that the polymer has strong blue fluorescence under ultraviolet light. The change of the body color and the fluorescence color of the polymer hydrogel after being stressed can be used as a stress test material.

Example 12

Weighing 5 molar equivalents of a compound (a), 50 molar equivalents of a brominated butyl rubber compound (b), 5 molar equivalents of 1, 6-hexanedithiol, 2 wt% of graphene nanosheets, 2 wt% of carbon nanotubes and 2 wt% of antioxidant CA, placing the obtained product in a reactor, performing ultrasonic dispersion by using toluene as a solvent, reacting for 30min under 300W ultraviolet irradiation by using DMPA as a photoinitiator, and performing thiol-olefin reaction to obtain the crosslinked butyl rubber. The triazolinedione produced by force can generate cyclization addition reaction with double bonds in the polymer under ultraviolet light to achieve the effect of force-induced enhancement, so that the polymer has higher breaking strength, and the stress-strain curve of the polymer rapidly rises before the polymer reaches the breaking stress; and the shape of the polymer can be fixed after the polymer is stretched and kept for a period of time, and the polymer can be recovered to the original shape after the stress is rapidly released after the polymer is stretched, so that the obtained polymer material can be used as a polymer material with antistatic and shape memory properties.

Example 13

Dissolving 1 molar equivalent of the compound (a) in sufficient acetone in a reactor, carrying out bubbling deoxygenation, adding 2.1 molar equivalent of polyethylene glycol (molecular weight 500) after uniformly stirring, adding 5 molar equivalent of N-hydroxysuccinimide and 5 molar equivalent of N, N' -dicyclohexylcarbodiimide after uniformly dissolving and mixing, then continuously stirring for 24 hours at room temperature, and removing the solvent to obtain a product 1. Dissolving 1 molar equivalent of the product 1 in tetrahydrofuran, adding 3 molar equivalents of 15 wt% phosgene toluene solution after complete dissolution, stirring at room temperature for 24h, then quenching the reaction with methanol/sodium hydroxide solution, and removing the solvent to obtain a product 2. Weighing 1 molar equivalent of high-purity ethyl glyoxylate, dissolving in sufficient dichloromethane, adding 0.0005 molar equivalent of triethylamine, stirring the reaction solution at-20 ℃ for 1h, adding 0.03 molar equivalent of the product 2, 0.1 molar equivalent of the compound (b), 2 wt% of cellulose nanocrystal and 0.01 molar equivalent of triethylamine, ultrasonically dispersing, heating the reaction solution to room temperature, stirring at room temperature for 16 h, and removing the solvent to obtain the polymer rubber-like substance. When the polymer is stretched and reaches a certain stress, the mechanical strength of the polymer begins to be reduced, the stress is maintained for a period of time, the polymer has a self-degradation phenomenon, the polymer can be used as an environment-friendly elastic material, and when the stress is overlarge, the polymer is automatically degraded after being damaged and does not pollute the environment.

Example 14

The polymer (a) with the ester group end capping is prepared by using polyethylene glycol (molecular weight 1000), 24 (allyloxy) methyl) oxirane and acetyl chloride as raw materials and potassium naphthalene as a catalyst.

Putting 5 molar equivalents of polymer (a), 1 molar equivalent of compound (b), 1 molar equivalent of ethanedithiol, 2 wt% of antioxidant 1010 and 0.1 molar equivalent of catalyst 2, 2-dimethoxy-2-phenylacetophenone (DMPA) into a reactor, taking methanol/water solution as a solvent, adding 2 wt% of nano palladium after complete dissolution, removing oxygen by nitrogen bubbling, putting under a 365nm ultraviolet lamp for irradiation for 3h, and cooling after the reaction is finished to prepare the polymer hydrogel. The polymer gel has good compatibility with organisms, releases nitric oxide gas when extruded or stretched, and can be used as a material for regulating the fluid balance in organisms.

Example 15

4-vinyl benzyl alcohol and acrylic acid are used as raw materials, AIBN is used as a catalyst, hydroxyl is protected by TMS, and a polymer (b) is prepared by free radical polymerization, wherein the molar ratio of carboxyl to hydroxyl is 10: 1. Dissolving 50 molar equivalents of polymer (b) in sufficient toluene in a reactor, bubbling for deoxygenation, adding 5 molar equivalents of compound (a), 5 molar equivalents of polytetrahydrofuran (molecular weight of 300) and 5 molar equivalents of vinyl alcohol after uniformly stirring, adding 5 molar equivalents of N-hydroxysuccinimide, 5 molar equivalents of N, N' -dicyclohexylcarbodiimide, 1 wt% of graphene nanosheet and 1 wt% of carbon fiber after uniformly dissolving and mixing, then continuing to stir at room temperature for 24 hours, then adding 20 wt% of acetic acid/tetrahydrofuran solution, continuing to stir for 6 hours, and removing the solvent to obtain the polymer elastomer. The polymer is made into a tensile sample for testing, and a stress strain curve has a plurality of fluctuations in the pulling process, because the pulled azacarbene ligand catalyzes the exchange reaction of polymer hydroxyl and ester groups, force-induced crosslinking is generated, the mechanical property of the polymer is improved, and meanwhile, the shape of the polymer can be fixed through new crosslinking. The polymer can be used as an antistatic shape memory material.

Example 16

Taking 0.5 molar equivalent of ethyl acrylate and 1 molar equivalent of acrylic acid, placing the ethyl acrylate and the 1 molar equivalent of acrylic acid in a reactor, and taking AIBN as an initiator to prepare the acrylic acid-ethyl acrylate copolymer. Taking 5 molar equivalents of acrylic acid-ethyl acrylate copolymer, 1 molar equivalent of compound (a), 1 molar equivalent of polyethylene glycol (molecular weight 200) and 1 wt% of gallium-indium alloy liquid metal, taking dichloromethane as a solvent, dissolving the materials uniformly, adding 0.1 molar equivalent of N, N-diisopropyl carbodiimide, 0.1 molar equivalent of diphenyl-4-thiophenyl phenyl sulfonium salt and 0.001 molar equivalent of terbium trichloride, and then stirring the mixture at room temperature for reaction for 24 hours. After the reaction is finished, pouring the reaction liquid into a mould, and removing the solvent to obtain the polymer elastomer. The sample is made into a test sample strip, a tensile tester is used for carrying out tensile test, the tensile strength of the sample is 7.73 +/-0.81 MPa, the elongation at break is 168.29 +/-37.28%, and the material gradually emits green fluorescence by being irradiated by 365nm ultraviolet light in the tensile process. The material can be used for stress warning materials, and when the material has strong fluorescence, managers are reminded to maintain the material, so that the safety is guaranteed.

Example 17

1 molar equivalent of the compound (a), 1 molar equivalent of the compound (b), 20 molar equivalent of the compound (c), 1 molar equivalent of polyethylene glycol (molecular weight 300) and 1 wt% of glass fiber were placed in a reactor, and stirred uniformly with methylene chloride as a solvent, and then 0.1 molar equivalent of N, N-diisopropylcarbodiimide and 0.1 molar equivalent of diphenyl-4-phenylthiophenylthiophenylsulfonium salt were added, and stirred and reacted at room temperature for 24 hours. After the reaction is finished, adding 0.01 molar equivalent of bis (acetylacetone) di-n-butyltin and 0.5 molar equivalent of dimethyl siloxane into a reactor, stirring uniformly, continuing to react for 12 hours at 50 ℃, pouring the reaction liquid into a mold, and removing the solvent to obtain the polysiloxane elastomer. The polymer is made into a test sample strip, a tensile testing machine is utilized to carry out tensile test, the tensile strength of the sample is 4.33 +/-0.36 MPa, the elongation at break is 113.34 +/-17.25%, in the process of stretching, under the irradiation of ultraviolet light, the polymer gradually emits strong blue fluorescence, and the current stress condition of the polymer can be fed back in a fluorescence change mode. It can be used as a stress measuring material.

Example 18

Weighing 1 molar equivalent of a force sensitive group compound (a), 10 molar equivalents of a carboxyl modified polyether ketone compound (b) and 1 molar equivalent of polytetrahydrofuran (molecular weight 500), taking DMF as a solvent, stirring uniformly, adding 0.1 molar equivalent of N, N-isopropyl carbodiimide and 0.1 molar equivalent of diphenyl-4-thiophenyl phenyl sulfonium salt, and stirring at room temperature for reaction for 24 hours. After the reaction is finished, the solvent is removed, and a polymer solid powder is prepared. When the polymer powder is ground, the fluorescence of the polymer powder under ultraviolet light is gradually obvious, blue fluorescence is emitted, and the polymer powder can be used as a logic control material.

Example 19

Weighing 5 molar equivalents of a compound (a), 50 molar equivalents of a brominated butyl rubber compound (b), 5 molar equivalents of mercapto-terminated polyethylene glycol (molecular weight 1000), 1 wt% of carbon nanotubes, 1 wt% of glass fibers and 2 wt% of antioxidant BHT, placing the mixture in a reactor, using toluene as a solvent, performing ultrasonic dispersion, using DMPA as a photoinitiator, reacting for 30min under 300W ultraviolet irradiation, and performing mercaptan-olefin reaction to obtain the cross-linked butyl rubber. The sample is made into a test sample strip for tensile test, the tensile strength of the sample is 14.23 +/-1.13 MPa, the elongation at break is 882.13 +/-92.49%, the toughness of the sample is greatly improved due to the existence of the hydrogen bond force sensitive groups, and the hydrogen bond force sensitive groups have the effect of toughening caused by force. The polymer can be used as an ultra-tough rubber material.

Example 20

Dissolving 4 molar equivalents of pentaerythritol tetra (3-hydroxypropionic acid) and 10 moles of a single compound (a) in acetone, adding 30 molar equivalents of dicyclohexylcarbodiimide and 5 molar equivalents of 4-dimethylaminopyridine, stirring at room temperature for reaction for 24 hours, adding 4 molar equivalents of 1, 8-octanediol, continuing the reaction for 12 hours, pouring the reaction solution into a mold, naturally drying, and removing the acetone solvent to obtain a polymer solid coating. The solid material has good toughness, the deformation area can be changed into green in the stretching process, the solid material can be used for monitoring the deformation of the material, and the color can gradually fade after the stretching is stopped. When the solid is pulled apart, rapid repair can be achieved by heating or ultraviolet light. The steel rope can be used as a steel rope coating material to warn the stress state of the steel rope.

Example 20

Taking 20 molar equivalents of brominated butyl rubber compound (a), 3 molar equivalents of compound (b), 5 molar equivalents of mercapto-terminated polyethylene glycol (molecular weight 200), 1 wt% of carbon fiber, 0.5 wt% of zinc oxide and 1 wt% of benzoin dimethyl ether, adding a proper amount of chloroform, pouring the mixed solution into a mold, and reacting for 30min under ultraviolet irradiation to obtain the butyl rubber elastomer. The elastic body can be stretched and extended in a large range under the action of external force, when the stretching strain reaches more than 200%, the elastic body can turn green, the stretching deformation is larger, the color is darker, and after the stretching strain is released, the color can fade. The elastomer material also has the characteristics of low permeability, aging resistance, weather resistance and the like, and can be used as an inner sealing material of a tire or a tire with a tire pressure/air pressure detection function.

Example 21

Dissolving 0.0015 molar equivalent of polyvinyl chloride (molecular weight is 60000), 2 molar equivalent of compound (a), 1 molar equivalent of sulfhydryl-terminated polyethylene glycol (molecular weight is 200), 6 molar equivalent of potassium carbonate and 1.5 molar equivalent of tetrabutylammonium bromide by using a proper amount of cyclohexane, stirring and reacting for 8 hours at 60 ℃ in an argon atmosphere, removing a catalyst and a solvent after the reaction is finished, and drying to obtain the crosslinked polyvinyl chloride. Taking 100 parts by mass of crosslinked polyvinyl chloride, 15 parts by mass of chlorinated polyethylene A135, 5 parts by mass of nano calcium carbonate, 0.5 part by mass of calcium stearate and 6 parts by mass of tribasic lead sulfate, mixing the materials in a high-speed mixer for 10min, placing the mixed materials on a double-roll open mill, mixing for 10min at the temperature of 160-plus-material 170 ℃, taking sheets, placing the sheets on a hydraulic press, carrying out die pressing for 10min at the pressure of 175-plus-material 180 ℃ and 10MPa, and then cooling to room temperature at the pressure of 8MPa to prepare the polyvinyl chloride plate. The tensile strength of the plate is 55MPa, and the bending strength is 89 MPa. Under the action of certain compressive stress, the floor can locally present dark green, can be used as a recording floor with a display/tracing function, and can be applied to sports projects, such as a pressure stress generated by the falling of athletes or other balls, and a force sensitive group is locally activated to obtain the color development/tracing function.

Example 22

Taking 4 molar equivalents of hydroxyl-terminated four-arm polyethylene glycol (with the molecular weight of 5000), 5 molar equivalents of dicyano tetraphenylethane derivative (a) and 1.5 molar equivalents of 1, 10-sebacic acid, dissolving with tetrahydrofuran, adding 30 molar equivalents of dicyclohexylcarbodiimide and 5 molar equivalents of 4-dimethylaminopyridine, stirring at room temperature for reaction for 24 hours, adding 2 molar equivalents of n-butanol, 2 molar equivalents of polyethylene glycol monomethyl ether and 5 wt% of aluminum nitride, continuing to react for 12 hours, and removing the solvent after the reaction is finished to obtain the solid polymer. The solid can be stretched and expanded in a large range, a polymer stretching area can generate pink, and yellow fluorescence can be generated under 365nm ultraviolet illumination; and with the increase of the stretching deformation, the color deepens firstly and then keeps unchanged, then the stretching is continued, the color deepens again, and finally the fracture is realized. The fractured sample can be placed in a mold and can be quickly recovered by heat preservation. The material can be used as a heat conduction/dissipation material, not only has the functions of heat conduction and heat dissipation, but also can warn the limit deformation and stress of the material.

Example 23

5 molar equivalents of the compound (a), 12 molar equivalents of 4-vinylbenzoic acid, 15 molar equivalents of 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide and 2.5 molar equivalents of 4-dimethylaminopyridine are taken and reacted for 24 hours at room temperature by using a dichloromethane solvent to prepare the stilbene derivative. Taking 100 mol equivalent of styrene, 10 mol equivalent of stilbene derivative, 10 mol equivalent of compound (b) and 5 wt% of azodimethoxy isoheptonitrile, taking toluene as a solvent, stirring and reacting for 72 hours at 40 ℃ under nitrogen atmosphere, pouring the reaction liquid into a glass mold after the reaction is finished, and obtaining the polymer film after the toluene solvent is volatilized. The film surface is scratched by a scraper or a glass plate, the scratched area shows purple red, and then the color gradually fades after about 30s-2min, so that the film can be used as an intelligent drawing board/demonstrator material.

Example 24

Taking 10 molar equivalents of hydroxyl-terminated four-arm polyethylene glycol (molecular weight is 4000), 5 molar equivalents of single-amount thioxanthone type pinacol compound (a) and 2 molar equivalents of carboxyl-terminated polyethylene glycol (molecular weight is 200), dissolving with tetrahydrofuran, adding 30 molar equivalents of dicyclohexylcarbodiimide and 5 molar equivalents of 4-dimethylaminopyridine, stirring at room temperature for reaction for 24 hours, adding 4 molar equivalents of n-butanol, continuing to react for 12 hours, and purifying to obtain the crosslinked polyethylene glycol. Taking 50 parts by mass of the crosslinked polyethylene glycol, 3 wt% of liquid metal gallium and 120 parts by mass of distilled water to prepare the polymer hydrogel. The gel material uniformly cracks the force sensitive groups under the action of stress to generate yellow-green free radicals, so that the stress warning function is obtained, the shape can be fixed after the fixed stretching deformation is carried out for a period of time, and the faster shape fixing effect can be realized through ultraviolet light or visible light irradiation; when heated, the polymer gradually recovers its shape, and can be used as a shape memory material having a stress warning function.

Example 25

Taking 8 molar equivalents of n-butyl acrylate, 2 molar equivalents of 2-bromoethyl acrylate and 0.1 molar equivalent of azobisisobutyronitrile, dissolving the mixture by tetrahydrofuran, and stirring and reacting for 24 hours at 70 ℃ under nitrogen atmosphere to obtain the acrylic ester copolymer (a).

Taking 3 molar equivalents of acrylate copolymer (a), 5 molar equivalents of compound (b), 2 molar equivalents of polyethylene glycol (molecular weight 300) and 10 molar equivalents of sodium hydroxide, dissolving with a proper amount of tetrahydrofuran, stirring at 50 ℃ for reaction for 6 hours, adding 2.5 wt% of liquid metal gallium and 10 wt% of dioctyl phthalate, stirring uniformly, pouring the reaction liquid into a flat plate mold, placing the flat plate mold in a vacuum oven for standing reaction for 6 hours, and reducing pressure to remove residual solvent, thus obtaining the final polymer film. The film material has good tensile toughness, the measured tensile strength is 5.1MPa, and the elongation at break is 543%. In the stretching process, the stretching deformation area is pink, and the color is gradually deepened along with the increase of the deformation amount; the film material also has good heat-conducting property, and can be used as a heat-conducting sticking film and a heat-radiating sticking material with a visual stress/strain monitoring function.

Example 26

Dissolving 5 molar equivalents of bifluorene compound (a), 10 molar equivalents of carboxyl double-terminated polyethylene glycol (molecular weight is 1000) and 3 molar equivalents of glycerol in tetrahydrofuran, adding 30 molar equivalents of dicyclohexylcarbodiimide and 5 molar equivalents of 4-dimethylaminopyridine, stirring at room temperature for reaction for 48 hours to ensure that active functional groups are completely reacted to prepare crosslinked polyethylene glycol, and swelling the crosslinked polyethylene glycol in an ethanol solvent to prepare the polymer organogel. The gel material has the force sensitive groups which are homolytic to crack under the action of stress, so that the crosslinking degree of the polymer is reduced, and the gel material can be used as a drug carrier material with the function of causing drug release.

Example 27

Taking 5 molar equivalents of xanthene type pinacol derivative (a), 10 molar equivalents of carboxyl terminated polytetrahydrofuran (molecular weight is 6000) and 10 molar equivalents of hydroxyl terminated four-arm polyethylene glycol (molecular weight is 4000), dissolving the materials by using tetrahydrofuran, adding 30 molar equivalents of dicyclohexylcarbodiimide and 5 molar equivalents of 4-dimethylaminopyridine, stirring at room temperature for reaction for 48 hours to ensure that active end groups are completely reacted, pouring a reaction solution into a mold after the reaction is finished, naturally drying, and then placing a product in an N-isopropylacrylamide aqueous solution for swelling for 24 hours to prepare the polymer hydrogel. After the hydrogel is stretched or compressed, the hydrogel can be switched between transparent and turbid by changing the temperature of the external environment, the propagation of a light path can be controlled by using the hydrogel, and the hydrogel can be used as a logic control material.

Example 28

1 molar equivalent of the compound (a), 5 molar equivalents of the compound (b) and 0.5 molar equivalent of polyethylene glycol (molecular weight 500) are uniformly stirred by taking methylene chloride as a solvent, 0.01 molar equivalent of N, N-diisopropylcarbodiimide and 0.01 molar equivalent of diphenyl-4-thiophenyl phenyl sulfonium salt are added, the mixture is stirred and reacted for 24 hours at room temperature, the reaction solution is poured into a mold, and the solvent is removed, so that the polysiloxane elastomer is prepared. When the elastic body is pulled to the elongation of 5%, green light is emitted, the emitted light has a certain time length and sensitive stress induction capability, and the elastic body can be used as a stress tracing material.

Example 29

Taking 5 molar equivalents of the compound (a), 10 molar equivalents of carboxyl terminated polyethylene glycol (molecular weight is 6000) and 10 molar equivalents of hydroxyl terminated four-arm polyethylene glycol (molecular weight is 4000), dissolving with tetrahydrofuran, adding 30 molar equivalents of dicyclohexylcarbodiimide and 5 molar equivalents of 4-dimethylaminopyridine, stirring at room temperature for reaction for 48 hours to ensure that active end groups are completely reacted, pouring a reaction solution into a mold after the reaction is finished, naturally drying, and then placing a product in a DMSO solution of the compound (b) for swelling for 24 hours to prepare the polymer organogel. After the organic gel is pressed, the organic gel is briefly irradiated by 420nm blue light, so that easily-perceived odor can be emitted, and the stress warning effect through olfaction can be realized; in addition, after the blue light irradiation, 365nm ultraviolet light is used for irradiation, blue fluorescence is found to diffuse from the pressing point to the periphery, and finally the whole gel has a fluorescence phenomenon, so that the material has multiple force response effects and can be used as a gel lining material.

Example 30

Adding 100 parts by mass of polyether polyol ED-28 (hydroxyl value is 26.5-29.5) and 11 parts by mass of compound (a) into a reactor, heating to 80 ℃, uniformly mixing, adding 50 parts by mass of carboxyl-terminated polyethylene glycol (molecular weight is 6000), 30 molar equivalent dicyclohexylcarbodiimide and 5 molar equivalent 4-dimethylaminopyridine, uniformly stirring, placing the mixed solution into a mold, standing in a 50 ℃ oven for 4 hours, taking out, cooling, and swelling in sufficient deionized water to obtain the gel material. The gel material can be used as an external application medical material, is applied to the skin symptom part, can release ketoconazole drug molecules to treat the symptom by using 420nm blue light irradiation after being pressed, and can not release the drug molecules under the condition of no pressing, thereby being beneficial to prolonging the drug effect time of the gel material.

Example 31

Taking 0.5 molar equivalent of ethyl acrylate and 1 molar equivalent of acrylic acid, placing the ethyl acrylate and the 1 molar equivalent of acrylic acid in a reactor, and taking AIBN as an initiator to prepare the acrylic acid-ethyl acrylate copolymer. After 5 molar equivalents of the acrylic acid-ethyl acrylate copolymer, 1 molar equivalent of the compound (a) and 1 molar equivalent of polyethylene glycol (molecular weight 200) were dissolved in methylene chloride as a solvent, 0.1 molar equivalent of N, N-isopropylcarbodiimide and 0.1 molar equivalent of diphenyl-4-phenylthiophenyl-phenylsulfonium salt were added, followed by stirring at room temperature for 24 hours. After the reaction is finished, pouring the reaction liquid into a mould, and removing the solvent to obtain the polymer elastomer. Compared with the traditional elastic material, the elastic body in the embodiment has the advantage that the stress-strain curve fluctuates along with the increase of the elongation in the stretching process, and the stress-strain curve is caused by the spontaneous generation of force-induced crosslinking in the polymer during stretching, so that the mechanical property of the material is improved. The bungee jumping rope can be made into a bungee jumping elastic rope for use, and the bungee jumping rope can enhance the mechanical property of the bungee jumping rope under the condition of high stress and guarantee the safety.

Example 32

0.5 molar equivalent of compound (a), 3 molar equivalent of modified brominated butyl rubber (b) and 0.5 molar equivalent of polyethylene glycol (molecular weight 500) are stirred uniformly by taking dichloromethane as a solvent, 0.05 molar equivalent of N, N-isopropyl carbodiimide and 0.05 molar equivalent of diphenyl-4-thiophenyl phenyl sulfonium salt are added, the mixture is stirred and reacted for 24 hours at room temperature, the reaction liquid is poured into a mold, and the solvent is removed to prepare the cross-linked butyl rubber with good resilience.

Example 33A crosslinked network, ferrocene

3g of ferrocene, 20mL of dry n-hexane, stirring or suspension, 20.7mL of butyllithium (1.6M n-hexane solution), 5.1mL of TMEDA (0.033mol), and stirring under Ar gas for reaction overnight are added into a dry two-necked flask. After removing the solvent and impurities, 50mL of dry ether is added and stirred to form a suspension, the reaction bottle is cooled to minus 78 ℃ in an ethanol dry ice bath, 1.5mL (1.9g, 0.013mol) of dry steamed trichlorosilane is added dropwise, then the temperature is raised to room temperature, and the reaction is stirred under the protection of Ar gas overnight. And removing the ether and the excessive methyltrichlorosilane in vacuum, placing the product in a vacuum tube sealing, and placing the product in a tubular muffle furnace for polymerization for 50 minutes at 250 ℃ to obtain the polyferrocenylmethyl chlorosilane. Placing 1.0g of polyferrocenylmethylchlorosilane in a dry two-necked bottle, adding 80mL of toluene, dissolving, adding 5.3mL of triethylamine, 10g of polyvinyl alcohol (molecular weight is 1000) and 6g of 1, 6-adipoyl chloride, stirring the solution under Ar atmosphere for reaction for 12 hours, coating the reaction solution on a polytetrafluoroethylene flat plate, and drying to obtain the polymer film. Through tests, the stressed area and the unstressed area of the polymer film have different magnetic responsivities, and the polymer film can be prepared into a functional film with force-induced magnetic transformation for use.

Example 34

Taking 1 molar equivalent of a compound (a), 5 molar equivalent of carboxyl-terminated polytetrahydrofuran (molecular weight of 6000) and 10 molar equivalent of hydroxyl-terminated four-arm polyethylene glycol (molecular weight of 4000), dissolving with tetrahydrofuran, adding 30 molar equivalent of dicyclohexylcarbodiimide and 5 molar equivalent of 4-dimethylaminopyridine, stirring at room temperature for reaction for 48 hours to ensure that active end groups are completely reacted, pouring a reaction solution into a mold after the reaction is finished, naturally drying, and then placing a product in 1-ethyl-3-methylimidazolium bromide ionic liquid for swelling for 24 hours to prepare the polymer ionic liquid swelling gel. The hydrogel has good tensile toughness, the electrical conductivity of the polymer can be changed in a tensile deformation area, the control can be realized through the electrical conductivity of the polymer, and the hydrogel can be used as a logic control material.

Example 35

Adding a sufficient amount of chloroform as a solvent into a dry clean reactor, adding 1 mol equivalent of the compound (a), stirring uniformly, cooling the solution to 0 ℃, adding 0.1 mol equivalent of the compound (d), stirring for 1.5min, adding 5 mol equivalent of the compound (b), stirring for 45s, adding 1 mol equivalent of the compound (a), reacting for 1.5min, quenching the reaction mixture with a few drops of ethyl vinyl ether, raising the temperature to room temperature, adding 2 mol equivalents of 1, 6-adipic acid, stirring uniformly, adding 0.02 mol equivalents of N, N-diisopropylcarbodiimide and 0.02 mol equivalents of diphenyl-4-thiophenylthiophenylsulfennium salt, reacting for 12h at room temperature, adding a sufficient amount of tetrahydrofuran, precipitating the product into methanol to obtain a polymer powder, it is then made into a polymeric ordinary solid. The polymer ordinary solid has good toughness under the action of stress, and can be used as an instrument shell material.

Example 36

Catalyzing ethyl glyoxylate to polymerize under the condition of assisting ring opening by a small amount of propylene oxide by using three-arm polyethylene glycol as an initiator and boron trifluoride diethyl etherate as a catalyst to obtain hydroxyl-terminated three-arm ethyl glyoxylate; mixing a certain amount of hydroxyl-terminated three-arm polyglyoxylic acid ethyl ester and DMF, adding phosphorus tribromide, stirring and reacting at 0 ℃ and 40 ℃ in sequence, and performing subsequent treatment to obtain bromine-terminated three-arm polyglyoxylic acid ethyl ester; mixing a certain amount of bromo-terminated three-arm polyglyoxylic acid ethyl ester and DMF, adding sodium azide, stirring at room temperature for reaction, and performing subsequent treatment to obtain azido-terminated three-arm polyglyoxylic acid ethyl ester. The elastomer is prepared by uniformly mixing 1 molar equivalent of azido-terminated ethyl polyuronate, 0.1 molar equivalent of compound (a), 0.1 molar equivalent of compound (b), 0.05 molar equivalent of sodium ascorbate and 0.05 molar equivalent of copper sulfate pentahydrate aqueous solution, and then placing the mixture in a nitrogen atmosphere for reaction for 24 hours. When the stress on the elastomer reaches a certain degree, the polymer can start to gradually degrade by itself; therefore, the material has the characteristic of forced degradation, and can be used as an environment-friendly material for areas which are not easy to replace and maintain.

Example 37

Weighing 1 molar equivalent of polymer (b) (with the molecular weight of 5000) in a dry clean flask, heating to 100 ℃, introducing nitrogen to remove water and oxygen for 1h, adding 0.01 molar equivalent of platinum dichloride, 0.4 molar equivalent of spirooxazine compound (a) and 0.2 molar equivalent of alkene double-terminated polydimethylsiloxane, continuing to react for 1h, after the reaction is finished, placing a polymer sample in a proper mold, placing in a vacuum oven to dry for 24h, and then cooling to room temperature to finally obtain the polysiloxane elastomer with high elasticity. Compared with the traditional polysiloxane material, the polymer prepared by the embodiment has the advantages that in the stretching process, the color is changed from transparent to red along with the increase of the elongation, the larger the stress is, the darker the color is, the stress condition of the material can be reflected through the change of the color depth, and the management and the maintenance are convenient; after releasing the stress, the color of the polymer can be quickly restored to the original shape (less than 1 second), and the polymer can be repeatedly used.

Example 38

And (2) taking dicumyl peroxide as an initiator, and grafting and modifying the low molecular weight polypropylene by using maleic anhydride through a melt grafting reaction to obtain the graft modified polypropylene, wherein the mass ratio of the dicumyl peroxide to the maleic anhydride is 1: 10. Weighing 50 parts by mass of graft modified polypropylene and 0.02 part by mass of BHT antioxidant, adding the materials into a dry and clean three-neck flask, heating the materials to 160 ℃ under the protection of nitrogen, stirring and melting the materials, then adding 10 parts by mass of a compound (a), 5.4 parts by mass of dihydroxy-terminated olefin-containing polytetrahydrofuran (molecular weight 500), 0.15 part by mass of p-toluenesulfonic acid, 2.0 parts by mass of plasticizer DOP and 0.25 part by mass of dimethyl silicone oil, and continuously reacting the materials for 3 hours under the condition of nitrogen to finally obtain a blocky polypropylene-based polymer sample. The polymer sample has glossy surface, certain strength and compressibility and can be stretched in a certain range. The polypropylene-based dynamic polymer material in the embodiment has good tensile toughness and deformability, can be used as a stress sensing material, the mechanical property of the material can be gradually improved during stretching, the polypropylene-based dynamic polymer material can be used for sealing precise instruments or electronic products, and the color of the material can be changed into green during illumination and stretching.

Example 39

And (2) taking dicumyl peroxide as an initiator, and grafting and modifying the low molecular weight polyethylene by using maleic anhydride through a melt grafting reaction to obtain the graft modified polyethylene, wherein the mass ratio of the dicumyl peroxide to the maleic anhydride is 1: 10. 50 parts by mass of maleic anhydride graft modified polyethylene (b), 15 parts by mass of dihydroxy terminated polysiloxane (molecular weight 1000), 9 parts by mass of dioctyl phthalate, 15 parts by mass of compound (a), 6.2 parts by mass of stearic acid, 5.4 parts by mass of tribasic basic lead sulfate, 1.6 parts by mass of di-n-butyltin dilaurate and 1.2 parts by mass of dimethyl silicone oil are uniformly mixed, added into a small internal mixer and mixed for 10min, then adding 10 parts by mass of carbon fiber for continuous mixing, taking out the mixed material after the mixing is finished, cooling, placing the material in a double-roller machine at 150 ℃ for pressing into sheets, cooling and cutting into pieces at room temperature, placing the sample in a proper mold, placing on a flat vulcanizing machine, heating at 160 ℃ for 10min, and then taking out, placing in a vacuum oven at 80 ℃ for 12h for further reaction, and finally obtaining the carbon fiber reinforced polyethylene polymer material. In the stretching process of the polymer material prepared by the embodiment, the color is changed from transparent to red along with the increase of the elongation, the larger the stress is, the darker the color is, the stress condition of the material can be reflected through the change of the color depth, and the management and the maintenance are convenient; after the stress is released, the color of the polymer can be rapidly recovered to the original shape (less than 1 second), and the polymer can be used as a plate with a stress discoloration function in the automobile field or the aerospace field, and can repeatedly induce the stress.

Example 40

Taking hydrogen-containing polysiloxane (the content of a silicon-hydrogen bond is 40 percent), methyl methacrylate as raw materials and Karstedt catalyst as a catalytic system to prepare a polymer (a) with the molecular weight of 20000; placing 5 molar equivalents of the compound (a), 0.4 molar equivalent of the compound (b) and 0.4 molar equivalent of dihydroxy-terminated polyethylene glycol (molecular weight 500) in a reactor, taking dichloromethane as a solvent, stirring uniformly, adding 0.01 molar equivalent of N, N-diisopropylcarbodiimide and 0.01 molar equivalent of diphenyl-4-thiophenyl phenyl sulfonium salt, stirring at room temperature for 24 hours, and removing the solvent and impurities to obtain a product 1. 10g of the product 1 was swollen in a dichloromethane solution, then 30mL of a 0.1g/mL zinc dichloride dichloromethane solution was added dropwise, and after stirring for 2 hours, the solvent and impurities were removed to prepare a polymer ordinary solid. The material is prepared into a test sample strip for testing, and the softer the material is, the more flexible the material is at higher temperature, the material is molded into a shape at higher temperature, and the shape can be fixed when the temperature is reduced, so that the material has good shape memory effect; when the tensile deformation reaches 5%, the deformation area gradually turns red, and the stress warning effect is achieved; after releasing the stress, the color can be recovered rapidly, and the stress discoloration can be repeated. By combining the various performance advantages, the medical polymer material with the stress indication function can be used as a medical polymer material with the stress indication function, such as a joint fixing plate and the like.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims

1. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein said crosslinked network comprises a polymer segment structure of at least two different types of chemical structures; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

2. The force-responsive crosslinked polymer of claim 1, wherein the force-responsive crosslinked polymer has one of the following network structures:

3. The force-responsive crosslinked polymer of claim 1, wherein the formulation components constituting the composition of the force-responsive crosslinked polymer comprise any one or more of the following additives/agents: auxiliaries/additives, fillers;

wherein, the additive/additive which can be added is selected from any one or more of the following: catalysts, initiators, redox agents, antioxidants, light stabilizers, heat stabilizers, toughening agents, lubricants, mold release agents, plasticizers, foaming agents, antistatic agents, emulsifiers, dispersing agents, colorants, fluorescent whitening agents, delustering agents, flame retardants, nucleating agents, rheological agents, thickeners, and leveling agents;

wherein, the filler which can be added is selected from any one or more of the following materials: inorganic non-metallic fillers, organic fillers, organometallic compound fillers.

4. The force-responsive crosslinked polymer of any of claims 1, 3, wherein the polymer morphology is any of: common solids, elastomers, foams, gels.

5. The force-responsive crosslinked polymer of claim 1, wherein the polymer is applied to a stress-sensitive material, a sensor material, an ion-detecting material, a bioanalytical material, a sealing material, a flexible material, a toy material, a stationery material, a shape memory material, an energy storage device material.

6. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein said crosslinked network comprises a polymer segment structure of at least two different types of chemical structures; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

7. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is a carbon chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

8. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is a carbon chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

9. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the cross-linked network is a carbon heterochain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

10. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the cross-linked network is a carbon heterochain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

11. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a carbon element chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

12. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a carbon element chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

13. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is a carbon hetero element chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

14. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is a carbon hetero element chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

15. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is an element organic heterochain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

16. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is an element organic heterochain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

17. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is a non-polyorganosiloxane organic chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

18. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein the crosslinking network is a non-polyorganosiloxane organic chain structure; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

19. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups based on a homolytic mechanism, covalent force sensitive groups based on a heterolytic mechanism, covalent force sensitive groups based on a reverse cyclization mechanism and covalent force sensitive groups based on a bending activation mechanism; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

20. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups based on a homolytic mechanism, covalent force sensitive groups based on a heterolytic mechanism and covalent force sensitive groups based on a bending activation mechanism; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

21. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from non-covalent force sensitive groups; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

22. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from non-covalent force sensitive groups; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

23. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive group is selected from covalent force sensitive groups of a three-membered ring electrocyclization mechanism; wherein, the force sensitive group can generate biological change under the action of mechanical force, so that the polymer realizes force-induced response.

24. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive group is selected from covalent force sensitive groups of a three-membered ring electrocyclization mechanism; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

25. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a five-membered ring electrocyclization mechanism; wherein, the force sensitive group can generate biological change under the action of mechanical force, so that the polymer realizes force-induced response.

26. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a five-membered ring electrocyclization mechanism; wherein, the force sensitive group can generate chemical and/or physical change under the action of mechanical force, so that the polymer realizes force-induced response.

27. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a six-membered ring electrocyclization mechanism; the force sensitive groups can perform biological change under the action of mechanical force, so that the polymer can realize force-induced response; wherein the six-membered ring force sensitive group motif in the covalent force sensitive group of the six-membered ring electrocyclization mechanism is selected from the following structures:

wherein X is selected from oxygen atom, sulfur atom, selenium atom, tellurium atom, C-R, N-R; y is selected from C-R and nitrogen atom; each R is independently an atom, a substituent, a substituted polymer chain; m is a metal atom selected from Be, Zn, Cu, Co, Hg, Pb, Pt, Fe, Cr, Ni.

28. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a six-membered ring electrocyclization mechanism; the force sensitive groups can generate chemical and/or physical changes under the action of mechanical force, so that the polymer realizes force-induced response; wherein the six-membered ring force sensitive group motif in the covalent force sensitive group of the six-membered ring electrocyclization mechanism is selected from the following structures:

29. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a six-membered ring electrocyclization mechanism; the force sensitive groups can perform biological change under the action of mechanical force, so that the polymer can realize force-induced response; wherein the six-membered ring force sensitive group motif in the covalent force sensitive group of the six-membered ring electrocyclization mechanism is selected from the following structures:

wherein X is selected from oxygen atom, sulfur atom, selenium atom, tellurium atom, C-R, N-R; y is a nitrogen atom; each R is independently an atom, a substituent, a substituted polymer chain.

30. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a six-membered ring electrocyclization mechanism; the force sensitive groups can generate chemical and/or physical changes under the action of mechanical force, so that the polymer realizes force-induced response; wherein the six-membered ring force sensitive group motif in the covalent force sensitive group of the six-membered ring electrocyclization mechanism is selected from the following structures:

31. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a six-membered ring electrocyclization mechanism; the force sensitive groups can perform biological change under the action of mechanical force, so that the polymer can realize force-induced response; wherein the six-membered ring force sensitive group motif in the covalent force sensitive group of the six-membered ring electrocyclization mechanism is selected from the following structures:

wherein X is selected from sulfur atom, selenium atom, tellurium atom, C-R, N-R; y is C-R; each R is independently an atom, a substituent, a substituted polymer chain.

32. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a six-membered ring electrocyclization mechanism; the force sensitive groups can generate chemical and/or physical changes under the action of mechanical force, so that the polymer realizes force-induced response; wherein the six-membered ring force sensitive group motif in the covalent force sensitive group of the six-membered ring electrocyclization mechanism is selected from the following structures:

33. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a six-membered ring electrocyclization mechanism; the force sensitive groups can perform biological change under the action of mechanical force, so that the polymer can realize force-induced response; wherein the six-membered ring force sensitive group motif in the covalent force sensitive group of the six-membered ring electrocyclization mechanism is selected from the following structures:

wherein, X, X₁Selected from oxygen atoms; y is C-R; y is₁Selected from C-R, nitrogen atom; each R is independently an atom, a substituent, a substituted polymer chain; z₁Is selected from C- (R)₂Nitrogen atom, sulfur atomA proton, an oxygen atom, a tellurium atom; z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂A nitrogen atom; when Z is₁Or Z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂When connected to it

The number is 0;

an aromatic ring having an arbitrary number of elements; n is the total number of hydrogen atoms, substituent atoms, substituents, and substituted polymer chains bonded to the atoms constituting the ring, and is 0, 1, or an integer greater than 1.

34. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a six-membered ring electrocyclization mechanism; the force sensitive groups can generate chemical and/or physical changes under the action of mechanical force, so that the polymer realizes force-induced response; wherein the six-membered ring force sensitive group motif in the covalent force sensitive group of the six-membered ring electrocyclization mechanism is selected from the following structures:

wherein, X, X₁Selected from oxygen atoms; y is C-R; y is₁Selected from C-R, nitrogen atom; each R is independently an atom, a substituent, a substituted polymer chain; z₁Is selected from C- (R)₂Nitrogen atom, sulfur atom, oxygen atom, tellurium atom; z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C-(R)₂A nitrogen atom; when Z is₁Or Z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂When connected to it

The number is 0;

35. A force-responsive crosslinked polymer comprising a force-sensitive group and only one crosslinked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a six-membered ring electrocyclization mechanism; the force sensitive groups can perform biological change under the action of mechanical force, so that the polymer can realize force-induced response; wherein the six-membered ring force sensitive group motif in the covalent force sensitive group of the six-membered ring electrocyclization mechanism is selected from the following structures:

wherein, X, X₁Selected from oxygen atoms; y is C-R; each R is independently an atom, a substituent, a substituted polymer chain; z₁Is selected from C- (R)₂Nitrogen atom, sulfur atom, oxygen atom, tellurium atom; z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂A nitrogen atom; when Z is₁Or Z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂When connected to it

The number is 0;

36. A method of achieving a force-responsive cross-linked polymer comprising a force-sensitive group and only one cross-linked network; the crosslinking network contains common covalent crosslinking and force sensitive group crosslinking at the same time, wherein the crosslinking degree of the common covalent crosslinking is above the gel point of the common covalent crosslinking, and the crosslinking degree of the force sensitive group crosslinking is above or below the gel point of the force sensitive group crosslinking; wherein, the crosslinking network is a polyorganosiloxane organic chain structure; wherein the force sensitive groups are selected from covalent force sensitive groups of a six-membered ring electrocyclization mechanism; the force sensitive groups can generate chemical and/or physical changes under the action of mechanical force, so that the polymer realizes force-induced response; wherein the six-membered ring force sensitive group motif in the covalent force sensitive group of the six-membered ring electrocyclization mechanism is selected from the following structures:

The number is 0;