CN109206628A

CN109206628A - A kind of energy-absorbing method based on hybrid cross-linked dynamic aggregation object

Info

Publication number: CN109206628A
Application number: CN201710523752.XA
Authority: CN
Inventors: 不公告发明人
Original assignee: Weng Qiumei
Current assignee: Xiamen Daimeng Sports Technology Co.,Ltd.
Priority date: 2017-06-30
Filing date: 2017-06-30
Publication date: 2019-01-15

Abstract

The invention discloses a kind of energy-absorbing method based on hybrid cross-linked dynamic aggregation object, the energy-absorbing method uses the hybrid cross-linked dynamic aggregation object constituted containing the covalent cross-linking and at least one second group of supermolecular mechanism and optional first group of supermolecular mechanism formed by covalent bond to carry out energy-absorbing；Wherein, second group of supermolecular mechanism includes ionization, ion-dipole effect, Host-guest effect, close metal function, dipole-dipole effect, halogen bond effect, cation-π effect, anion-π effect, benzene-fluorobenzene effect, the effect of π-π stacking, ion hydrogen bond action, radical cation dimerization, and first group of supermolecular mechanism includes hydrogen bond action, metal-ligand effect.The dynamic aggregation object carries out being especially applied to body protection, explosion-proof, airborne and air-drop protection, automobile collision preventing, electric equipment products defense of resistance to impact etc. using that can provide the functions such as good damping, damping, sound insulation, noise elimination, shock resistance as energy-absorbing material.

Description

A kind of energy-absorbing method based on hybrid cross-linked dynamic aggregation object

Technical field:

The present invention relates to a kind of energy-absorbing methods, and in particular to a kind of miscellaneous based on being made of supermolecular mechanism and covalent cross-linking Change the energy-absorbing method of crosslinking dynamic aggregation object.

Background technique:

In daily life and actual production process, it is often necessary to which application method or means avoid or slow down shock, vibration Physical impact bring caused by the forms such as dynamic, vibration, explosion, sound influences, wherein widely used is to use A kind of energy-absorbing material progress energy absorption, to play effective protective action to physical impact.Material for energy-absorbing is main There are metal, polymer, composite material etc..Wherein, polymer material energy loss source mainly include the following types: 1, using poly- Close object has the phenomenon that high fissipation factor energy-absorbing near its glass transition temperature.This method is in vitrifying due to material Near transition temperature, the mechanical property of material is sensitive to temperature change, and the mechanical property of material is easily with environment in use The variation of temperature and acute variation, bring difficulty to using；2, it is produced using the fracture of the chemical bonds such as covalent bond and material internal The processes energy-absorbings such as the life crackle even fracture of material entirety, during above-mentioned each, the fracture of covalent bond and macroscopical crackle break Splitting can not only restore, and the mechanical property that also will lead to material reduces, and after primary or a small number of endergonic process several times, material is necessary Replacement could maintain original performance in time；3, the larger deformation institute of deformation, especially polymer rubber state or viscoelastic state is utilized Interior friction energy-absorbing between bring molecule segment, this method, which usually requires the biggish deformation of material generation, could generate significantly Effect, and after the deformation of energy height loss occurs for material, it can not be often restored to original shape, can not be continued to use, it must It must be replaced.Novel shock-resistant and energy-absorbing material are a kind of new material proposed in recent years, choosing of its appearance for material It selects and its performance study has important practical value.The shock resistance energy-absorbing material of various configuration in addition to excellent mechanics, Carrying, shock resistance outside energy absorption characteristics, also have the other functions such as damping, vibration damping, sqouynd absorption lowering noise, stimuli responsive, to meet boat The demand that the high-technology fields such as empty space flight, precision instrument, auto industry propose material.

In the prior art, the common structure of polymer material for being used as energy-absorbing has based on above-mentioned various energy loss mechanism And design obtained polymer alloy, polymer interpenetration network, polymer elastomer etc..These are often for structures of energy-absorbing The simple superposition of above-mentioned each mechanism improves although expanding energy-absorbing range to a certain extent compared with single above-mentioned mechanism Energy absorbing efficiency, but still not can avoid its deficiency.Therefore, it is necessary to develop a kind of new energy-absorbing method, in particular with introducing one The polymer of new energy absorption and loss mechanism is planted to carry out energy-absorbing, to solve problems of the prior art.

Summary of the invention

The present invention is directed to above-mentioned background, provides a kind of energy-absorbing method based on hybrid cross-linked dynamic aggregation object, described Hybrid cross-linked dynamic aggregation object, contains covalent cross-linking and supermolecular mechanism；Wherein, covalent cross-linking is at least one cross-linked network In reach the gel point of covalent cross-linking or more.The hybrid cross-linked dynamic aggregation object is with good mechanical strength and centainly Toughness while, also show good dynamic reversibility, and energy can be absorbed by the reversible fracture of supermolecular mechanism, Dynamic aggregation object is assigned with good defense of resistance to impact, stimulating responsive and bionical mechanical property are also reflected, to mention A kind of novel energy-absorbing method is supplied.

The present invention can be achieved by following technical solution:

The present invention relates to a kind of energy-absorbing methods based on hybrid cross-linked dynamic aggregation object, and it is poly- to provide a kind of hybrid cross-linked dynamic Object or its composition are closed, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object, contains The covalent cross-linking and at least one second group of supermolecular mechanism that formed by covalent bond and optional first group of supermolecular mechanism；Its In, it is more than the gel point that covalent cross-linking reaches covalent cross-linking at least one cross-linked network；Wherein, second group of oversubscription Son effect includes ionization, ion-dipole effect, Host-guest effect, close metal function, dipole-dipole effect, halogen key Effect, cation-π effect, anion-π effect, benzene-fluorobenzene effect, the effect of π-π stacking, ion hydrogen bond action, free radical sun Ion dimerization, first group of supermolecular mechanism include hydrogen bond action, metal-ligand effect.

A preferred embodiment (the first polymer network structure) according to the present invention provides a kind of hybrid cross-linked dynamic State polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and simultaneously containing covalent cross-linking and at least one second group of supermolecular mechanism in this cross-linked network Crosslinking, wherein the degree of cross linking of covalent cross-linking more than its gel point, supermolecule provided by second group of supermolecular mechanism crosslinking The degree of cross linking is in its gel point above and below.

Another preferred embodiment (second polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object is only Make simultaneously containing covalent cross-linking and at least one second group of supermolecule containing a cross-linked network, and in this cross-linked network With crosslinking and at least one first group of supermolecular mechanism crosslinking, wherein the degree of cross linking of covalent cross-linking is more than its gel point, and second The degree of cross linking of supermolecule crosslinking is in its gel point above and below, first group of supermolecular mechanism institute provided by group supermolecular mechanism The degree of cross linking of the supermolecular mechanism crosslinking of offer is in its gel point above and below.

Another preferred embodiment (the third polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, one of cross-linked network contains covalent cross-linking simultaneously and at least one second group of supermolecular mechanism is handed over Connection, wherein the degree of cross linking of covalent cross-linking is more than its gel point, the friendship of the crosslinking of supermolecule provided by second group of supermolecular mechanism Connection degree is in its gel point above and below；Another cross-linked network only contains at least one first group of supermolecular mechanism, wherein The degree of cross linking of the crosslinking of supermolecule provided by least one first group of supermolecular mechanism is more than its gel point.

Another preferred embodiment (the 4th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking its gel point with On；Another cross-linked network contains at least one second group of supermolecular mechanism, wherein at least one second group of supermolecular mechanism The degree of cross linking of provided supermolecule crosslinking is more than its gel point.

Another preferred embodiment (the 5th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, one of cross-linked network contains the degree of cross linking of covalent cross-linking and covalent cross-linking more than its gel point； Another cross-linked network contains at least one second group of supermolecular mechanism, wherein at least one second group of supermolecular mechanism institute The degree of cross linking of the supermolecule crosslinking of offer is more than its gel point；Simultaneously also containing at least one at least one cross-linked network First group of supermolecular mechanism, wherein supermolecule provided by first group of supermolecular mechanism crosslinking the degree of cross linking its gel point with It is upper or following.

Another preferred embodiment (the 6th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are three cross-linked network, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking its gel point with On；Another cross-linked network only contains at least one second group of supermolecular mechanism crosslinking, wherein at least one second group of oversubscription Son acts on the degree of cross linking of provided supermolecule crosslinking more than its gel point；Third cross-linked network only contains at least one the One group of supermolecular mechanism crosslinking, wherein the degree of cross linking of the crosslinking of supermolecule provided by least one first group of supermolecular mechanism exists It is more than its gel point.

Another preferred embodiment (the 7th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking its gel point with On；Another cross-linked network is simultaneously containing covalent cross-linking and the crosslinking of at least one second group of supermolecular mechanism and covalent cross-linking The degree of cross linking is more than its gel point, wherein the degree of cross linking of the crosslinking of supermolecule provided by second group of supermolecular mechanism is in its gel Point above and below.

Another preferred embodiment (the 8th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, one of cross-linked network contains the degree of cross linking of covalent cross-linking and covalent cross-linking more than its gel point； Another cross-linked network is simultaneously containing covalent cross-linking and the crosslinking of at least one second group of supermolecular mechanism and the friendship of covalent cross-linking Connection degree is more than its gel point, wherein the degree of cross linking of the crosslinking of supermolecule provided by second group of supermolecular mechanism is in its gel point Above and below；Simultaneously also containing at least one first group of supermolecular mechanism at least one cross-linked network, wherein first group The degree of cross linking of the crosslinking of supermolecular mechanism provided by supermolecular mechanism is in its gel point above and below.

Another preferred embodiment (the 9th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one crosslinking Network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and disperses in wherein at least one network The noncrosslinking supermolecule polymer containing at least one second group of supermolecular mechanism.

Another preferred embodiment (the tenth kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one crosslinking Network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and disperses in wherein at least one network It is noncrosslinking contain the supermolecule of at least one second group of supermolecular mechanism and at least one first group of supermolecular mechanism polymerization Object.

Another preferred embodiment (a kind of the tenth polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one friendship Networking network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and divide in wherein at least one network Dissipate the existing cross-linked polymer for containing at least one second group of supermolecular mechanism in granular form.

Another preferred embodiment (the 12nd kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one friendship Networking network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and divide in wherein at least one network It dissipates existing containing at least one second group of supermolecular mechanism and at least one first group of supermolecular mechanism in granular form Cross-linked polymer.

Another preferred embodiment (the 13rd kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and acted on simultaneously containing covalent cross-linking and ion-dipole in this cross-linked network, wherein covalently For the degree of cross linking of crosslinking more than its gel point, ion-dipole acts on the degree of cross linking of provided supermolecule crosslinking in its gel point Above and below.

Another preferred embodiment (the 14th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and contain covalent cross-linking and ionization simultaneously in this cross-linked network, wherein covalent cross-linking The degree of cross linking more than its gel point, supermolecular mechanism provided by ionization crosslinking the degree of cross linking more than its gel point or with Under.

Another preferred embodiment (the 15th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and contains covalent cross-linking and ion-dipole simultaneously in this cross-linked network Effect and ionization, wherein for the degree of cross linking of covalent cross-linking more than its gel point, ion-dipole acts on provided oversubscription The degree of cross linking of son crosslinking is in its gel point above and below, and the degree of cross linking of the crosslinking of supermolecular mechanism provided by ionization is at it Gel point above and below.

Another preferred embodiment (the 16th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and acted on simultaneously containing covalent cross-linking and dipole-dipole in this cross-linked network, wherein covalently For the degree of cross linking of crosslinking more than its gel point, the degree of cross linking that dipole-dipole acts on provided supermolecular mechanism crosslinking is solidifying at it Glue point above and below.

Another preferred embodiment (the 17th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object Only contain a cross-linked network, and simultaneously containing covalent cross-linking and ion-dipole effect and dipole-in this cross-linked network Dipole effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, ion-dipole acts on provided supermolecule crosslinking The degree of cross linking in its gel point above and below, dipole-dipole act on provided by supermolecular mechanism crosslinking the degree of cross linking at it Gel point above and below.

Another preferred embodiment (the 18th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object Only contain a cross-linked network, and simultaneously containing covalent cross-linking and ion-dipole effect and metal-in this cross-linked network Ligand effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, ion-dipole acts on provided supermolecule crosslinking The degree of cross linking in its gel point above and below, metal-ligand act on provided by supermolecular mechanism crosslinking the degree of cross linking at it Gel point above and below.

Another preferred embodiment (the 19th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object Only contain a cross-linked network, and simultaneously containing covalent cross-linking and ion-dipole effect and hydrogen bond in this cross-linked network Effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, ion-dipole acts on the friendship of provided supermolecule crosslinking Connection degree is in its gel point above and below, and the degree of cross linking of the crosslinking of supermolecular mechanism provided by hydrogen bond action is more than its gel point Or it is following.

Another preferred embodiment (the 20th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object Only contain a cross-linked network, and acted on simultaneously containing covalent cross-linking and Host-guest in this cross-linked network, wherein For the degree of cross linking of covalent cross-linking more than its gel point, the degree of cross linking that Host-guest acts on provided supermolecule crosslinking is solidifying at it Glue point above and below.

Another preferred embodiment (a kind of the 20th polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and ion-dipole effect and master in this cross-linked network Body-object effect, wherein more than its gel point, ion-dipole acts on provided supermolecule and hands over the degree of cross linking of covalent cross-linking In its gel point above and below, the degree of cross linking that Host-guest acts on provided supermolecular mechanism crosslinking exists the degree of cross linking of connection Its gel point above and below.

Another preferred embodiment (the 22nd kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and Host-guest effect and hydrogen in this cross-linked network Key effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, Host-guest acts on provided supermolecule crosslinking The degree of cross linking in its gel point above and below, the degree of cross linking of the crosslinking of supermolecular mechanism provided by hydrogen bond action its gel point with It is upper or following.

Another preferred embodiment (the 23rd kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and Host-guest effect and gold in this cross-linked network Category-ligand effect, wherein more than its gel point, Host-guest acts on provided supermolecule and hands over the degree of cross linking of covalent cross-linking In its gel point above and below, the degree of cross linking that metal-ligand acts on provided supermolecular mechanism crosslinking exists the degree of cross linking of connection Its gel point above and below.

Another preferred embodiment (the 24th kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and in this cross-linked network simultaneously containing covalent cross-linking and Host-guest effect and from Sub- hydrogen bond action, wherein more than its gel point, Host-guest acts on provided supermolecule and hands over the degree of cross linking of covalent cross-linking The degree of cross linking of connection is in its gel point above and below, and the degree of cross linking of the crosslinking of supermolecular mechanism provided by ion hydrogen bond action is at it Gel point above and below.

Another preferred embodiment (the 25th kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and acts on simultaneously containing covalent cross-linking and π-π stacking in this cross-linked network, wherein For the degree of cross linking of covalent cross-linking more than its gel point, π-π stacking acts on the degree of cross linking of provided supermolecule crosslinking in its gel Point above and below.

Another preferred embodiment (the 26th kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and the effect of π-π stacking and ion-in this cross-linked network Dipole effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, π-π stacking acts on provided supermolecule crosslinking For the degree of cross linking in its gel point above and below, ion-dipole acts on the degree of cross linking of provided supermolecule crosslinking in its gel point Above and below.

Another preferred embodiment (the 27th kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and the effect of π-π stacking and main body-in this cross-linked network Object effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, π-π stacking acts on provided supermolecule crosslinking For the degree of cross linking in its gel point above and below, Host-guest acts on the degree of cross linking of provided supermolecule crosslinking in its gel point Above and below.

Another preferred embodiment (the 28th kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and the effect of π-π stacking and hydrogen bond in this cross-linked network Effect, and the effect of π-π stacking and hydrogen bond action are mutually indepedent；Wherein, the degree of cross linking of covalent cross-linking is more than its gel point, π-π Stacking act on provided by supermolecule crosslinking the degree of cross linking in its gel point above and below, supermolecule provided by hydrogen bond action The degree of cross linking of crosslinking is in its gel point above and below.

Another preferred embodiment (the 29th kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and the effect of π-π stacking and metal-in this cross-linked network Ligand effect, and the effect of π-π stacking and metal-ligand effect are mutually indepedent；Wherein, the degree of cross linking of covalent cross-linking is in its gel point More than, π-π stacking acts on the degree of cross linking of provided supermolecule crosslinking in its gel point above and below, metal-ligand effect The degree of cross linking of provided supermolecule crosslinking is in its gel point above and below.

Another preferred embodiment (the 30th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object Only contain a cross-linked network, and simultaneously containing covalent cross-linking and the effect of π-π stacking and ionic hydrogen in this cross-linked network Key effect, and the effect of π-π stacking and ion hydrogen bond action are mutually indepedent；Wherein, the degree of cross linking of covalent cross-linking its gel point with On, π-π stacking acts on the degree of cross linking of provided supermolecule crosslinking in its gel point above and below, and ion hydrogen bond action is mentioned The degree of cross linking of the supermolecule crosslinking of confession is in its gel point above and below.

In addition to the embodiment of above-mentioned hybridization network structure, the present invention can also have other diversified hybridization network knots Structure embodiment, can contain in an embodiment there are three or the above identical or different network, can in the same network To contain different covalent cross-linkings and/or different supermolecular mechanisms.Those skilled in the art according to the present invention can patrol Volume and train of thought, rationally and effectively realize.

In embodiments of the present invention, the ionization refers at least containing one in dynamic aggregation object structure To the ionic group of oppositely charged, ionization is formed by Coulomb force between cation group and anion group.

In embodiments of the present invention, ion-dipole effect refers to the atom different when two kinds of electronegativity When bonding, since electronegativity makes distribution of charges uneven compared with the inducing action of thick atom, lead to the mal-distribution of electronics, produces Raw eelctric dipole, the eelctric dipole and electrically charged ionic group interact, and form ion-dipole effect.

In embodiments of the present invention, the main body (being indicated with H) in the host-guest interaction is that one kind can be realized The compound (macromolecular or inorganic organic ion skeleton) with hole of molecular recognition；Object (being indicated with G) is that one kind can be by Main body identifies and is embedded in the compound in the hole of main body (small molecule or ion cluster).One host molecule can identify that bonding is more A guest molecule, in embodiments of the present invention, a preferably host molecule at most with two guest molecule phase recognition reactions. The host molecule includes but are not limited to the host molecule and includes but are not limited to ether (including crown ether, cave ether, ball Ether, hemisphere ether, pod-like ether, lasso trick ether, benzo-crown ether, miscellaneous crown ether, miscellaneous cave ether, mixing cave ether), cyclodextrin, ring be luxuriant, Cucurbituril, Calixarenes, column aromatic hydrocarbons and suitable inorganic organic ion skeleton.The guest molecule include but are not limited to long chain alkane, It is cycloalkane, heterocycloalkane, aromatic hydrocarbons, heteroaryl hydrocarbon, condensed cyclic structure compound, heterocycle structure compound, single ring architecture compound, polycyclic Structural compounds, spirane structure compound, caged scaffold compound, suitable ion cluster.

In embodiments of the present invention, the close metal function refers to that when two outermost electron structures be d¹⁰ Or d⁸Generate interaction force when metal ion is close to less than the sum of its van der Waals radius, form close metal function.

In embodiments of the present invention, dipole-dipole effect refers to the atom different when two kinds of electronegativity When bonding, since electronegativity makes distribution of charges uneven compared with the inducing action of thick atom, lead to the mal-distribution of electronics, produces Eelctric dipole is given birth to, is interacted between two eelctric dipoles, dipole-dipole effect is formed.

In embodiments of the present invention, the halogen bond effect is referred to by halogen atom or lewis acid and neutrality Or the noncovalent interaction formed between electronegative lewis base.

In embodiments of the present invention, cation-π effect is referred to by the π of cation and armaticity system The noncovalent interaction formed between electron system.

In embodiments of the present invention, anion-π effect, refers to by anion and electron-deficient aromatic π body The noncovalent interaction formed between system.

In embodiments of the present invention, the benzene-fluorobenzene effect, refers to by leading between aromatic hydrocarbons and more fluorinated aromatic hydrocarbons It crosses dispersion force and quadrupole moment acts on the noncovalent interaction collectively constituted.

In embodiments of the present invention, the described π-π stacking effect refers in dynamic aggregation object containing being capable of providing The structure of pi bond electron cloud is acted on by the mutual overlapping π-π stacking that formed of pi bond electron cloud.

In embodiments of the present invention, the ion hydrogen bond action, by the radical cation that can form hydrogen bond action Group and anion group are constituted, the coulomb interaction being formed simultaneously between hydrogen bond action and negative ions, or by that can form hydrogen bond action Positive/negative ionic group and neutral hydrogen bond group constitute, be formed simultaneously between hydrogen bond action and positive/negative ion and neutral group from Son-dipole effect.

In embodiments of the present invention, the radical cation dimerization, construction unit are to contain simultaneously The group of free radical and cation.

In embodiments of the present invention, the hydrogen bond action, the hydrogen bond group preferably comprise with flowering structure at Point:

At least one of further preferably following constituent:

Wherein,Indicate with polymer chain, crosslinking link or any other suitable group/atom (including hydrogen original Son) connection.

In embodiments of the present invention, metal-ligand effect, the ligand groups (being indicated with L) are selected from ring Pentadiene and the structural unit for containing at least one coordination atom (indicating with A).One coordination atom can with one or Multiple metal centers (include but are not limited to metal ion, the metal center of metallo-chelate, metal-organic metal Metal center in center, metal inorganic compound, is indicated with M) one or more coordinate bonds are formed, a metal center can also To form one or more coordinate bond with one or more coordination atom.One ligand groups is matched with what metal center was formed The quantity of position key is known as the numbers of teeth of ligand groups, and in embodiments of the present invention, in the same system, metal center can be with One of one tooth ligand, bidentate ligand, tridentate ligand or multiple ligands form metal-ligand effect, go back between different ligands Cyclization may be connected by metal center, therefore the present invention can effectively provide type, quantity and performance dynamic abundant enough Property metal-ligand effect, structure shown in the following general formula is some to provide example, but the present invention is not limited only to this:

Wherein, A is coordination atom, and M is metal center, and each ligand groups and metal center are formed by an A-M key For a tooth, A, which is connected, with singly-bound in formula indicates that the coordination atom belongs to the same ligand groups, when in a ligand groups When containing two or more coordination atoms, A can be identical atom and be also possible to different atoms, including but not only limit In boron, nitrogen, oxygen, sulphur, phosphorus, silicon, arsenic, selenium, tellurium；It is preferred that boron, nitrogen, oxygen, sulphur, phosphorus；More preferable nitrogen, oxygen；Nitrogen.It needs to illustrate , A exists in the form of anion sometimes；It is cyclopentadiene ligand.In the present invention, it is preferred to which a coordination atom is only A coordinate bond is formed with a metal center, therefore the quantity of the coordination atom contained in ligand groups is ligand groups The number of teeth.The metal-ligand that the ligand groups and metal center are formed acts on (with M-L_xIt indicates, in x expression and the same metal The quantity of the ligand groups of heart phase separation) power and the type and quantity of coordination atom in ligand groups, metal center Type and valence state and ion pair etc. are related.

The metal center M can be the metal center of any appropriate metal ion or compound/chelate etc., It can be selected from any appropriate ionic species of any one metal, compound/chelate and combinations thereof in the periodic table of elements.

In embodiments of the present invention, the effect group for providing the supermolecular mechanism may be at dynamic aggregation object In any appropriate position, including any place in dynamic aggregation object chain backbone (including side chain/branch/bifurcated chain), side group, end group Or the supermolecular mechanism formed between the supermolecular mechanism group of many places.

In embodiments of the present invention, a kind of hybrid cross-linked dynamic aggregation object or its composition are provided, and using it as suction It can material progress energy-absorbing；Wherein, the hybrid cross-linked dynamic aggregation object form can be ordinary solid, gel (including water-setting Glue, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid swell gel), elastomer, foamed material Deng.

In embodiments of the present invention, it is poly- to constitute dynamic for a kind of energy-absorbing method based on hybrid cross-linked dynamic aggregation object Close that the raw material components of object further include following any or any two can additive: other polymers, auxiliary agent, filler；

Wherein, addible other polymers are selected from following any or appoint several: natural polymer, synthesis tree Rouge, synthetic rubber, synthetic fibers；

Wherein, addible auxiliary agent is selected from following any or appoints several: catalyst, initiator, antioxidant, light are stablized Agent, heat stabilizer, chain extender, toughener, coupling agent, lubricant, release agent, plasticizer, foaming agent, antistatic agent, emulsifier, Dispersing agent, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickener, levelling agent, antibacterial agent；

Wherein, addible filler be selected from it is following any or appoint several fillers: inorganic non-metallic filler, metal packing, Organic filler.

The energy-absorbing method based on hybrid cross-linked dynamic aggregation object in embodiments of the present invention, can be applied to prevent Quick-fried, defense of resistance to impact, sound insulation, noise elimination, damping, vibration damping, damping, buffering.

Compared with prior art, the invention has the following advantages:

(1) in energy-absorbing method provided by the invention, for the hybrid cross-linked dynamic aggregation object of energy-absorbing, contained by it is super The dynamic of molecular action is strong, energy-absorbing effect is prominent.Supermolecular mechanism can rely on its higher dynamic reversibility and stress Sensibility enables cross-linked polymer to make a response in time, promptly to external force, so that the energy-absorbing for preferably promoting material is special Property.By the strong dynamic based at least one supermolecular mechanism, polymer can show sensitive and regulatable dilatant Property, it both can produce pure viscosity enhancing, and also can produce from creep properties to elastomeric transformation, greatly improve to impact energy The absorption and dispersibility of amount, to reach excellent shock resistance effect；And the presence of covalent cross-linking, so that polymer has certainly Supportive has excellent practicability.Further, since supermolecular mechanism is reversible, it is recoverable, and impart polymeric material Material is with good durability, and after the releasing of extraneous impact stress, supermolecular mechanism can be bonded again again, so that dynamic aggregation object It still is able to maintain higher energy-absorbing effect after this multiple use, this is also that it is had compared with existing energy-absorbing method and technology Some huge advantages, this is difficult to realize in existing polymeric system.

(2) in energy-absorbing method provided by the invention, for the hybrid cross-linked dynamic aggregation object of energy-absorbing, component structure is rich Richness, performance multiplicity, raw material sources are extensive, and Modulatory character is strong.Combined in dynamic aggregation object structure second group of supermolecular mechanism, Covalent cross-linking and optional first group of effect will carry out sufficient utilization and combination the advantages of various effects, keep dynamic poly- Object is closed in addition to there is the dynamic for usually containing supermolecular mechanism polymer and generally having, self-repairability, repeatable processability, There is also various other performances: such as the directionality of halogen bond effect, cation-π effect, anion-π effect, Host-guest effect In to small molecule/controllable selectivity of ion/group and controllable identity, benzene-fluorobenzene effect, the effect of π-π stacking order, Ionization, ion-dipole effect, the pH of ion hydrogen bond action, concentration sensitive, electric conductivity, the temperature of dipole-dipole effect Sensibility, the characteristics such as special photo electric of close metal interaction, radical cation dimerization can according to demand rationally Supermolecular mechanism group/unit is selected to carry out MOLECULE DESIGN.It is unique that material is assigned on the basis of with good energy absorption performance Functional characteristic.In addition, the dynamic sex differernce based on different types of supermolecular mechanism, can obtain structure more horn of plenty, performance More various, dynamic reversible effect has more the energy-absorbing material of hierarchy.

(3) in the present invention dynamic aggregation object dynamic effect is good, dynamic condition is mild.Compared to other dynamic systems, Dynamic aggregation object provided by the invention can dynamically gather without catalyst, without realizing under conditions of high temperature, illumination or specific pH The synthesis and dynamic reversibility for closing object also reduce the limitation of use environment, extend while improving preparation efficiency The application range of polymer.In addition, other additives can also be added according to actual needs during the preparation process to dynamic aggregation object Material is modified, and extends the application performance of material.

With reference to following embodiments explanation, embodiment and the appended claims, these and other features of the invention with And advantage will become obvious.

Specific embodiment

The present invention relates to a kind of energy-absorbing methods based on hybrid cross-linked dynamic aggregation object, and it is poly- to provide a kind of hybrid cross-linked dynamic Object or its composition are closed, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object, contains The covalent cross-linking and at least one second group of supermolecular mechanism that formed by covalent bond and optional first group of supermolecular mechanism；Its In, it is more than the gel point that covalent cross-linking reaches covalent cross-linking at least one cross-linked network；Wherein, second group of supermolecular mechanism Include but are not limited to ionization, ion-dipole effect, Host-guest effect, close metal function, dipole-dipole effect, Halogen bond effect, cation-π effect, anion-π effect, benzene-fluorobenzene effect, the effect of π-π stacking, ion hydrogen bond action, freedom Base cation dimerization, first group of supermolecular mechanism include hydrogen bond action, metal-ligand effect.

In the present invention, for describing the quantifier " kind " of different structure, " class ", the range organized in " group " are greater than class, the model of class Enclose and be greater than kind, i.e. a group can have many classes, one kind can there are many kinds of.Even if the supermolecular mechanism has same Primitive structure, but because of the differences such as linker, substituent group, isomers, it is also possible to lead to the difference of its performance.In the present invention, The supermolecule with same primitive structure is usually considered as same structure；If because of differences such as linker, substituent group, isomers And lead to the difference of performance, still it is considered as same structure.The present invention, which can according to need, reasonably to be designed, selected and is adjusted Control, obtains optimal performance, this is also advantage of the invention.In the present invention, it is preferred to using inhomogeneous structure, so as to more preferable Ground carries out orthogonality regulation.

Term " energy-absorbing " used refers to for caused by the forms such as shock, vibration, vibration, explosion, sound in the present invention The absorption of energy that generates of physical impact, but do not include the only absorption to thermal energy and/or electric energy.

Term " polymerization " reaction/action used refers to the reactant of lower molecular weight if not otherwise indicated in the present invention Propagation process/the effect with the product of higher molecular weight is formed by reaction formations such as polycondensation, addition polymerization, ring-opening polymerisations.Its In, reactant can be that (can spontaneously be polymerize with polymerizing power, or in initiator or can add outside and can act on It is lower to be polymerize) the compounds such as monomer, oligomer, prepolymer.It is referred to as equal by a kind of product that reactant is polymerize Polymers.Copolymer is known as by the product that two or more reactant is polymerize.Described in the present invention is " poly- Close " comprising linear growth process, branching process, annulation process and cross-linking process of reactant molecule chain etc.；In the present invention Embodiment in, " polymerization " includes propagation process caused by bonding and noncovalent interaction as covalent bond.

Term " crosslinking " reaction/action used in the present invention, if not otherwise indicated, refer between reactant molecule and/or The physical action of chemical bonds and metal-ligand effect and/or hydrogen bond action in reactant molecule between covalent bond forms tool There is the process of three-dimensional unlimited reticular pattern product.In cross-linking process, polymer chain is general first to be increased in two-dimensional/three-dimensional direction It is long, two dimension or three-dimensional cluster are gradually formed, developing deeply is three-dimensional infinite network structure.It should be noted that the friendship in the present invention It is coupled structure, refers in particular to the three-dimensional infinite network structure of gel point or more (containing gel point, similarly hereinafter), and non-crosslinking structure then refers to The structures such as line style, ring-type, branching and gel point two dimension below, three-dimensional cluster structure.Heretofore described " gel point " (also referred to as percolation threshold) refers to reactant in cross-linking process, and viscosity is uprushed, and starts gel phenomenon occur, opens for the first time Begin to be crosslinked reflecting point when reaching a three-dimensional infinite network.Cross-linking products more than gel point (containing gel point), tool There is three-dimensional infinite network structure, cross-linked network constitutes an entirety and across entire polymer architecture, and cross-linked structure is relatively stable With it is secured；In gel point cross-linking products below, and not formed three-dimensional infinite network structure, and be not belonging to across entire polymerization The cross-linked network that can constitute an entirety of object structure.When there are a variety of crosslinked actions, except covalent cross-linking is at least one It is outer to reach its gel point or more in network, other crosslinked actions can be in its gel point above and below.

In embodiments of the present invention, covalent cross-linking can have one or more than one kinds of, also can be using any Suitable covalent cross-linking chemical structure, topological structure, degree of cross linking and combinations thereof.In embodiments of the present invention, cross-linked network There can be at least one, namely can be single one network, there can also be the multiple networks being mutually blended, there can also be interpenetrating Multiple networks.But in embodiments of the present invention, the covalent cross-linking must reach covalent at least one network It is more than the gel point of crosslinking.In this way, can just guarantee all to dissociate even if in supermolecular mechanism for polymer of the invention In the case where, polymer can also keep balanced structure, namely can be the insoluble structure not melted in the normal state.It removes Outside covalent cross-linking network, polymer, small point can also be included but are not limited to containing other crosslinkings or noncrosslinking ingredient Son, inorganic material ingredient；Wherein the topological structure of component of polymer may include but be not limited only to line style, branching, ring-type, group Cluster, crosslinking.

In embodiments of the present invention, supermolecular mechanism by any suitable location in dynamic aggregation object includes but not only It is limited to polymer backbone, side group, the supermolecular mechanism group in end group/unit interaction and realizes.And any position Supermolecular mechanism in chain can be formed between supermolecular mechanism group under certain condition, supermolecular mechanism is not direct in such chain Crosslinked action is generated, but if generating nested rings can then cause to be crosslinked.In addition, in the present invention under normal conditions, by bone Polymer can be caused to form microphase-separated, skeleton oversubscription under the supermolecular mechanism certain condition that frame supermolecular mechanism group provides Son effect is present in hard phase and constitutes strong non-covalent together with hard phase, on the one hand play increase balanced structure stability and On the other hand the effect of mechanical strength promotes toughness based on its non-covalent character.In the present invention, same polymer chain/molecule/ May exist one or a supermolecular mechanism equivalent in meaning or different in network, the supermolecule in any one network is made With can be in any crosslinking degree.

In embodiments of the present invention, the skeleton supermolecular mechanism group/unit, refers in the group/unit At least one atom directly participate in the continuous main polymer chain of building or main polymer chain or crosslinking on cross-linked network skeleton Link；The side group supermolecular mechanism group/unit, refers to all atoms on the group/unit in side group；It is described End group supermolecular mechanism group/unit, refer to all atoms on the group/unit on end group.The skeleton oversubscription Son effect group/unit can be to be generated in polymer polymerizing/cross-linking process, namely by forming the supermolecular mechanism base Group/unit and generate polymerized/cross-linked；It is also possible to pre-generate and carries out polymerized/cross-linked again；It is preferred that pre-generated.The side group Supermolecular mechanism group/unit can before polymerized/cross-linked, later or in the process generate, before or after the number that generates Amount can be than relatively freely controlling.

In the present invention, " main polymer chain " refers to having most in polymer architecture if not otherwise indicated The chain of multichain joint number." side chain " refers in polymer architecture with main polymer chain skeleton/cross-linked network chain backbone The molecular weight for being connected and being distributed in its skeleton side is more than the chain structure of 1000Da；Wherein, the branch, bifurcated chain refer to It is the link that the molecular weight come out from main polymer chain skeleton/cross-linked network chain backbone or any other chain bifurcated is more than 1000Da Structure；For the sake of simplicity, the molecular weight of side chain, branch, bifurcated chain if not otherwise indicated, is then collectively referred to as side when being more than 1000Da Chain." side group ", refer to being connected in polymer architecture with main polymer chain skeleton/cross-linked network main chain backbone and Chemical group of the molecular weight not higher than 1000Da and molecular weight that are distributed in main chain backbone side are not higher than the short-side chain of 1000Da. For side chain and side group, can have multilevel structure namely side chain that can continue with side group and side chain, the side chain of side chain can be with Continue have side group and side chain, side chain therein also includes branch and bifurcated chain isodesmic structure." end group " is referred to poly- Close the chemical group for being connected and being located at chain backbone end in object structure with polymer chain skeleton；In the present invention, under specific condition Side group can also have end group.

A preferred embodiment (the first polymer network structure) according to the present invention provides a kind of hybrid cross-linked dynamic State polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and simultaneously containing covalent cross-linking and at least one second group of supermolecular mechanism in this cross-linked network Crosslinking, wherein the degree of cross linking of covalent cross-linking more than its gel point, supermolecule provided by second group of supermolecular mechanism crosslinking The degree of cross linking is in its gel point above and below.For the embodiment, only contain a cross-linked network, the covalent friendship in system It is combined in providing balanced structure, passes through the dynamic and dilatancy realization energy-absorbing effect of second group of supermolecular mechanism；And it is making It is standby more convenient.

Another preferred embodiment (second polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object is only Make simultaneously containing covalent cross-linking and at least one second group of supermolecule containing a cross-linked network, and in this cross-linked network With crosslinking and at least one first group of supermolecular mechanism crosslinking, wherein the degree of cross linking of covalent cross-linking is more than its gel point, and second The degree of cross linking of supermolecule crosslinking is in its gel point above and below, first group of supermolecular mechanism institute provided by group supermolecular mechanism The degree of cross linking of the supermolecular mechanism crosslinking of offer is in its gel point above and below.In this embodiment, by single friendship First group of supermolecular mechanism is introduced in connection network structure, a supplement as second group of supermolecular mechanism is made it possible to, makes It obtains polymer and reflects dynamic reversible and energy-absorbing effect with hierarchy.

Another preferred embodiment (the third polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, one of cross-linked network contains covalent cross-linking simultaneously and at least one second group of supermolecular mechanism is handed over Connection, wherein the degree of cross linking of covalent cross-linking is more than its gel point, the friendship of the crosslinking of supermolecule provided by second group of supermolecular mechanism Connection degree is in its gel point above and below；Another cross-linked network only contains at least one first group of supermolecular mechanism, wherein The degree of cross linking of the crosslinking of supermolecule provided by least one first group of supermolecular mechanism is more than its gel point.Preferably In, by additionally introducing independent first group of supermolecular mechanism cross-linked network, make it possible to as second group of supermolecular mechanism One supplement of dynamic, so that polymer reflects dynamic reversible and energy-absorbing effect with hierarchy.

Another preferred embodiment (the 4th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking its gel point with On；Another cross-linked network contains at least one second group of supermolecular mechanism, wherein at least one second group of supermolecular mechanism The degree of cross linking of provided supermolecule crosslinking is more than its gel point.In this embodiment, covalent cross-linking network is responsible for holding Balanced structure, the network based on second group of supermolecular mechanism are responsible for providing dynamic property, covalent cross-linking network and second group of oversubscription The advantages of son effect network can form interpenetrating or semi-intercrossing network, make full use of the two, reaches collaboration and/or orthogonal energy-absorbing Effect.

Another preferred embodiment (the 5th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, one of cross-linked network contains the degree of cross linking of covalent cross-linking and covalent cross-linking more than its gel point； Another cross-linked network contains at least one second group of supermolecular mechanism, wherein at least one second group of supermolecular mechanism institute The degree of cross linking of the supermolecule crosslinking of offer is more than its gel point；Simultaneously also containing at least one at least one cross-linked network First group of supermolecular mechanism, wherein supermolecule provided by first group of supermolecular mechanism crosslinking the degree of cross linking its gel point with It is upper or following.In this embodiment, second group of Supramolecular Network and covalent cross-linking network be directly in the same network, and And the first group of supermolecular mechanism introduced can also make the dynamic ability of regulation and control of polymer stronger, synergy is more preferable.

Another preferred embodiment (the 6th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are three cross-linked network, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking its gel point with On；Another cross-linked network only contains at least one second group of supermolecular mechanism crosslinking, wherein at least one second group of oversubscription Son acts on the degree of cross linking of provided supermolecule crosslinking more than its gel point；Third cross-linked network only contains at least one the One group of supermolecular mechanism crosslinking, wherein the degree of cross linking of the crosslinking of supermolecule provided by least one first group of supermolecular mechanism exists It is more than its gel point.In this embodiment, second group of supermolecular mechanism cross-linked network, first group of supermolecular mechanism cross-linked network Network, covalent cross-linking network are respectively individually present, to be made using the difference of dynamic and stability between different cross-linked networks Dynamic aggregation object reveals different orthogonality and concertedness, reaches better energy-absorbing effect.

Another preferred embodiment (the 7th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking its gel point with On；Another cross-linked network is simultaneously containing covalent cross-linking and the crosslinking of at least one second group of supermolecular mechanism and covalent cross-linking The degree of cross linking is more than its gel point, wherein the degree of cross linking of the crosslinking of supermolecule provided by second group of supermolecular mechanism is in its gel Point above and below.In this embodiment, by controlling the structure of two covalent cross-linking networks, it is dynamic to can achieve Reasonable Regulation And Control The purpose of state polymer balanced structure and mechanical property.

Another preferred embodiment (the 8th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, one of cross-linked network contains the degree of cross linking of covalent cross-linking and covalent cross-linking more than its gel point； Another cross-linked network is simultaneously containing covalent cross-linking and the crosslinking of at least one second group of supermolecular mechanism and the friendship of covalent cross-linking Connection degree is more than its gel point, wherein the degree of cross linking of the crosslinking of supermolecule provided by second group of supermolecular mechanism is in its gel point Above and below；Simultaneously also containing at least one first group of supermolecular mechanism at least one cross-linked network, wherein first group The degree of cross linking of the crosslinking of supermolecular mechanism provided by supermolecular mechanism is in its gel point above and below.In this embodiment, By controlling the structure of two covalent cross-linking networks, Reasonable Regulation And Control dynamic aggregation object balanced structure and mechanical property can achieve Purpose, and the first group of supermolecular mechanism introduced can also make the dynamic ability of regulation and control of polymer stronger, collaboration and energy-absorbing Effect is more preferable.

Another preferred embodiment (the 9th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one crosslinking Network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and disperses in wherein at least one network The noncrosslinking supermolecule polymer containing at least one second group of supermolecular mechanism.It is described super containing at least one second group The non-crosslinked supermolecule polymer of molecular action does not generate the transformation of visco-elastic when by physical impact, can be more The consume of energy is carried out, energy absorption performance is improved.

Another preferred embodiment (the tenth kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one crosslinking Network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and disperses in wherein at least one network It is noncrosslinking contain the supermolecule of at least one second group of supermolecular mechanism and at least one first group of supermolecular mechanism polymerization Object.The non-crosslinked supermolecule polymer containing at least one second group of supermolecular mechanism does not produce when by physical impact The transformation of raw visco-elastic, can more carry out the consume of energy, improve energy absorption performance, and the first group of oversubscription introduced Son effect can also make the dynamic ability of regulation and control of polymer stronger, and collaboration and energy-absorbing effect are more preferable.

Another preferred embodiment (a kind of the tenth polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one friendship Networking network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and divide in wherein at least one network Dissipate the existing cross-linked polymer for containing at least one second group of supermolecular mechanism in granular form.It is described existing for particle For cross-linked polymer containing at least one second group of supermolecular mechanism when by physical impact, not generating can be with visco-elastic Change or elasticity enhances, is able to carry out the consume and dispersion of energy, energy absorption performance is strong and has promotion toughness Effect.

Another preferred embodiment (the 12nd kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one friendship Networking network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and divide in wherein at least one network It dissipates existing containing at least one second group of supermolecular mechanism and at least one first group of supermolecular mechanism in granular form Cross-linked polymer.The cross-linked polymer with existing for particle containing at least one second group of supermolecular mechanism is by physics When impact, the consume and dispersion of energy, energy absorption performance can be able to carry out with visco-elastic transformation or elasticity enhancing by not generating By force and have the function of promoting toughness, and the first group of supermolecular mechanism introduced can also make the dynamic of polymer Property ability of regulation and control it is stronger, collaboration and energy-absorbing effect it is more preferable.

Another preferred embodiment (the 13rd kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and acted on simultaneously containing covalent cross-linking and ion-dipole in this cross-linked network, wherein covalently For the degree of cross linking of crosslinking more than its gel point, ion-dipole acts on the degree of cross linking of provided supermolecule crosslinking in its gel point Above and below.In this embodiment, only contain a cross-linked network, the covalent cross-linking in system is for providing balance knot Structure makes polymer material can be achieved with dynamic effect at room temperature, without outer by ion-dipole effect dynamic The stimulation on boundary.

Another preferred embodiment (the 14th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and contain covalent cross-linking and ionization simultaneously in this cross-linked network, wherein covalent cross-linking The degree of cross linking more than its gel point, supermolecular mechanism provided by ionization crosslinking the degree of cross linking more than its gel point or with Under.In this embodiment, only contain a cross-linked network, the covalent cross-linking in system passes through for providing balanced structure The dynamic of ionization realizes dynamic effect；Ionization can steadily be present in polymer, and by change from The concentration and type of subbase group can control the power of ionization well；The concentration of salt is higher in system simultaneously When, ionization can be weakened, therefore the power of ionization can also be adjusted by the salinity in adjustment and control system.

Another preferred embodiment (the 15th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and contains covalent cross-linking and ion-dipole simultaneously in this cross-linked network Effect and ionization, wherein for the degree of cross linking of covalent cross-linking more than its gel point, ion-dipole acts on provided oversubscription The degree of cross linking of son crosslinking is in its gel point above and below, and the degree of cross linking of the crosslinking of supermolecular mechanism provided by ionization is at it Gel point above and below.In this embodiment, possessed ionic group is more in dynamic aggregation object, and electric conductivity is more It is good, there is special advantage in preparing fexible conductor and energy storage device material.

Another preferred embodiment (the 16th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and acted on simultaneously containing covalent cross-linking and dipole-dipole in this cross-linked network, wherein covalently For the degree of cross linking of crosslinking more than its gel point, the degree of cross linking that dipole-dipole acts on provided supermolecular mechanism crosslinking is solidifying at it Glue point above and below.In this embodiment, only contain a cross-linked network, the covalent cross-linking in system is flat for providing Weigh structure, realizes dynamic effect by the dynamic of dipole-dipole；Dipole-dipole effect can be stable be present in it is poly- It closes in object, is easy to regulate and control, the pairing for acting on group can produce microdomai pi, make to interact more stable；It is even when temperature is higher The effect of pole-dipole, which can weaken, even to disappear, thus the polymer containing dipole-dipole effect can according to the difference of temperature body Reveal the difference of dynamic.

Another preferred embodiment (the 17th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object Only contain a cross-linked network, and simultaneously containing covalent cross-linking and ion-dipole effect and dipole-in this cross-linked network Dipole effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, ion-dipole acts on provided supermolecule crosslinking The degree of cross linking in its gel point above and below, dipole-dipole act on provided by supermolecular mechanism crosslinking the degree of cross linking at it Gel point above and below.In this embodiment, the active dipole group content of ion-dipole is increased, it will be able to make Standby to go out to act on the dynamic aggregation object with dipole-dipole effect containing ion-dipole simultaneously, preparation is simple, and increased dipole- Dipolar interaction energy further promotes the mechanical property of dynamic aggregation object

Another preferred embodiment (the 18th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object Only contain a cross-linked network, and simultaneously containing covalent cross-linking and ion-dipole effect and metal-in this cross-linked network Ligand effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, ion-dipole acts on provided supermolecule crosslinking The degree of cross linking in its gel point above and below, metal-ligand act on provided by supermolecular mechanism crosslinking the degree of cross linking at it Gel point above and below.In this embodiment, by parameters such as control ligand groups, metal centers, can prepare has Different structure and adjustable, the widely used dynamic aggregation object of appearance features, performance.

Another preferred embodiment (the 19th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object Only contain a cross-linked network, and simultaneously containing covalent cross-linking and ion-dipole effect and hydrogen bond in this cross-linked network Effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, ion-dipole acts on the friendship of provided supermolecule crosslinking Connection degree is in its gel point above and below, and the degree of cross linking of the crosslinking of supermolecular mechanism provided by hydrogen bond action is more than its gel point Or it is following.In this embodiment, since hydrogen bond group has structure diversity, by the type sum number for controlling hydrogen bond group Mesh can be combined collocation and regulation to the dynamic of polymer in a wider context, dynamic with ion-dipole effect based on it The difference of state property can obtain the polymeric material that structure more horn of plenty, performance are more various, dynamic reversible effect has more hierarchy Material.

Another preferred embodiment (the 20th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object Only contain a cross-linked network, and acted on simultaneously containing covalent cross-linking and Host-guest in this cross-linked network, wherein For the degree of cross linking of covalent cross-linking more than its gel point, the degree of cross linking that Host-guest acts on provided supermolecule crosslinking is solidifying at it Glue point above and below.In this embodiment, only contain a cross-linked network, the covalent cross-linking in system is flat for providing Weigh structure, realizes dynamic effect by the dynamic that Host-guest acts on；Host-guest, which acts through, selects different main bodys Molecule and guest molecule can prepare temperature sensitive, photaesthesia, isotope of redox-sensitive, pH sensitivity and electric field-sensitive etc. no With the dynamic aggregation object of sensibility.

Another preferred embodiment (a kind of the 20th polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and ion-dipole effect and master in this cross-linked network Body-object effect, wherein more than its gel point, ion-dipole acts on provided supermolecule and hands over the degree of cross linking of covalent cross-linking In its gel point above and below, the degree of cross linking that Host-guest acts on provided supermolecular mechanism crosslinking exists the degree of cross linking of connection Its gel point above and below.In this embodiment, the environmental sensitivity of Host-guest effect and ion-dipole are acted on Combine, makes dynamic aggregation object obtained that there is good functional characteristic and mechanical stability；

Another preferred embodiment (the 22nd kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and Host-guest effect and hydrogen in this cross-linked network Key effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, Host-guest acts on provided supermolecule crosslinking The degree of cross linking in its gel point above and below, the degree of cross linking of the crosslinking of supermolecular mechanism provided by hydrogen bond action its gel point with It is upper or following.In this embodiment, since hydrogen bond group has structure diversity, by the type sum number for controlling hydrogen bond group Mesh can be combined collocation and regulation to the dynamic of polymer in a wider context, dynamic with Host-guest effect based on it The difference of state property can obtain the polymeric material that structure more horn of plenty, performance are more various, dynamic reversible effect has more hierarchy Material.

Another preferred embodiment (the 23rd kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and Host-guest effect and gold in this cross-linked network Category-ligand effect, wherein more than its gel point, Host-guest acts on provided supermolecule and hands over the degree of cross linking of covalent cross-linking In its gel point above and below, the degree of cross linking that metal-ligand acts on provided supermolecular mechanism crosslinking exists the degree of cross linking of connection Its gel point above and below.In this embodiment, by parameters such as control ligand groups, metal centers, it can prepare and provide There are different structure and adjustable, the widely used dynamic aggregation object of appearance features, performance.

Another preferred embodiment (the 24th kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and in this cross-linked network simultaneously containing covalent cross-linking and Host-guest effect and from Sub- hydrogen bond action, wherein more than its gel point, Host-guest acts on provided supermolecule and hands over the degree of cross linking of covalent cross-linking The degree of cross linking of connection is in its gel point above and below, and the degree of cross linking of the crosslinking of supermolecular mechanism provided by ion hydrogen bond action is at it Gel point above and below.In this embodiment, ion hydrogen bond has very strong sensibility to pH, by control system PH value can be realized the adjusting to dynamic aggregation object dynamic, along with the environmental sensitivity of Host-guest effect, can prepare Provide the dynamic aggregation object of answering property of multiplephase.

Another preferred embodiment (the 25th kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and acts on simultaneously containing covalent cross-linking and π-π stacking in this cross-linked network, wherein For the degree of cross linking of covalent cross-linking more than its gel point, π-π stacking acts on the degree of cross linking of provided supermolecule crosslinking in its gel Point above and below.In this embodiment, only contain a cross-linked network, the covalent cross-linking in system is for providing balance Structure realizes dynamic effect by the dynamic that π-π stacking acts on；When temperature is higher, pi-electron cloud is more active, and π-π is stacked The effect of effect is more obvious, therefore the polymer containing the effect of π-π stacking can adjust it by adjusting the height of temperature Dynamic.

Another preferred embodiment (the 26th kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and the effect of π-π stacking and ion-in this cross-linked network Dipole effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, π-π stacking acts on provided supermolecule crosslinking For the degree of cross linking in its gel point above and below, ion-dipole acts on the degree of cross linking of provided supermolecule crosslinking in its gel point Above and below.In this embodiment, it is realized by the dynamic sex differernce of the effect of π-π stacking and ion-dipole effect orthogonal Cooperate with dynamic effect；It is easy to prepare the dynamic aggregation object with hierarchy dynamic effect.

Another preferred embodiment (the 27th kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and the effect of π-π stacking and main body-in this cross-linked network Object effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, π-π stacking acts on provided supermolecule crosslinking For the degree of cross linking in its gel point above and below, Host-guest acts on the degree of cross linking of provided supermolecule crosslinking in its gel point Above and below.In this embodiment, the environmental sensitivity of Host-guest effect is combined with the effect of π-π stacking, is made Dynamic aggregation object obtained has good functional characteristic and mechanical stability.

Another preferred embodiment (the 28th kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and the effect of π-π stacking and hydrogen bond in this cross-linked network Effect, and the effect of π-π stacking and hydrogen bond action are mutually indepedent；Wherein, the degree of cross linking of covalent cross-linking is more than its gel point, π-π Stacking act on provided by supermolecule crosslinking the degree of cross linking in its gel point above and below, supermolecule provided by hydrogen bond action The degree of cross linking of crosslinking is in its gel point above and below.In this embodiment, since hydrogen bond group has structure diversity, lead to The type and number for crossing control hydrogen bond group, can be combined collocation and tune to the dynamic of polymer in a wider context Control can obtain that structure more horn of plenty, performance be more various, dynamic reversible based on the difference of itself and π-π stacking effect dynamic Effect has more the polymer material of hierarchy.

Another preferred embodiment (the 29th kind of polymer network structure) according to the present invention, provides a kind of hydridization It is crosslinked dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and simultaneously containing covalent cross-linking and the effect of π-π stacking and metal-in this cross-linked network Ligand effect, and the effect of π-π stacking and metal-ligand effect are mutually indepedent；Wherein, the degree of cross linking of covalent cross-linking is in its gel point More than, π-π stacking acts on the degree of cross linking of provided supermolecule crosslinking in its gel point above and below, metal-ligand effect The degree of cross linking of provided supermolecule crosslinking is in its gel point above and below.In this embodiment, by controlling ligand base The parameters such as group, metal center can prepare the dynamic aggregation adjustable, widely used with different structure and appearance features, performance Object.

Another preferred embodiment (the 30th kind of polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object Only contain a cross-linked network, and simultaneously containing covalent cross-linking and the effect of π-π stacking and ionic hydrogen in this cross-linked network Key effect, and the effect of π-π stacking and ion hydrogen bond action are mutually indepedent；Wherein, the degree of cross linking of covalent cross-linking its gel point with On, π-π stacking acts on the degree of cross linking of provided supermolecule crosslinking in its gel point above and below, and ion hydrogen bond action is mentioned The degree of cross linking of the supermolecule crosslinking of confession is in its gel point above and below.In this embodiment, using π-π stacking act on and from Sub- hydrogen bond action can prepare the dynamic aggregation object with multiple sensitizing effect to the special sensibility of varying environment.

The present invention can also have other diversified hybridization network structural implementations, can contain in an embodiment There are three or above identical or different network, can be containing different covalent cross-linking and/or different in the same network First group of supermolecular mechanism, while also optionally containing second group of identical or different supermolecular mechanism.Those skilled in the art Member can rationally and effectively be realized with logic according to the present invention and train of thought.

In embodiments of the present invention, the ionization, at least containing a pair in dynamic aggregation object structure The ionic group of oppositely charged forms ionization by Coulomb force between cation group and anion group.It is described Cation group be a kind of organic group for being easier to receive proton, by way of example, it is included but are not limited to: It is preferred thatThe anion group is a kind of ratio It is easier to lose the organic group of proton, by way of example, it is included but are not limited to:It is preferred thatUnder particular case, cation Group and anion group may be in the same compound structure, such as choline glycerophosphate, 2- methacryloxy The compounds such as Ethylphosphocholine, L-carnitine, methacryloylethyl sulfobetaines.Ionization can steadily exist In polymer, and concentration and type by changing ionic group, the power of ionization can be controlled well System.

In embodiments of the present invention, there is no particular restriction for the combination of cation group and anion group, as long as just Ionic group can form suitable ionization with anion group.Some suitable combinations can be exemplified below, but The present invention is not limited only to this:

In embodiments of the present invention, ion-dipole effect, when the different atomic bonding of two kinds of electronegativity When, since electronegativity makes distribution of charges uneven compared with the inducing action of thick atom, lead to the mal-distribution of electronics, generates electricity Dipole, the eelctric dipole and electrically charged ionic group interact, and form ion-dipole effect.Wherein, the ionic group It can be any appropriate charged groups, be exemplified below, but the present invention is not limited to this: It is preferred that Wherein, the eelctric dipole can be produced by two kinds of any appropriate different atomic bondings of electronegativity It is raw, it is exemplified below, but the present invention is not limited to this: C-N, C=N, C ≡ N, C=O, C-O, C-S, C=S, C-F, C-Cl, C- Br, C-I, H-O, H-S, H-N, preferably C ≡ N, C=O, C-F, H-O.Ion-dipole acts in the environment of electrochemistry can be steady Fixed to exist, amount of force is easy to regulate and control, and active force generates and the condition of dissociation is milder.

In embodiments of the present invention, there is no particular restriction for the combination of ionic group and eelctric dipole, as long as ionic group Suitable ion-dipole effect can be formed with eelctric dipole.Some suitable combinations can be exemplified below, but the present invention is not It is only limitted to this:

In embodiments of the present invention, Host-guest effect, main body (being indicated with H) is that one kind can be realized The compound (macromolecular or inorganic organic ion skeleton) with hole of molecular recognition；Object (being indicated with G) is that one kind can be by Main body identifies and is embedded in the compound in the hole of main body (small molecule or ion cluster).One host molecule can identify that bonding is more A guest molecule, in embodiments of the present invention, a preferably host molecule at most with two guest molecule phase recognition reactions. The host molecule includes but are not limited to the host molecule and includes but are not limited to ether (including crown ether, cave ether, ball Ether, hemisphere ether, pod-like ether, lasso trick ether, benzo-crown ether, miscellaneous crown ether, miscellaneous cave ether, mixing cave ether), cyclodextrin, ring be luxuriant, Cucurbituril, Calixarenes, column aromatic hydrocarbons and suitable inorganic organic ion skeleton, preferably crown ether, beta-cyclodextrin, cucurbit [8] urea, cup [4] virtue Hydrocarbon, column [5] aromatic hydrocarbons.The guest molecule includes but are not limited to long chain alkane, cycloalkane, heterocycloalkane, aromatic hydrocarbons, heteroaryl Hydrocarbon, condensed cyclic structure compound, heterocycle structure compound, single ring architecture compound, multiring structure compound, spirane structure chemical combination Object, caged scaffold compound, suitable ion cluster, preferably long chain alkane, heterocyclic compound, polycyclic compound, endocyclic compound, Suitable ion cluster.Host molecule and guest molecule can stable presence in the polymer, the host-guest interaction formed is strong It spends moderate, can interact or dissociate under the conditions of relatively mild, make the dynamic of dynamic aggregation object under ordinary conditions It will be achieved.

Suitable main group can be exemplified below, but the present invention is not limited only to this:

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

Suitable guest moieties can be exemplified below, but the present invention is not limited only to this:

In embodiments of the present invention, there is no particular restriction for the combination of main group and guest moieties, as long as main body energy Enough and object forms suitable host-guest interaction.Some suitable combinations can be exemplified below, but the present invention is not limited only to This:

In embodiments of the present invention, the close metal function, when two outermost electron structures are d¹⁰Or d⁸'s When metal ion is close to less than the sum of its van der Waals radius, interaction force can be generated, two metals of close metal function from Son can be the same or different.The outermost electron structure is d¹⁰Metal ion include but are not limited to Cu⁺、Ag⁺、 Au⁺、 Zn²⁺、Hg²⁺、Cd²⁺, preferably Au⁺、Cd²⁺；The outermost electron structure is d⁸Metal ion include but are not limited to Co⁺、Ir⁺、Rh⁺、Ni²⁺、Pt²⁺、Pb²⁺, preferably Pt²⁺、Pb²⁺.Close metal function can be stabilized in the polymer, and effect is strong Spend it is moderate, and have certain directionality, do not have apparent saturability, can assemble and form polynuclear complex, by external environment Influence it is smaller, the dynamic of prepared polymer can be made more sufficient.

In embodiments of the present invention, forming the combination of close metal function, there is no particular restriction, if metal ion it Between form suitable close metal function.Some suitable combinations can be exemplified below, but the present invention is not limited only to this:

Cu—Cu、Ag—Ag、Au—Au、Zn—Zn、Hg—Hg、Cd—Cd、Co—Co、Ir—Ir、Rh—Rh、Ni— Ni、Pt—Pt、Pb—Pb、Cu—Ag、Cu—Au、Ag—Au、Cu—Zn、Cu—Co、Cu—Pt、Zn—Co、 Zn—Pt、 Co—Pt、Co—Rh、Ni—Pb。

In embodiments of the present invention, dipole-dipole effect, when the different atomic bonding of two kinds of electronegativity When, since electronegativity makes distribution of charges uneven compared with the inducing action of thick atom, lead to the mal-distribution of electronics, generates electricity Dipole interacts between two eelctric dipoles, forms dipole-dipole effect.Wherein, the eelctric dipole can be by any appropriate Two kinds of different atomic bondings of electronegativity and generate, be exemplified below, but the present invention is not limited to this: C-N, C=N, C ≡ N, C=O, C-O, C-S, C=S, C-F, C-CI, C-Br, C-I, H-O, H-S, H-N, preferably C ≡ N, C=O, C-F, H-O, it is more excellent Select C ≡ N.Dipole-dipole effect can be stable be present in polymer, be easy to regulate and control, the pairing for acting on group can be with Microdomai pi is generated, makes to interact more stable；When temperature is higher, dipole-dipole effect, which can weaken, even to disappear, therefore contains The polymer of dipole-dipole effect can embody the difference of dynamic according to the difference of temperature.

In embodiments of the present invention, there is no particular restriction for the combination between dipole, as long as can be formed between dipole properly Dipole-dipole effect.Some suitable combinations can be exemplified below, but the present invention is not limited only to this:

In embodiments of the present invention, the halogen bond effect is by halogen atom and neutral or electronegative road The noncovalent interaction formed between this easy alkali, essence are the σ antibonding orbital of halogen atom and the atom with lone electron pair Or the interaction between pi-electron system.The interaction of halogen key can use-XY-expression, wherein X can be selected from Cl, Br, I, preferably Br, I；Y can be selected from F, Cl, Br, I, N, O, S, pi bond, preferably Br, I, N, O.Halogen key has directionality, it is intended to line The geometrical characteristic of property；With the increase of halogen atom ordinal number, combinative electron donor number can also increase, the halogen key of formation Intensity is also higher.Based on halogen bond effect, the dynamic aggregation object of order, self-repairability can be designed that.

In embodiments of the present invention, there is no restriction for the formation atom combination of halogen bond effect, as long as can be in dynamic aggregation Stable halogen bond effect is formed in object.Some suitable combinations can be exemplified below, but the present invention is not limited only to this:

—Cl···Cl—、—Cl···F—、—Cl···Br—、—Cl···I—、—Cl··· N—、—Cl···O—、—Cl···S—、—Cl···π—、—Br···Br—、—Br···F—、— Br···I—、—Br···N—、—Br···O—、—Br···S—、—Br···π—、—I··· I—、—I···F—、—I···N—、—I···O—、—I···S—、—I···π—。

In embodiments of the present invention, cation-π effect is by the pi-electron of cation and armaticity system The noncovalent interaction formed between system.Cation-π effect mainly has three categories, and first group is simple inorganic cation Or ion cluster (such as Na⁺、K⁺、Mg²⁺、NH₄ ⁺、Ca²⁺) and aroma system between effect；Second group is organic cation (such as quaternary ammonium Cation) and aroma system between effect；Third class is atom positively charged in dipolar bond (H atom in such as N-H key) Effect between aroma system.The type of cation-π effect is abundant, and moderate strength can steadily be present in various environment In, performance dynamic aggregation object abundant can be prepared based on cation-π effect.

In embodiments of the present invention, the type of cation-π effect is not particularly limited, as long as long as can be Stable cation-π effect is formed in dynamic aggregation object.Some suitable cation groups can be exemplified below, but this Invention is not limited only to this:

Na⁺、 K⁺、Li⁺、Mg²⁺、Ca²⁺、Be²⁺、H-O、H-S、H-N。

In embodiments of the present invention, the described anion-π effect, be by anion and electron-deficient aromatic π system it Between the noncovalent interaction that is formed.The anion can be simple inorganic non-metallic ion or ion cluster (such as Cl^-、 Br^-、I^-, OH-)；It is also possible to organic anionic groups (such as benzene sulfonic acid base)；It can also be atom negatively charged in dipolar bond (chlorine atom in such as C-Cl key).The electron-deficient aromatic π system refers to the difference due to ring member nitrogen atoms electronegativity, the π electricity of ring Sub- cloud Density Distribution is simultaneously uneven, and pi-electron is mainly to the high atomic orientation offset of electronegativity, so as to cause the pi-electron cloud of aromatic rings Distribution density decline, such as pyridine, fluorobenzene.Anion-π effect has invertibity and controllable identity, can be constructed with it Dynamic aggregation object with property.

In embodiments of the present invention, the type of anion-π effect is not particularly limited, as long as long as can be Stable anion-π effect is formed in dynamic aggregation object.Some suitable anion can be exemplified below, but the present invention It is not limited only to this:

Cl^-、Br^-、I^-、OH^-、SCN^-。

Some suitable electron-deficient aromatic π systems can be exemplified below, but the present invention is not limited only to this: pyridine, pyridazine, fluorine Benzene, nitrobenzene, four oxa- cup [2] aromatic hydrocarbons [2] triazines, three acid imide of benzene.

In embodiments of the present invention, the benzene-fluorobenzene effect, is by passing through color between aromatic hydrocarbons and more fluorinated aromatic hydrocarbons It dissipates power and quadrupole moment acts on the noncovalent interaction collectively constituted.Due to the ionization potential of fluorine atom is very high and atomic polarizability and Atomic radius is all smaller, in more fluorinated aromatic hydrocarbons the fluorine atom of surrounding because electronegativity it is big and negatively charged, center carbocyclic skeleton electricity is negative Property it is smaller and have positive charge.Because the electronegativity of carbon atom is greater than hydrogen atom, the electric direction of aromatic hydrocarbons and polyfluoro It is contrary for the electric of aromatic hydrocarbons, and due to the volume very little of fluorine atom, the volume of more fluorinated aromatic hydrocarbons and aromatic hydrocarbons is close, institute By aromatic hydrocarbons and more fluorinated aromatic hydrocarbons by it is alternate face-to-face in a manner of sedimentation, form column packed structures, and this accumulation mode Substantially it is not influenced by functional group is introduced.Using benzene-fluorobenzene effect invertibity and sedimentation, can prepare with special The dynamic aggregation object of function.

In embodiments of the present invention, benzene-fluorobenzene effect type is not restricted, as long as can be in dynamic aggregation object Form stable benzene-fluorobenzene effect.Some suitable benzene-fluorobenzene effect can be exemplified below, but the present invention is not limited only to This:

In embodiments of the present invention, the π-π stacking acts on, electric containing pi bond is capable of providing in dynamic aggregation object The structure of sub- cloud is acted on by the mutual overlapping π-π stacking that formed of pi bond electron cloud.There are three types of the modes of action that π-π is stacked, packet Include the accumulation of face face, offset accumulation and the accumulation of side face.Wherein, the accumulation of face face refers to that the anchor ring of interaction is parallel to each other, and flat The distance and the distance between anchor ring at row anchor ring center are almost equal, and the π-π effect of this accumulation mode is electrostatic repulsion, than It is more unstable, but when the substituent group connected on anchor ring is electron-withdrawing stronger, the π-π effect of face face accumulation becomes brighter It is aobvious；Offset accumulation refers to that effect anchor ring is parallel to each other, but there is certain deviation at ring center, i.e. the distance at ring center is greater than between anchor ring Distance, this accumulation mode alleviate the mutual repulsion effect between two anchor rings, have increase accordingly the attraction of σ-π, are that comparison is normal The accumulation mode seen；Accumulation mode other than accumulating in addition to face face and deviating accumulation is known as the accumulation of side face, this accumulation mode energy Amount is minimum, and intermolecular repulsion is minimum, is common between the lesser Circlewise conjugated molecule in Van der Waals surface or the ring of flexible connexon Between conjugated molecule.

It is capable of providing the compound structure of pi bond electron cloud, including but not limited to most fused ring compound and some is deposited In the pi-conjugated heterocyclic compound of π-, suitable group can be exemplified below, but the present invention is not limited only to this:

It is preferred thatπ-π is stacked It is simple to act on generation type, can be stable in the presence of in polymer, influenced by external environment it is smaller, can be convenient by changing Become conjugated compound and content regulates and controls it.

In embodiments of the present invention, providing the combination of the compound of pi bond electron cloud, there is no particular restriction, as long as chemical combination Suitable π-π stacking effect is formed between object.Some suitable combinations can be exemplified below, but the present invention is not limited only to This:

In embodiments of the present invention, the combination of some suitable ion hydrogen bond actions can be exemplified below, but this hair It is bright to be not limited only to this:

In embodiments of the present invention, the radical cation dimerization, construction unit are to contain simultaneously The group of free radical and cation.As an example, it is described formed radical cation dimerization include but is not limited to It is lower to be lifted:

In embodiments of the present invention, the combination of some suitable radical cation dimerizations can illustrate such as Under, but the present invention is not limited only to this:

In embodiments of the present invention, the hydrogen bond action is surpassed by any appropriate by what hydrogen bond was established Molecular action, the hydrogen atom being covalently attached to generally by the atom Z big with electronegativity and the atom that electronegativity is big, radius is small Y, using hydrogen as medium, generates the hydrogen bond link of Z-H ... Y shape formula, wherein described Z, the Y is any appropriate electricity between Z and Y Negativity is big and atom that radius is small, can may be not same element for same element, can be selected from F, N, O, C, S, Cl, P, the atoms such as Br, I, more preferably F, N, O atom, more preferably O, N atom.Wherein, the hydrogen bond action can be used as super Ring formation exists in molecule aggregation and/or crosslinking and/or chain namely hydrogen bond can be played only and connect two or more chains Segment unit, which plays to increase polymer chain dimensions but do not play supermolecule crosslinked action or hydrogen bond, only plays the crosslinking of interchain supermolecule, Or only play in chain in combination of any two or more in ring formation or three of the above.The present invention is also not excluded for hydrogen Key plays the role of grafting.

In embodiments of the present invention, the hydrogen bond can be optional tooth number.Wherein, the number of teeth refer to by The donor (H, that is, hydrogen atom) and receptor (Y, that is, receive the electronegative atom of hydrogen atom) of hydrogen bond group are formed by Hydrogen bond quantity, each H ... Y group are combined into a tooth.In following formula, the hydrogen of the schematically illustrate tooth of difference, two teeth and three tooth hydrogen bond groups Key bonding situation.

The bonding situation of one tooth, two teeth and three tooth hydrogen bonds can concrete example it is as follows:

The number of teeth of hydrogen bond is more, and synergistic effect is bigger, and the intensity of hydrogen bond is bigger.In embodiments of the present invention, right The number of teeth of hydrogen bond does not limit.If the number of teeth of hydrogen bond is more, intensity is big, then the dynamic of hydrogen bond action is with regard to weak, Ke Yiqi To the effect for promoting dynamic aggregation object to keep balanced structure and raising mechanical property (modulus and intensity).If the number of teeth of hydrogen bond Few, then intensity is low, and the dynamic of hydrogen bond action is with regard to strong.In embodiments of the present invention, the hydrogen bond of preferably more than four teeth is made With.

In embodiments of the present invention, the hydrogen bond action can be by existing between any appropriate hydrogen bond group Noncovalent interaction generates.Wherein, the hydrogen bond group can only contain hydrogen bond donor, or only contain hydrogen bond receptor, or Contain hydrogen bond donor and receptor simultaneously, preferably contains hydrogen bond donor and receptor simultaneously.Wherein, the hydrogen bond group preferably comprises Following constituent:

At least one of further preferably following constituent:

Wherein,Indicate with polymer chain, crosslinking link or any other suitable group/atom (including hydrogen original Son) connection.In embodiments of the present invention, hydrogen bond group preferably is selected from amide groups, carbamate groups, urea groups, thio ammonia Carbamate base and the derivative of the above group etc..

In the present invention, the hydrogen bond group can be only present on polymer chain skeleton (including side chain/branch/point Fork chain), referred to as skeleton hydrogen bond group；Also it can be only present in polymer chain side group (also including the multilevel structure of side group), referred to as Side group hydrogen bond group；Also it can be only present on polymer chain/small molecule end group, referred to as end group hydrogen bond group；It can also be simultaneously On being present at least two in polymer chain skeleton, polymer chain side group, polymer chain/small molecule end group.When existing simultaneously In polymer chain skeleton, polymer chain side group, polymer chain/small molecule end group at least two on when, under specific circumstances, Hydrogen bond can be formed between the hydrogen bond group of different location, such as skeleton hydrogen bond group can be formed between side group hydrogen bond group Hydrogen bond.

Wherein, suitable skeleton hydrogen bond group citing such as (but the present invention is not limited only to this):

Wherein, suitable side group hydrogen bond group/end group hydrogen bond group is in addition to it can have above-mentioned skeleton hydrogen bond group structure, More citings such as (but the present invention is not limited only to this):

Wherein, m, n are the quantity of repetitive unit, can be fixed value, are also possible to average value, preferably smaller than 20, more excellent Choosing is less than 5.

It in the present invention, can be same containing one or more kinds of hydrogen bond groups in same polymeric system It can also be a kind of or more containing that can contain in one or more kinds of hydrogen bond group namely dynamic aggregation object in cross-linked network The combination of kind hydrogen bond group.The hydrogen bond group can be formed by the reaction between any appropriate group, such as: it is logical The covalent reaction crossed between carboxyl, acyl halide group, anhydride group, ester group, amide groups, isocyanate groups and amino is formed；It is logical Cross isocyanate groups and hydroxyl, sulfydryl, the covalent reaction between carboxyl are formed；Pass through succinimide group and amino, hydroxyl Covalent reaction between base, sulfydryl is formed.

In energy-absorbing method provided by the invention, for the dynamic aggregation object of energy-absorbing, component structure is abundant, and performance is more Sample, raw material sources are extensive, and Modulatory character is strong.By the molecular structure, functional group number, the molecular weight that control the compound as raw material Etc. parameters, can prepare with different appearance features, the dynamic aggregation object that performance is adjustable, widely used.For example, being made by control For the functional group number and other reactive group numbers of the compound of raw material, it is poly- that the dynamic with different topology structure can be prepared Object is closed, to prepare the polymer material with different energy-absorbing effects.

In the present invention, the hydrogen bond action can be raw during dynamic aggregation object carries out the crosslinking of dynamic supermolecule At；Dynamic supermolecule crosslinking is carried out again after being also possible to pre-generated hydrogen bond action；It can also be cross-linked to form in dynamic supermolecule Afterwards, hydrogen bond action is generated during dynamic aggregation object subsequent forming, but the present invention is not limited only to this.

In embodiments of the present invention, in order to form the crosslinking based on metal-ligand effect, a metal center is extremely It wants that metal-ligand effect (i.e. M-L can be formed with ligand groups described in two parts less₂Structure), there can also be multiple match Body and the same metal center form metal-ligand effect, and two of them or multiple ligand groups can be identical or different.One The ligancy of metal center is limited, and the coordination atom of ligand groups is more, and the amount of ligand that a metal center can be coordinated is got over It is few, it is lower based on metal-ligand effect supermolecule degree of cross linking；But each ligand is formed by the number of teeth with metal center and gets over More coordinations are stronger, and dynamic is lower, therefore the ligand groups of three teeth are preferably more than in the present invention.

In embodiments of the present invention, can only have one kind in a polymer chain or a dynamic polymer systems to match Body can also exist simultaneously any appropriate combination of multiple ligands.A kind of ligand refers to a kind of core ligand knot Structure, a framework counterpart, pendant ligands, end group ligand can have same core ligand structure, their difference exists The tie point and/or position difference of polymer chain or small molecule are accessed in core ligand structure.Suitable ligand combination can be with The dynamic aggregation object with particular characteristic is be effectivelyed prepared, such as plays collaboration and/or orthogonal effect, promotes the synthesis of material Performance.Suitable ligand groups (core ligand structure) can be exemplified below, but the present invention is not limited only to this:

One tooth ligand groups are exemplified below:

-C≡N；

Bidentate ligand group is exemplified below:

Tridentate ligand group is exemplified below:

Tetradentate ligands group is exemplified below:

Multidentate ligand is exemplified below:

In embodiments of the present invention, when there are the polymer of non-covalent or small molecules in dynamic polymer systems When compound, the core ligand structure can also be made in the polymer of the non-covalent or the end of small molecule compound For end group.

In embodiments of the present invention, the metal center M can be any appropriate metal ion or compound/ The metal center of chelate etc. can be selected from any appropriate ionic species, the chemical combination of any one metal in the periodic table of elements Object/chelate and combinations thereof.

Related metal is preferably the metal in the first subgroup to the 7th subgroup and the 8th race.First subgroup Metal into the 7th subgroup and the 8th race further include lanthanide series metal (i.e. La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and actinide metals (i.e. Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr).

Related metal is more preferably the first subgroup (Cu, Ag, Au) metal, the second subgroup (Zn, Cd) metal, the 8th race (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt) metal, group of the lanthanides (La, Eu, Tb, Ho, Tm, Lu) metal, actinium series (Th) metal.Into One step is preferably Cu, Zn, Fe, Co, Ni, Pd, Ag, Pt, Au, La, Ce, Eu, Tb, Th, to obtain stronger dynamic.

In embodiments of the present invention, there is no restriction for related metallo-organic compound, and suitable example can be lifted Under such as:

Other suitable metal organic compounds for being capable of providing metal center include but is not limited to the organic cage of metal-, metal- Organic frame.This metalloid-organic compound can be used alone, or is introduced by suitable covalent chemical on-link mode (OLM) The suitable position of polymer chain.Those skilled in the art can rationally and effectively be realized with logic according to the present invention and train of thought.

In embodiments of the present invention, the oxide of the preferably above-mentioned metal of related metal inorganic compound, vulcanization Composition granule, especially nano particle.

In embodiments of the present invention, the metallo-chelate that can provide suitable metal center preferably has coordination site empty Scarce chelate or some ligands can the chelate replaced the framework counterpart of the invention.

In embodiments of the present invention, there is no particular restriction for the combination of ligand groups and metal center, as long as matching physical efficiency Enough and metal center forms suitable metal-ligand and acts on.Some suitable combinations can be exemplified below, but the present invention is not It is only limitted to this:

In embodiments of the present invention, the generation or introducing of supermolecular mechanism group can use any appropriate reaction, Include but are not limited to Types Below: isocyanates and amino, hydroxyl, sulfydryl, carboxyl react, and the parental materials of heterocycle are anti- It answers, the nucleophilic substitution of heterocycle, double bond radical reaction, the side chain reaction of heterocycle, nitrine-alkynes click-reaction, sulfydryl-is bis- Key/alkynes click-reaction, the reaction of urea-amine, amidation process, tetrazine-norbornene reaction, active ester are reacted with amino； Preferred isocyanate and amino, hydroxyl, sulfydryl react, nitrine-alkynes click-reaction, the reaction of urea-amine, amidation process, Active ester is reacted with amino, sulfydryl-double bond/alkynes click-reaction；More preferable isocyanates and amino, hydroxyl, sulfydryl react, Sulfydryl-double bond/alkynes click-reaction, nitrine-alkynes click-reaction.

In embodiments of the present invention, the introducing of metal center can carry out on any suitable opportunity.At least one Lower three kinds of methods can introduce before generating ligand groups, and the composition of metal-ligand effect can be formerly formed with ligand Polymerized/cross-linked is carried out again, can also be re-introduced into after completing polymerized/cross-linked.It is preferred that being introduced after generating ligand groups.

The present invention will have been carried out the advantages of various effects it is sufficient using and combination, make dynamic aggregation object remove have usually contain Other than the dynamic that has supermolecular mechanism polymer generally to have, self-repairability, repeatable processability, there is also various other property Can: such as the directionality of halogen bond effect, cation-π effect, anion-π effect, in Host-guest effect to small molecule/ion/ The controllable selectivity and controllable identity of group, the order that benzene-fluorobenzene effect, π-π stacking act on, ionization, ion-idol Pole effect, the pH of ion hydrogen bond action, concentration sensitive, electric conductivity, the temperature sensitivity of dipole-dipole effect, close metal phase Interaction, radical cation dimerization the characteristics such as special photo electric, can reasonable selection supermolecular mechanism according to demand Group/unit carries out MOLECULE DESIGN.Material unique functional characteristic is assigned on the basis of with good energy absorption performance.In addition, Dynamic sex differernce based on different types of supermolecular mechanism, can obtain that structure more horn of plenty, performance is more various, dynamically may be used Reverse effect has more the energy-absorbing material of hierarchy.

The relative molecular mass of term " molecular weight " used representative species in the present invention, for small molecule compound, small Molecular radical and certain macromolecular compounds with fixed structure, for macro-radical, molecular weight generally has single point Property is dissipated, namely there is fixed member amount；And there is polydispersion for oligomer, high polymer, oligomer residue, high polymer residue etc. The substance of property molecular weight, molecular weight generally refer to average molecular weight.Wherein, the small molecule compound in the present invention, small molecule Group refers in particular to the compound or group that molecular weight is no more than 1000Da；Macromolecular compound, that macro-radical refers in particular to molecular weight is big In the compound or group of 1000 Da.

Heretofore described " organic group " refers to the base mainly constituted using carbon and protium as skeleton Group can be the small molecule group that molecular weight is no more than 1000Da, be also possible to the polymer chain that molecular weight is greater than 1000Da Residue, suitable group are illustrated such as: methyl, ethyl, vinyl, phenyl, benzyl, carboxyl, aldehyde radical, acetyl group, acetonyl.

Term " hetero atom " used refers to nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms, silicon atom, boron atom in the present invention Etc. common non-carbon.

Term " alkyl " used refers to the saturated hydrocarbyl with straight or branched structure in the present invention.In appropriate situation Under, alkyl can have specified carbon atom number, for example, C_1-4Alkyl, the alkyl be included in linear chain or branched chain arrangement in have 1, 2, the alkyl of 3 or 4 carbon atoms.The example of suitable alkyl includes but is not limited to methyl, ethyl, propyl, normal-butyl, isobutyl Base, tert-butyl, n-pentyl, 2- methyl butyl, 3- methyl butyl, 4- methyl butyl, n-hexyl, 2- methyl amyl, 3- methylpent Base, 4- methyl amyl, 5- methyl amyl, 2- ethyl-butyl, 3- ethyl-butyl, heptyl, octyl, nonyl, decyl.

The single ring architecture being previously mentioned in the present invention is referred to containing only a ring in cyclic structure, be illustrated such as:

The multiring structure being previously mentioned refers to illustrating such as in cyclic structure containing two or more independent rings:

The spirane structure being previously mentioned refers to containing in cyclic structure by two or more rings to each other by sharing one The cyclic structure of a atomic building is illustrated such as:

The condensed cyclic structure (it also includes two rings, virtue and ring structure) being previously mentioned, refers in cyclic structure containing by two A or multiple rings to each other by sharing the cyclic structure of two adjacent atomic buildings, citing such as:

The caged scaffold being previously mentioned refers to containing in cyclic structure by two or more rings to each other by sharing two The cyclic structure of a above adjacent atomic building, has three-dimensional cage structure, illustrates such as:

The nested ring structure being previously mentioned refers in cyclic structure containing connected or embedding to each other by two or more rings The cyclic structure constituted is covered, is illustrated such as:

The heterocycle structure being previously mentioned refers to participating in the cyclic annular knot to be formed containing at least one hetero atom in cyclic structure Structure is illustrated such as:

It, all can be in the case where not specifying when the structure being related in the present invention has isomer Any one of them isomers comprising position isomery, conformational isomerism, chiral photo-isomerisation, cis-trans isomerism etc..

In the present invention " substituted ", by taking " substituted alkyl " as an example, refer to any of any position in substituted " alkyl " A or more than one hydrogen atom can be replaced any substituent group.In the case where being not particularly limited, substituent group therein It is not particularly limited.

For a compound, a group or an atom, can be substituted simultaneously and by hydridization, such as nitrobenzophenone Replace hydrogen atom, for another example-CH₂-CH₂-CH₂It is replaced by-CH₂-S-CH(CH₃)-。

In order to illustrate simplicity the term is indicated using conjunction "and/or" in the description of the invention It may include the option selected from the conjunction "and/or" foregoing description, or described option after conjunction "and/or", Or it is simultaneously selected from described these three situations of option before and after conjunction "and/or".

In embodiments of the present invention, the form of the dynamic aggregation object or its composition can be ordinary solid, coagulate Glue (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid swell gel), elasticity Body, foamed material etc., wherein the dissolvable small-molecular-weight component content contained in ordinary solid and foamed material is generally not more than 10 wt%, and the small-molecular-weight component content contained in gel is generally not less than 50wt%.The shape and volume ratio of ordinary solid It is relatively fixed, there is better mechanical strength, it can not be by the constraint of organic sweller or water.Elastomer has the general of ordinary solid All over property, but there is preferable elasticity, and softer simultaneously, is conducive to provide damping/energy-absorbing ability.Gel then has Good flexibility can embody preferable energy absorption characteristics and resilience, suitable for preparing the energy-absorbing material with damping Material, preferably by the gel of plasticizer, ionic liquid, oligomer and boiling point the organic solvent swelling higher than water.Foamed material then has Have the advantages that density is low, light, the mechanical strength of the brittleness and organogel that can also overcome part ordinary solid is relatively low to ask Topic, soft foam material also have the characteristic of good elasticity and energy absorption capacity and soft comfortable.The material of different shape can be not Same field has suitable purposes.

In embodiments of the present invention, dynamic aggregation object gel can by carrying out being crosslinked acquisition in sweller, Sweller can be recycled to carry out swelling acquisition after the completion of prepared by dynamic aggregation object.Certainly, the present invention not only limit and this, ability Field technique personnel can rationally and effectively be realized with logic according to the present invention and train of thought.

In the preparation process of dynamic aggregation object, mechanical foaming method, physical blowing method, three kinds of chemical blowing process are mainly used Method foams to dynamic aggregation object.

Wherein, the mechanical foaming method is by strong stirring in the preparation process of dynamic aggregation object a large amount of empty Gas or other gases are introduced into lotion, suspension or the solution of polymer and make uniform foams, then pass through physics Or chemical change is allowed to be gelled, solidifies and become foamed material.For shorten molding cycle can be passed through air and be added emulsifier or Surfactant.

Wherein, the physical blowing method, be realized in the preparation process of dynamic aggregation object using physical principle it is poly- Close the foaming of object comprising but it is not limited only to following methods: (1) inert gas blown method, i.e., indifferent gas under pressurized condition Body is pressed into molten polymer or pasty material, then decompression heating, is made the gas expansion of dissolution and is foamed；(2) low boiling is utilized Point liquid evaporation gasification foaming makes liquid that is, in low-boiling point liquid indentation polymer or under certain pressure, temperature regime It dissolves in polymer (particle), then heats and softens polymer, liquid also gasifies therewith evaporation and foamed；(3) leaching, i.e., It is immersed in polymer with liquid medium and dissolves added solid matter in advance, make to occur a large amount of holes in polymer and be in hair Blister, such as by solable matter salt elder generation and mixed with polymers, put in water repeatedly after being shaped to product, then by product Processing dissolves out solable matter to get open-celled foam product is arrived；(4) hollow microsphere method is added hollow micro- in the material It is combined after ball as obturator-type foamed polymer；(5) expandable particles method is filled, first mixing filling expandable particles, Expandable particles are made to foam in molding or mixed process with the polymer material of activity foaming；Wherein, preferably by polymer In dissolve in inert gas and the method for low-boiling point liquid foams.Using physical blowing method, have operation Poisoning smaller, hair The advantages that bubble cost of material is lower, foaming agent noresidue body.Further, it is also possible to be prepared using freeze-drying.

Wherein, the chemical blowing process is to generate gas along with chemical reaction in dynamic aggregation object foaming process And the method to foam, generally comprise following two method: (1) thermal decomposable foaming agent foaming utilizes chemical foaming agent The gas decomposed to give off after heating foams.(2) it interacts between polymers compositions and generates the foaming of gas, that is, utilize hair The chemical reaction occurred between two or more components in foam system, generating inert gas (such as carbon dioxide or nitrogen) causes Polymer is expanded and is foamed.It is carried out in foaming process for control polymerization reaction and foamable reaction balance, to guarantee that product has preferably Quality, a small amount of catalyst and foam stabiliser (or surfactant) is generally added.Wherein, preferably by adding in the polymer The method of chemical foaming agent is added to foam.

In the preparation process of dynamic aggregation object, mainly using moulded from foam molding, injection-expansion molded and extrusion hair Three kinds of methods of type are soaked to form dynamic aggregation object foamed material.

Wherein, moulded from foam molding, technical process is simpler, is easy to control, and can be divided into one-step method and two Two kinds of footwork.One step processing refers to that mixed material, which is direct plungeed into die cavity, carries out foaming；Two-step method, which refers to, first will The material prefoam processing mixed, is then placed in die cavity and carries out foaming.Wherein, since one-step method moulded from foam forms ratio Two-step method is easy to operate and high production efficiency, therefore it is preferred that one-step method carries out moulded from foam molding.

Wherein, described injection-expansion molded, technique and equipment are similar with common injection moulding, bubble nucleating rank Section is after screw rod is added in material, by heating and friction is made material become melt state, the control that foaming agent is passed through metering valve Then foaming agent is uniformly mixed by the hybrid element of screw head, in nucleating agent in certain flow rate injecting material melt Under the action of form nuclei of bubbles.Expansion stage and solidifying and setting stage all occur after full of die cavity, when under cavity pressure When drop, the expansion process of gassing core, while making foam solidifying and setting with the cooling of mold.

Wherein, the foam shaping by extrusion, technique and equipment are similar with common extrusion molding, before extrusion or Foaming agent is added in extruder in extrusion process, melt flows through pressure at head and declines, and foaming agent volatilizees and forms requirement Foaming structure.It is more more competitive than injection-expansion molded since it can not only realize continuous production, and in cost, because This is current most widely used foaming technology.

In the preparation process of dynamic aggregation object, those skilled in the art can be poly- according to practical preparation situation and target Closing physical performance selects suitable foaming method and foamed material forming method to prepare dynamic aggregation object foamed material.

In embodiments of the present invention, the structure of dynamic aggregation object foamed material is related to open-celled structure, hole-closing structure, half Open three kinds of semi-closure structure.It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional or three-dimensional can lead to Gas or liquid are crossed, abscess diameter is that 0.01-3mm is differed.Hole-closing structure, has an individual blisters structure, inner cell and abscess it Between there is wall film to separate, the overwhelming majority be not interconnected, abscess diameter be 0.01-3mm differ.The existing phase interconnection of contained abscess It is then half open-celled structure that leading to again, which has mutual disconnected structure,.It, can also be by mechanical compression for having formed the foaming structure of closed pore Or chemical method becomes open-celled structure, those skilled in the art can select according to actual needs.

In embodiments of the present invention, dynamic aggregation object foamed material can be divided into soft, hard according to its softness With semi-rigid three classes: (1) flexible foam, 23 DEG C and 50% relative humidity under, the elasticity modulus of foamed plastics is less than 70MPa；(2) rigid foam, 23 DEG C and 50% relative humidity under, elasticity modulus be greater than 700MPa；(3) semi-rigid (or half It is soft) foam, the foams between above two class, elasticity modulus is between 70MPa and 700MPa.

In embodiments of the present invention, dynamic aggregation object foamed material can be divided into low ratio foamed, middle hair according to its density again Bubble and high-foaming.The foamed material of low ratio foamed, density are greater than 0.4g/cm³, expansion ratio is less than 1.5；The foam material of middle foaming Material, density are 0.1~0.4g/cm³, expansion ratio is 1.5~9；And the foamed material of high-foaming, density are less than 0.1g/ cm³, expansion ratio is greater than 9.

During the preparation process, certain other polymers, auxiliary agent, filler, sweller can also be added to be total in dynamic aggregation object With composition dynamic aggregation object material, but these additives it is not necessary to.

Wherein, the other polymers can play in system as additive and improve material property, assign material Material new capability improves materials'use and economic benefit, has the function that material comprehensively utilizes.Addible other polymers, It can be selected from natural polymer, synthetic macromolecular compound.The present invention is to the character of added polymer and is had Some molecular weight can be oligomer or high polymer according to the difference of molecular weight, not according to polymeric species without limitation Together, it can be homopolymer or copolymer, should be prepared in the specific use process according to the performance of target material and actually The needs of journey and selected.

When the other polymers are selected from natural polymer, it can be selected from following any or appoint several days Right high-molecular compound: natural rubber, chitosan, chitin, native protein, polysaccharide etc..

When the other polymers are selected from synthetic macromolecular compound, it can be selected from following any or appoint several: Polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, polyvinyl chloride, Vingon, low density polyethylene (LDPE), middle density Polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, melamine formaldehyde resin, polyamide, polyacrylic acid, polypropylene Acid esters, polyacrylamide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate Ester, polycarbonate, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, tetrafluoroethylene-perfluoro propane copolymer, polyamides Imines, polyacrylate, polyacrylonitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high-impact polyphenyl second Alkene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, ethylene-propylene copolymer, ethane-acetic acid ethyenyl ester are total Polymers, AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-acetate Ester copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, Lauxite, unsaturated polyester (UP), polyisoprene, gather it is suitable Butadiene, styrene-butadiene copolymer, hycar, poly- (the chloro- 1,3- butadiene of 2-), isobutene-are different Pentadiene copolymer, ethylene-propylene-Isosorbide-5-Nitrae-hexadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene- Ethylidene norbornene copolymer, dimethyl silicone polymer, Polymethyl methacrylate, polymethylphenylsiloxane, poly- methyl Vinyl benzene radical siloxane, poly- methyl ethylene trifluoropropyl siloxane, vinylidene-chlorotrifluoroethylene, inclined fluorine second Alkene-hexafluoropropylene copolymer, vinylidene-tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene propylene copolymer, polycyclic oxygen Chloropropane, epichlorohydrin ethylene oxide copoymer, epoxychloropropane-ethylene oxide-propylene oxide copolymer etc..

In the preparation process of dynamic aggregation object material, the certain addible auxiliary agents being added can improve material Preparation process improves product quality and yield, reduces product cost or assign certain distinctive application performance of product.Described Addible auxiliary agent is selected from following any or several auxiliary agents: additive synthesis, including catalyst, initiator；Stabilizing additive, Including antioxidant, light stabilizer, heat stabilizer；Improve the auxiliary agent of mechanical property, including toughener；Improve helping for processing performance Agent, including lubricant, release agent；The auxiliary agent of softness and lighting, including plasticizer, foaming agent；Change helping for surface property Agent, including antistatic agent, emulsifier, dispersing agent；Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, delustering agent；It is difficult Burning and suppression cigarette auxiliary agent, including fire retardant；Other auxiliary agents, including nucleating agent, rheological agent, thickener, levelling agent, antibacterial agent.

Catalyst in the addible auxiliary agent can reduce reaction activity by changing reaction path Accelerate the reaction rate of reactant during the reaction.It includes but are not limited to following any or appoints several catalyst: 1. Polyurethane catalyst for synthesizing: amines catalyst, such as triethylamine, triethylenediamine, bis- (dimethylaminoethyl) ethers, 2- (2- Dimethylamino-ethoxy) ethyl alcohol, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (dimethylamino-propyl) diisopropanolamine (DIPA), four Methyl dipropylenetriamine, N, N- dimethyl cyclohexyl amine, N, N, N ', N '-tetramethyl Alkylenediamine, N, N, N ', N ', N '-five Methyl diethylenetriamines, N, N- dimethylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl- N-2- hydroxypropyl caproic acid, N, N- dimethyl benzylamine, N, N- dimethyl cetylamine etc.；Organometallic catalysts, such as octanoic acid are sub- Tin, dibutyltin dilaurate, dioctyl tin dilaurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, ring Alkanoic acid cobalt, ferric acetyl acetonade, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc.；② Polyolefin catalyst for synthesizing: such as Ziegler-Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalysis Agent, aluminium diethyl monochloride, titanium tetrachloride, titanium trichloride, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, Triethylamine, tetraphenylboron sodium, antimony oxide, sesquialter ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, aphthenic acids Rare earth etc.；3. CuAAC catalysts: sharing concerted catalysis by monovalence copper compound and amine ligand；Monovalence copper compound is optional From Cu (I) salt, such as CuCl, CuBr, CuI, CuCN, CuOAc；Also selected from Cu (I) complex compound, such as [Cu (CH₃CN)₄]PF₆、 [Cu(CH₃CN)₄]OTf、CuBr(PPh₃)₃Deng；Amine ligand can be selected from three [(1- benzyl -1H-1,2,3- triazole-4-yl) methyl] Amine (TBTA), three [(1- tert-butyl -1H-1,2,3- triazole-4-yl) methyl] amine (TTTA), three (2- benzimidazole methyl) amine (TBIA), it is hydrated bathophenanthroline disulfonic acid sodium etc.；4. thiol-ene catalysts: photochemical catalyst, as dimethoxybenzoin, 2- hydroxy-2-methyl phenylacetone, 2,2- dimethoxy -2- phenyl acetophenone etc.；Nucleopilic reagent catalyst, such as ethylenediamine, three Ethanol amine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazoles, diisopropyl ethyl amine etc..Catalyst amount used does not have It is particularly limited to, generally 0.01-0.5wt%.

Initiator in the addible auxiliary agent, can cause in polymerization process monomer molecule activate and Free radical is generated, reaction rate is improved, reaction is promoted to carry out, include but are not limited to following any or appoints several initiators: 1. radical polymerization shares initiator: organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), two carbon of peroxidating Sour diisopropyl ester, di-cyclohexylperoxy di-carbonate, dicetyl peroxydicarbonate bis- (4- tert-butylcyclohexyl) esters, tert-butyl hydroperoxide Benzoic ether, tert-butyl hydroperoxide pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, such as Azodiisobutyronitrile (AIBN), azobisisoheptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；2. living polymerization With initiator: such as 2,2,6,6- tetramethyl -1- oxygroup piperidines, 1- chloro-1-phenyl ethane/stannous chloride/bis- pyridines ternary system Deng；3. ionic polymerization initiator: such as butyl lithium, sodium/naphthalene system, boron trifluoride/aqueous systems, tin tetrachloride/alkyl halide system Deng；4. coordination polymerization initiator: such as titanium tetrachloride/triethyl aluminum system, two zirconium cyclopentadienyl of dichloro/methylaluminoxane system；⑤ Ring-opening polymerisation initiator: such as sodium methoxide, potassium methoxide, ethylenediamine, hexamethylene diisocyanate, stannous octoate.Wherein, cause The preferred lauroyl peroxide of agent, benzoyl peroxide, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is without spy It does not limit, generally 0.1-1wt%.

Antioxidant in the addible auxiliary agent can delay the oxidation process of polymer material, guarantee material Successfully it can be processed and be prolonged its service life, include but are not limited to following any or appoint several antioxidant: by Hinder phenols, such as 2,6- di-tert-butyl-4-methy phenol, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyl of 2- methyl) butane, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert butyl benzene Phenol)；Sulfur-bearing Hinered phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl-6-tert Butylphenol]；Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-hexahydros equal three Piperazine；Isocyanuric acid ester Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '-two (betanaphthyl) p-phenylenediamine, N, N '-diphenyl-para-phenylene diamine, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as Dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, Asia Tricresyl phosphate nonyl phenyl ester, three [2.4- di-tert-butyl-phenyl] phosphite esters etc., wherein the preferred tea polyphenols of antioxidant (TP), butyl Hydroxyanisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyls] Phosphite ester (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010).Antioxidant dosage used is not particularly limited, generally 0.01-1wt%.

Light stabilizer in the addible auxiliary agent can prevent polymer material from light aging occurs, and extending it makes With the service life comprising but be not limited only to following any or appoint several light stabilizers: photomask agent, such as carbon black, titanium dioxide, oxygen Change zinc, calcium sulfite；Ultraviolet absorbing agent, such as ESCALOL 567,2- hydroxyl -4- n-octyloxy hexichol first Ketone, 2- (2- hydroxyl -3,5- di-tert-butyl-phenyl) -5- chlorobenzotriazole, 2- (2- hydroxy-5-methyl base phenyl) benzotriazole, 2, 4,6- tri- (2- hydroxyl -4- n-butoxyphenyl) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethylhexyl； Pioneer's type ultraviolet absorbing agent, such as the p- tert-butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as bis- (3, 5- di-t-butyl -4- benzylphosphonic acid mono ethyl ester), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light stabilizer Agent, as bis- (2,2,6, the 6- tetramethyl piperidine) esters of decanedioic acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2,2,6, 6- pentamethvl base) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acid (2,4- bis- tertiary fourths Base benzene) ester, alkyl phosphoric acid amide, N, N '-zinc dibutyl dithiocaarbamate, N, the positive fourth positive group dithiocarbamates of N '-two Nickel formate etc..Wherein, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid, institute Light stabilizer dosage is not particularly limited, generally 0.01-0.5wt%.

Heat stabilizer in the addible auxiliary agent, enable to polymer material in processing or use process not Chemical change occurs because heated, or delays these variations to achieve the purpose that prolong the service life comprising but not only limit In following any or several heat stabilizers: lead salts, as lead sulfate tribasic, dibasic lead phosphite, dibasic are stearic Lead plumbate, dibasic phthalic acid lead, tribasic Malaysia lead plumbate, lead stearate, lead salicylate, Dythal, alkali Formula ceruse；Metal soap: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate；Organo-tin compound Class, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two (just) butyl tin, double single-ethylhexyl maleates Dioctyltin, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, dimercapto acetic acid isooctyl stannous methide, two sulphur Alcohol stannous methide and its compound；Antimony stabilizer, such as mercaptan antimonic salt, mercaptoacetate mercaptans type, mercapto-carboxylic ester antimony, carboxylate Antimony；Epoxy compound species, such as epoxidized oil, epoxy aliphatic ester, epoxy resin；Phosphorous acid esters, such as three aromatic ester of phosphorous acid, Asia Tricresyl phosphate alkyl ester, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, aggretion type phosphite ester；Polyalcohols, such as pentaerythrite, xylose Alcohol, mannitol, D-sorbite, trimethylolpropane；It is compound steady to be such as co-precipitated metallic soap, liquid metal soap for composite thermal stabilizer Determine agent, organotin compound stabilizer etc..Wherein, the preferred barium stearate of heat stabilizer, calcium stearate, tin dilaurate di-n-butyl Tin, maleic acid two (just) butyl tin, heat stabilizer dosage used are not particularly limited, generally 0.1-0.5wt%.

Toughener in the addible auxiliary agent can reduce polymer material brittleness, increase toughness, improve material Bearing strength comprising but be not limited only to following any or appoint several toughener: methyl methacrylate-butadiene-benzene second Alkene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, acrylic nitrile-butadiene two Alkene-styrol copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, styrene-fourth Styrene block copolymer etc..Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene copolymer (ABS), Styrene-Butadiene-Styrene Block Copolymer (SBS), Methyl Methacrylate-Butadiene-Styrene Copolymer Resin (MBS), chlorinated polyethylene resin (CPE), toughener dosage used are not particularly limited, generally 5-10wt%.

Lubricant in the addible auxiliary agent can be improved material lubricity, reduce friction, reduce Interface Adhesion Performance comprising but be not limited only to following any or appoint several lubricants: saturated hydrocarbons and halogenated hydrocarbon, such as solid paraffin, micro- Spar wax, atoleine, low molecular weight polyethylene, oxidized polyethylene wax；Fatty acid, such as stearic acid；Fatty acid ester, such as rouge Fat acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax；Aliphatic amide type, such as stearmide or tristearin Sour amide, oleamide or oleamide, erucyl amide, N, N '-ethylene bis stearamide；Fatty alcohol and polyalcohols, it is such as stearic Alcohol, cetanol, pentaerythrite；Metal soap, such as lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate. Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight polyethylene, lubricant quantity used is without spy It does not limit, generally 0.5-1wt%.

Release agent in the addible auxiliary agent, it can make polymer samples be easy to demould, and surface is smooth, clean, It includes but are not limited to following any or appoints several release agents: paraffin hydrocarbon, soaps, dimethicone, ethyl silicon oil, methyl Phenyl silicone oil, castor oil, used oil, mineral oil, molybdenum disulfide, vinyl chloride resin, polystyrene, silicon rubber, polyvinyl alcohol etc.. Wherein, the preferred dimethicone of release agent, remover dosage used are not particularly limited, generally 0.5-2wt%.

Plasticizer in the addible auxiliary agent, can increase the plasticity of polymer material, so that polymer Hardness, modulus, softening temperature and brittle temperature decline, elongation at break, flexibility and flexibility improve comprising but not only limit In following any or several plasticizer: Phthalates: dibutyl phthalate, dioctyl phthalate, neighbour Phthalic acid di-isooctyl, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, adjacent benzene Dioctyl phthalate butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid are bis- (13) Ester, terephthalic acid (TPA) two (2- ethyl) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyl) own ester；Rouge Fat esters of gallic acid, such as the own ester of adipic acid two (2- ethyl), decanedioic acid two (2- ethyl) own ester；Epoxy compound species, such as epoxy glycerite Esters, epoxy fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, epoxystearic acid (2- ethyl) oneself Ester, epoxy soybean oleic acid 2- ethylhexyl, the own ester of 4,5- epoxy tetrahydrophthalic acid two (2- ethyl), Chinese littleleaf box acetylated castor oil Sour methyl esters, dihydric alcohol lipid, such as C_5~9Sour glycol ester, C_5~9Sour Triethylene Glycol；Class containing chlorine such as afforests paraffin class, chlorine Fat subsitutes acid esters；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Phenyl alkylsulfonate, Trimellitate, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, plasticizer pref-erable dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisooctyl phthalate (DIDP), tricresyl phosphate (TCP), plasticizer consumption used do not limit especially It is fixed, generally 5-20wt%.

Foaming agent in the addible auxiliary agent, can make polymer samples foam pore-forming, thus obtain it is light, every Heat, sound insulation, softness or firm polymer material comprising but be not limited only to following any or appoint several foaming agents: physics Foaming agent, such as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, fourth Alkane, ether, chloromethanes, methylene chloride, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, such as bicarbonate Sodium, ammonium carbonate, ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitro, N, N '-dimethyl-N, N '-two Nitroso terephthalamide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide first Sour potassium, azodiisobutyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide, connection Benzene -4,4 '-disulfonyl nitrine；Physical microballoon/granule foaming agent, such as the production of Akzo Nobel company are expandable micro- Ball；Foamed promoter, such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, tristearin Lead plumbate, cadmium stearate, zinc stearate, zinc oxide；Frothing inhibitor, as maleic acid, fumaric acid, stearyl chloride, phthalyl chloride, Maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, oxime, isocyanates, mercaptan, thiophenol, thiocarbamide, Sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl maleic acid tin etc..Wherein, the preferred bicarbonate of foaming agent Sodium, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine (blowing agent H) of N '-dinitro, N, N '-diformazan Base-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent, foaming agent consumption used do not have It is particularly limited to, generally 0.1-30wt%.

The deleterious charge assembled in polymer samples can be guided or be disappeared by the antistatic agent in the addible auxiliary agent It removes, it is made production and life not brought inconvenience or be endangered comprising but be not limited only to following any or appoint several antistatic Agent: anionic antistatic agent, as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethanolamine salt, To nonyl diphenyl ether potassium sulfonate, phosphate derivative, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, phosphate derivative, Fatty amine sulfonate, butyrate sodium sulfonate；Cationic antistatic agent, as aliphatic ammonium salt hydrochlorate, lauryl trimethyl ammonium chloride, Dodecyl trimethylamine bromide；Amphoteric ion type antistatic agent, as alkyl dicarboxyl methyl ammonium second inner salt, lauryl betaine, N, N, N- trialkyl ammonium acetyl (N '-alkyl) amine second inner salt, bis- polyethylene oxide base-N- ethylphosphonic acid of N- lauryl-N, N- Sodium, N- alkylaminoacid salts；Non-ionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide addition Object, alkyl phenol ethylene oxide addition product, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid glyceride；Polymer Antistatic Agent, such as Polyene propionamide N- quaternary ammonium salt substituent, poly- 4- vinyl -1- acetone yl pyridines phosphoric acid-are to butyl phenyl ester salt etc.；Wherein, resist quiet The preferred lauryl trimethyl ammonium chloride of electric agent, alkyl phosphate diethanolamine salt (antistatic agent P), antistatic agent dosage used It is not particularly limited, generally 0.3-3wt%.

Emulsifier in the addible auxiliary agent can improve various compositions in the mixed with polymers liquid containing auxiliary agent Surface tension between phase is allowed to form uniform and stable dispersion or emulsion comprising but be not limited only to following any Kind appoints several emulsifiers: anionic, such as higher fatty acid salt, alkylsulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonic acid Sodium, sulphosuccinates, petroleum sulfonate, aliphatic alcohol sulfate, castor oil salt, sulphation butyl ricinoleate salt, Phosphate ester salt, fatty acyl-peptide condensation product；Cationic, such as alkylammonium salt, alkyl quaternary ammonium salts, Fixanol；Amphoteric ion Type, such as carboxylic acid ester type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；It is non-ionic, as fatty alcohol polyoxyethylene ether, alkyl phenol are poly- Ethylene oxide ether, polyoxyethylene carboxylate, polypropylene oxide-ethylene oxide adduct, fatty acid glyceride, pentaerythrite fat Acid esters, sorbierite and sorbitan fatty acid ester, sucrose fatty ester, hydramine fatty acid amide etc..Wherein, preferred dodecyl Benzene sulfonic acid sodium salt, sorbitan fatty acid ester, triethanolamine stearate (Emulphor FM), emulsifier used is without spy It does not limit, generally 1-5wt%.

Dispersing agent in the addible auxiliary agent enables to solid flocculation group in mixed with polymers liquid to be separated into carefully Small particle and be suspended in liquid, those are poorly soluble the solid and liquid particles in liquid for uniform dispersion, while can also prevent The only sedimentation and cohesion of particle forms stable suspension comprising but be not limited only to following any or appoint several dispersing agents: yin Ionic, such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；It is non-ionic, such as poly alkyl alcohol Ethylene oxide ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Polymer electrolyte, it is such as bright Glue, water-soluble glue, lecithin, sodium alginate, lignosulfonates, polyvinyl alcohol etc..Wherein, the preferred detergent alkylate of dispersing agent Sodium sulfonate, naphthalene system methylene sulfonate (dispersing agent N), fatty alcohol polyoxyethylene ether, dispersant dosage used do not limit especially It is fixed, generally 0.3-0.8wt%.

Colorant in the addible auxiliary agent can make polymeric articles show required color, increase Surface color and polish comprising but be not limited only to it is following any or appoint several colorants: inorganic pigment, as titanium white, chrome yellow, cadmium red, Iron oxide red, molybdate red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalocyanine Red, fast carmine HF3C, the bright red R of plastics and the not red BR of Crow, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, Permanent yellow H₂G, phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, such as thioindigo red, vat yellow 4GF, indanthrene blue RSN, slag rhodamine toner, Oil Yellow etc..Wherein, the selection of colorant does not need especially to limit depending on color sample demand Fixed, colorant concentrations used are not particularly limited, generally 0.3-0.8wt%.

Fluorescent whitening agent in the addible auxiliary agent can make contaminated substance obtain the sparkling of similar fluorite Effect comprising but be not limited only to following any or appoint several fluorescent whitening agents: Stilbene-based, coumarin type, pyrazoline Type, benzo oxygen nitrogen type, phthalimide type etc..Wherein, (fluorescence increases the preferred stilbene biphenyl sodium disulfonate of fluorescent whitening agent White dose of CBS), 4,4- bis- (5 methyl -2- benzoxazolyl) talan (fluorescent whitening agent KSN), 2,2- (4,4 '-talan Base) double benzoxazoles (fluorescent whitening agent OB -1), fluorescent whitening agent dosage used is not particularly limited, generally 0.002- 0.03 wt%.

Delustering agent in the addible auxiliary agent when incident light being enabled to reach polymer surfaces, occurs unrestrained anti- It penetrates, generates the matt and delustring appearance of low gloss comprising but be not limited only to following any or appoint several delustering agents: sedimentation sulphur Sour barium, silica, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc..Wherein, the preferred titanium dioxide of delustering agent Silicon, delustering agent dosage used are not particularly limited, generally 2-5wt%.

Fire retardant in the addible auxiliary agent, can increase the flame resistance of material comprising but be not limited only to Under it is any or appoint several fire retardants: phosphorus system, such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, phosphoric acid Toluene diphenyl ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Organic halogen Compound, such as high chlorine contents chlorinated paraffin, 1,1,2,2- tetrabromoethane, deca-BDE, penta decane of perchloro- ring；Inorganic fire retardants, Such as antimony oxide, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as chlorendic anhydride, bis- (2,3- dibromos third Base) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride etc..Wherein, the preferred deca-BDE of fire retardant, phosphoric acid Triphenylmethyl methacrylate, tricresyl phosphate, phosphate toluene diphenyl ester, antimony oxide, amount of flame-retardant agent used are not particularly limited, and one As be 1-20wt%.

Nucleating agent in the addible auxiliary agent can accelerate crystallization speed by the crystallization behavior of change polymer Rate increases crystal density and promotes fine grain size, reaches and shortens material molding cycle, improves the product transparency, surface The purpose of the physical mechanical properties such as gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance comprising but Be not limited only to it is following any or appoint several nucleating agents: benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid's sodium, Silica, benzylidene sorbitol and its derivative, EP rubbers, ethylene propylene diene rubber etc..Wherein, the preferred dioxy of nucleating agent SiClx, benzylidene sorbitol (DBS), ethylene propylene diene rubber, nucleating agent dosage used are not particularly limited, generally 0.1-1wt%.

Rheological agent in the addible auxiliary agent can guarantee that polymer has good brushing during film Property and coating thickness appropriate, the sedimentation of solid particle when preventing storage, can be improved its redispersibility comprising but not only limit In following any or several rheological agents: inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, calcium carbonate, chlorination Lithium, sodium sulphate, magnesium silicate, fumed silica, waterglass, colloidal silicon dioxide；Organo-metallic compound, as aluminum stearate, Aluminium alkoxide, titanium chelate, aluminium chelate compound；Organic, such as organobentonite, castor oil derivative, isocyanate derivates, propylene Yogurt liquid, acrylic copolymer, polyvinyl alcohol, polyethylene wax etc..Wherein, preferably organobentonite, polyethylene wax, hydrophobically modified Alkali-swellable emulsions (HASE), alkali-swellable emulsions (ASE), rheological agent dosage used are not particularly limited, generally 0.1-1wt%.

Thickener in the addible auxiliary agent can assign the good thixotropy of mixed with polymers liquid and appropriate Consistency is wrapped to meet various demands such as its stability and application performance in production, storage and use process It includes but is not limited only to following any or appoints several thickeners: lower-molecular substance, such as fatty acid salt, fatty alcohol polyoxyethylene ether sulphur Hydrochlorate, alkyldimethylamine oxide, fatty monoethanol amide, fatty diglycollic amide, fatty acid Isopropamide, dehydration mountain Pears alcohol tricarboxylic ester, glycerol trioleate, coamidopropyl glycine betaine；Polymer substance, such as bentonite, artificial hectorite, micro- Powder silica, colloidal aluminum, plant polyose class, microbial polysaccharide class, animal protein, seaweed acids, poly-methyl acrylate, first Base acrylic copolymer, cis-butenedioic anhydride copolymer, polyacrylamide, polyvinyl pyrrolidone, polyvinyl alcohol, polyethers, polyvinyl methyl ether urea Alkane polymer etc..Wherein, the preferred coconut oil diethanol amide of thickener, acrylic acid-methacrylic acid copolymer, thickening used Agent dosage is not particularly limited, generally 0.1-1.5wt%.

Levelling agent in the addible auxiliary agent can guarantee the flat and smooth uniform of polymer coating film, improve and apply Film surface quality improves dicoration comprising but be not limited only to following any or appoint several levelling agents: polyacrylate, Organic siliconresin etc..Wherein, the preferred polyacrylate of levelling agent, levelling agent dosage used are not particularly limited, generally 0.5-1.5wt%.

Antibacterial agent in the addible auxiliary agent, can within a certain period of time, make certain micro-organisms (bacterium, fungi, Saccharomycete, algae and virus etc.) growth or breeding be maintained at necessary below horizontal, be generally divided into inorganic antiseptic, You Jikang Microbial inoculum and natural antibacterial agent.Wherein, inorganic antiseptic include but are not limited to silver, copper, zinc, nickel, cadmium, lead, mercury, zinc oxide, Copper oxide, ammonium dihydrogen phosphate, lithium carbonate etc.；Organic antibacterial agent includes but are not limited to vanilla aldehydes, ethyl vanillin aldehydes, acyl group The organic compounds such as phenyl amines, imidazoles, thiazoles, isothiazolone derivative, quaternary ammonium salt, double croak classes, phenols；Natural antibacterial Agent includes but are not limited to chitin, mustard, castor oil, horseradish etc..Wherein, antibacterial agent preferably silver, zinc, vanilla aldehydes chemical combination Object, ethyl vanillin aldehydes compound, antibacterial agent dosage used are not particularly limited, generally 0.05-0.5wt%.

The addible filler, primarily serves following effect in the polymeric material: 1. reducing molded article Shrinking percentage improves dimensional stability, surface smoothness, flatness and the zero diopter of product or without photosensitiveness etc.；2. adjusting material Viscosity；3. meeting different performance requirement, such as raising material impact intensity and compressive strength, hardness, rigidity and modulus, raising are resistance to Mill property improves heat distortion temperature, improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. assigning photostability And chemical corrosion resistance；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.

The addible filler, selected from following any or several fillers: inorganic non-metallic filler, metal are filled out Material, organic filler.

The addible inorganic non-metallic filler includes but are not limited to following any or appoints several: calcium carbonate, Clay, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos, asbestos fibre, just Feldspar, chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, graphene oxide, carbon nanotube, fullerene, two Molybdenum sulfide, slag, flue dust, wood powder and shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, Flyash, oil shale powder, swelling perlite powder, conductive black, vermiculite, iron cement, white clay, alkali mud, boron mud, (hollow) glass are micro- Pearl, foam microspheres, expandable particles, glass powder, cement, glass fibre, carbon fiber, quartz fibre, charcoal core boron fibre, two boronations Titanium fiber, calcium titanium fiber, carbon silica fibre, ceramic fibre, whisker etc..

The addible metal packing, including metal simple-substance, metal alloy, metal oxide, metal inorganic chemical combination Object, metallo-organic compound etc. comprising but be not limited only to following any or appoint several: copper, silver, nickel, iron, gold etc. and its conjunction Powder, nano particle and the fiber of gold；Wherein, nano particle includes but are not limited to nanogold particle, nano-Ag particles, nanometer Palladium particle, nano cobalt granule, nano nickle granules, nano magnetic particle (such as γ-Fe₂O₃、CoFe₂O₄、NiFe₂O₄、MnFe₂O₄、 Fe₃O₄、FeN、Fe₂N、ε-Fe₃N、Fe₁₆N etc.)；It additionally include liquid metal comprising but it is not limited only to mercury, gallium, gallium indium liquid State alloy, gallium indium tin liquid alloy, other gallium base liquid metal alloys；Wherein, metallo-organic compound includes some ultraviolet The metallo-organic compound molecule or crystal that can be generated heat under line, infrared ray or electromagnetic action.

The addible organic filler includes but are not limited to following any or appoints several: fur, natural rubber Glue, cotton, velveteen, fiber crops, jute, flax, asbestos, shellac, lignin, protein, enzyme, hormone, raw lacquer, wood powder, shell powder, wood Sugar, silk, artificial silk, vinylon, phenolic aldehyde microballon, resin microbeads etc..

Wherein, the wire feeding of addition does not limit, mainly depending on required material property, preferably calcium carbonate, sulphur Sour barium, talcum powder, carbon black, graphene, (hollow) glass microballoon, foam microspheres, expandable particles, glass fibre, carbon fiber, gold Belong to powder, natural rubber, protein, resin microbeads, amount of filler used is not particularly limited, generally 1-30wt%.

In the preparation process of dynamic aggregation object material, the preferred antioxidant of addible auxiliary agent, light stabilizer, thermostabilization Agent, toughener, plasticizer, foaming agent, fire retardant.The preferred calcium carbonate of addible filler, barium sulfate, talcum powder, carbon black, glass Microballon, graphene, glass fibre, carbon fiber.

In the preparation process of dynamic aggregation object, special limit is not done to the additive amount of dynamic aggregation object each component raw material Fixed, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.

The manufacturing method of composition of the invention is not particularly limited, for example, roller, kneader, extruder, ten thousand can be passed through Can blender etc. additive the subsequent operations such as be blended to prepolymer as needed, then be crosslinked, foamed.

The gold of dynamic aggregation object elastomer of the invention due to the good dynamic characteristics formed in skeleton with ligand groups Category-ligand effect, dynamic aggregation object obtained have certain modulus, toughness, self-healing properties simultaneously, can be extensive Applied to the elastic component etc. in adhesive, coating, film and structural composite material with energy absorption ability.

It is provided by the present invention a kind of with hybrid cross-linked dynamic aggregation object gel rubber material, preferably aqueous solution type gel material Material, organic solvent type gel rubber material and plasticizer swell gel material, more preferable plasticizer swell gel.

A kind of preparation method of dynamic aggregation object aqueous solution type gel rubber material of the invention, includes the following steps: for parent Aqueous monomers, by the raw material of hybrid cross-linked dynamic aggregation object (including the molecule containing ligand, metal center, chain extender, crosslinking agent And various auxiliary agents etc.) be added in aqueous solution, make prepared hybrid cross-linked dynamic aggregation object (reality according to the present invention Apply mode or be the dynamic aggregation object of single network or be interpenetrating networks dynamic aggregation object) mass fraction be 0.5 ~50%, covalent cross-linking is carried out by appropriate means, after reaction, a kind of dynamic aggregation object water-setting is made in natural cooling Glue, that is, one-step method prepare gel rubber material；The polymer chain network containing ligand can also be first prepared, makes it in aqueous solution Metal center is added after middle swelling, extra aqueous solution is removed after its gelation reaction.The aqueous solution is deionized water.

A kind of preparation method of dynamic aggregation object organic solvent type gel rubber material of the invention, include the following steps: for The raw material of hybrid cross-linked dynamic aggregation object is added in suitable organic solvent, makes prepared hydridization by the monomer of hydrophily difference The mass fraction for being crosslinked dynamic aggregation object is 0.5~50%, carries out covalent cross-linking by appropriate means, after reaction, natural It is cooling, that is, a kind of dynamic aggregation object organic solvent type gel rubber material is made, that is, one-step method prepares gel rubber material；It can also be first The polymer chain network containing ligand is prepared, metal center is added after being swollen it in suitable organic solution, it is solidifying to it It is taken out after gelatinization reaction and removes extra organic solvent.The organic solvent be acetone, butanone, N,N-dimethylformamide, One of chloroform, methylene chloride, dimethyl sulfoxide, tetrahydrofuran, methanol, dehydrated alcohol, ether, pentane and toluene Or it is a variety of.

A kind of dynamic aggregation object plasticizer swell gel material preparation method of the invention, includes the following steps: will have The raw material of hybrid cross-linked dynamic aggregation object is added in suitable plasticizer, makes the matter of prepared hybrid cross-linked dynamic aggregation object Measuring score is 0.5~50%, carries out covalent cross-linking by suitable method, after reaction, one kind is made in natural cooling Dynamic aggregation object is plasticized the gel of solvent swell, that is, one-step method prepares gel rubber material；It can also first prepare containing ligand Metal center is added after being swollen it in suitable plasticizer in polymer chain network, takes out and removes after its gelation reaction Extra plasticizer.Upper the plasticizer is selected from following any or appoints several: Phthalates: two fourth of phthalic acid Ester, dioctyl phthalate, diisooctyl phthalate, dibutyl phthalate (DHP), diisooctyl phthalate, neighbour Phthalic acid dinonyl, BBP(Butyl Benzyl Phthalate, butyl phthalate butyl glycolate, dicyclohexyl Bis- (13) esters of ester, phthalic acid, terephthalic acid (TPA) two (2- ethyl) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyl) own ester；Fatty acid ester, such as the own ester of adipic acid two (2- ethyl), decanedioic acid two (2- ethyl) own ester；Ring Oxygen compound class, as epoxy glycerite esters, epoxy fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, The own ester of epoxystearic acid (2- ethyl), epoxy soybean oleic acid 2- ethylhexyl, two (2- second of 4,5- epoxy tetrahydrophthalic acid Base) own ester, Chinese littleleaf box methyl acetylricinolate, dihydric alcohol lipid, such as C_5~9Sour glycol ester, C_5~9Sour Triethylene Glycol； Class containing chlorine such as afforests paraffin class, chloro fat acid esters；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2- third Diol polyester；Phenyl alkylsulfonate, trimellitate, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, epoxy Change a kind of Environment-friendlyplastic plastic plasticizer of function admirable of soybean oil, epoxidation reaction system occurs for refined soybean oil and peroxide It is standby.It is resistance in polrvinyl chloride product to volatilize, is not easy to migrate, not easy to lose.This is to holding product light, thermal stability and extends use Service life is highly beneficial.Epoxidised soybean oil toxicity is minimum, is allowed for the packing timber of food and medicine by many countries Material is the epoxy plasticiser that uniquely can be used for packaging material for food of Food and Drug Adminstration of the US's approval.Of the invention In a kind of gel preparation of dynamic aggregation object plasticising solvent swell, the preferred epoxidized soybean oil of plasticizer.

In embodiments of the present invention, the oligomer is included but are not limited to: epoxy acrylate, modified epoxy third Olefin(e) acid ester, epoxy linseed oil triacrylate, polyester acrylic ester prepolymer, polyether acrylate, urethane acrylate Prepolymer, tripropylene glycol methoxy-ether mono acrylic ester, methoxy-ether neopentyl glycol propoxyl group mono acrylic ester, methoxy-ether three Hydroxymethyl-propane ethyoxyl diacrylate, the polymerization of amine modification acrylate, atoleine, number-average molecular weight less than 10000 Object；It is preferred that epoxy acrylate, polyester acrylate, polyether acrylate prepolymer, number-average molecular weight are poly- less than 10000 Urea, polycarbonate, polyester, polyethers or polyamide.

In embodiments of the present invention, the ionic liquid is included but are not limited to: glyoxaline ion liquid, pyridines Ionic liquid, quaternary ammonium ionic liquid, quaternary phosphine class ionic liquid, pyrrolidines ionic liquid, piperidines ionic liquid, alkenyl function Ionic liquid, Hydroxyl-functionalized Ionic Liquids, ether functionalized ion liquid, ester group functionalized ion liquid, carboxyl function can be changed Ionic liquid, itrile group functionalized ion liquid, amino functional ionic liquid, sulfonic acid funtionalized ionic liquid, benzyl function can be changed Ionic liquid, guanidine ionic liquid can be changed；It preferably specifically is selected from: 1- ethyl-3-methylimidazole tetrafluoroborate, 1- hexyl -2,3- Methylimidazole hexafluorophosphate, 1- ethyl-3-methylimidazole bromide, N- octylpyridinium bromide, tributyhnethylammonium chloride, four Butyl bromide phosphine, N- butyl-N- crassitude bromide, N- butyl-N- methyl piperidine bromide, 1- vinyl -3- butyl imidazole Hexafluorophosphate, 1,2- dimethyl -3- hydroxyethyl imidazole toluenesulfonate, 1- ethyl diethyldithiocarbamate ether -3- methylimidazole hexafluoro Phosphate, 1- ethyl acetate base -3- methylimidazole hexafluorophosphate, 1- carboxyethyl -3- methylimidazole bromide, 1- nitrile propyl -3- Methylimidazole hexafluorophosphate, 1- amine propyl -3- methylimidazole hexafluorophosphate, N- sulfonic acid butyl-pyridinium fluoroform sulphonate, 1- benzyl -3- methyl imidazolium tetrafluoroborate, tetramethylguanidine trifluoro-methanyl sulfonate.

It is provided by the present invention it is a kind of have hybrid cross-linked dynamic aggregation object foamed material can be soft, semi-rigid or Person's rigid foam.Foam can have water or it is anhydrous under the conditions of prepare, foaming method can be physical blowing, chemistry hair One of bubble, mechanical foaming are a variety of.Further, it is non-reacted that suitable auxiliary type known in the art can be used in foam Foaming agent.

A kind of preparation method of dynamic aggregation object foamed material of the invention includes the following steps: in preparation single network When dynamic aggregation object foamed material, reaction mass component A and reaction mass component B is first independently made；Reaction mass component A It is by 8 parts~20 parts of polyol compound, 0.05 part~1.0 parts of chain extender, 0.05 part~1.0 parts of crosslinking agent, organic metal class 0.01-0.5 parts of catalyst, 0.01-0.5 parts of amines catalyst, in 5-35 DEG C of material temperature, the condition of mixing speed 50-200r/min Under stir evenly it is obtained；Reaction mass component B is by 10 parts~20 parts of polyisocyanate compound, foaming agent 0.5 part~3.5 Part, 0.05 part~0.2 part of foam stabiliser, the system of stirring evenly under conditions of 5-35 DEG C of mixing speed 50-200r/min of material temperature ?；Then reaction mass component A is mixed with reaction mass component B according to 1.0~1.5:1 mass ratio, it is quick through professional equipment Stir to get the single network dynamic aggregation object of foaming.Finally, the single network dynamic aggregation object after foaming is added to mold In, solidify 30min~60min at room temperature, then solidifies at high temperature and steeped to get to the dynamic aggregation object based on single network Foam material.At least one component contains ligand groups in the component A and component B.It is cured as at a high temperature of described in temperature Degree is solidifies 6h at 60 DEG C, or in temperature is 80 DEG C of solidification 4h, or in temperature is 120 DEG C of solidification 2h.Above-mentioned polyol compound In hydroxyl (OH) group and polyisocyanate compound in isocyanates (NCO) group molar ratio may make it is final poly- Urethane foam is free of free-end NCO group.The molar ratio of NCO/OH is preferably 0.9/1 to 1.2/1.NCO/OH is 1/1 Molar ratio correspond to isocyanate index be 100.In the case where water is used as foaming agent, the isocyanate index is preferably big In 100, such isocyanate groups can be reacted with water.

In dynamic aggregation object foamed material preparation method of the invention, binary hybrid crosslinking dynamic aggregation object foam is being prepared When material, the step of according to above-mentioned preparation single network dynamic aggregation object, the 1st network is first prepared；Then the 2nd network mistake is being prepared The 1st network is added in the reaction mass A ' by Cheng Zhong, i.e., reaction mass component A ' at this time be 8 parts~20 parts of polyol compound, 0.05 part~1 part of chain extender, 0.05 part~0.4 part of crosslinking agent, 0.01~0.5 part of organometallic catalysts, amines catalyst 0.01~0.5 part, the 1st 0.1 part of network polymer~15 parts, under conditions of 5-35 DEG C of mixing speed 50-200r/min of material temperature It stirs evenly obtained；Reaction mass component B ' is 10 parts~20 parts of polyisocyanate compound, 2 parts of foaming agent~3.5 parts, foam It 0.05 part~0.2 part of stabilizer, is stirred evenly under conditions of 5-50 DEG C of mixing speed 50-200r/min of material temperature obtained.Then Reaction mass component A ' is mixed with reaction mass component B ' according to 1.0~1.5:1 mass ratio, is quickly stirred through professional equipment To the hybrid cross-linked dynamic aggregation object of foaming.Finally, the hybrid cross-linked dynamic aggregation object after foaming is added in mold, in room Temperature is lower to solidify 30min~60min, then solidifies at high temperature to get to based on hybrid cross-linked dynamic aggregation object foamed material. At least one component contains ligand groups in the component A ' and component B '.Be cured as at a high temperature of described be in temperature Solidify 6h at 60 DEG C, or in temperature be 80 DEG C of solidification 4h, or in temperature is 120 DEG C of solidification 2h.And so on, it is miscellaneous in preparation ternary When changing crosslinking dynamic aggregation object foamed material, the 1st network and the 2nd network are first prepared, then when preparing 3 network, the 1st net is added Network and the 2nd network are sufficiently mixed and foam.

In the preparation process of hybrid cross-linked dynamic aggregation object, the additive amount of dynamic aggregation object each component raw material is not done Special to limit, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.

In the present invention, the dynamic reversibility with optional hydrogen bond action is acted on using metal-ligand in dynamic aggregation object, When by external impacts, on the one hand polymer can show thickening responsiveness, on the other hand can also be made by metal-ligand Reach multi-absorption and the dissipation to impact energy with the reversible fracture with optional hydrogen bond action.By to dynamic aggregation object into The suitable component selection of row and formula design, can prepare polymer fiber with excellent energy-absorbing effect, film, plate, Foam, gel etc..Using this dynamic aggregation object as energy-absorbing material carry out energy-absorbing, can embody good damping, damping, every The effects of sound, noise elimination, shock resistance, thus in fields such as life, production, movement, leisure, amusement, military affairs, police service, security, medical cares There is extensive purposes.For example, polymer material can be applied to production damping shock absorber, it to be used for various motor vehicles, machinery Equipment, bridge, building vibration isolation, when being vibrated, the big energy that can dissipate plays damping, thus effectively The vibration of ground mitigation vibration body；Stress response possessed by dynamic aggregation object can also be used, generate the variation of the degree of cross linking, occur Flexible and strong elasticity transformation, plays the role of effective disperses impact forces, so as to be applied to buffering as energy-absorbing buffering material Packaging material, athletic protective article, the police protective materials of surge guard product and army etc. reduce article or human body outside Power effect lower suffered vibration and impact, the shock wave etc. generated including explosion；It can be devised by with shape memory function The energy-absorbing material of energy is applied to specific occasion, such as the energy-absorbing protector of personalized customization.It is provided by the present invention to be handed over based on hydridization Link the energy-absorbing method of state polymer, especially suitable for carrying out defense of resistance to impact to human body, animal body, article etc., such as with institute Material is stated as protector, body is protected in daily life, production and movement；It is prepared into explosion-proof tent, blanket, wall, prevents Glass sandwich glue, sandwich plate etc. are played, explosive-proof protector is carried out to article；Other protective article for cell/apparatus are prepared into, are applied to airborne With air-drop protection, automobile collision preventing, the defense of resistance to impact of electronic apparatus article etc..

Dynamic aggregation object material of the present invention is described further below with reference to some specific embodiments.Specifically Embodiment is that present invention be described in more detail, non-limiting protection scope of the present invention.

Embodiment 1

The acrylamide of 1 molar equivalent, the acryloyloxyethyl trimethyl of 2 molar equivalents are added in No. 1 reactor Ammonium chloride, and then as crosslinking agent enough water is added into No. 1 reactor in the 1,3-butadiene that 0.5 molar equivalent is added Reactant is sufficiently dissolved, and the potassium peroxydisulfate of 0.02 molar equivalent and the tetramethylethylenediamine of 0.02 molar equivalent is added (TEMED), mixed liquor is put into after mixing evenly after standing 12h in 30 DEG C of insulating boxs, a kind of dynamic aggregation object hydrogel is made. It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, extension test is carried out using cupping machine, stretches speed Rate is 50mm/min, and measuring sample tensile strength is 1.43 ± 0.34MPa, and elongation at break is 286.87 ± 48.32, the dynamic Polyalcohol hydrogel have good toughness and self-repairability, can be made into cushioning piece carry out using.

Embodiment 2

3.8 mass parts anisaldehydes and 2.3 mass parts aniline are added in No. 1 reactor, are dissolved in 250 mass parts first together Alcohol is heated to reflux 12h in a nitrogen atmosphere.Then 1.5 mass parts NaBH are added₄And continue at room temperature stir 12h, then plus Enter the hydrochloric acid solution of 10 mass parts 2mol/L, NH is added after stirring 10min₄PF₆Saturated aqueous solution, use deionized water after filtering Washing precipitating, obtains the object crosslinking agent of white solid；42 mass parts methyl acrylates, 18 matter are added in No. 2 reactors Measure part 3- butene-2 -ol, 5 mass parts 4- acrylamide Benzo-18-crown-6s, 6 mass parts (butylamino)-N- propyl- 2- alkene Base formamide, 0.12 mass parts dibenzoyl peroxide (BPO), 0.12 mass parts N, N- dimethylaniline, 4.6 mass parts objects are handed over Join agent, 150 mass parts DMF, after being stirred to react 1h at room temperature, it is different that 50 mass parts dimethyl sulfoxides (DMSO), 10 mass parts are added Ethyl cyanate, 10 mass parts TDI, 0.5 mass parts triethylamine continue to stir 12h, mixed liquor are put into 20 DEG C of insulating boxs and is stood After 12h, a kind of dynamic aggregation object organogel is made.The dynamic aggregation object organogel has good toughness, is made into The dumbbell shape batten of 80.0 × 10.0 × 2.0mm size carries out extension test, rate of extension 50mm/ using cupping machine Min, measuring sample tensile strength is 1.85 ± 0.33MPa, and elongation at break is 484.23 ± 73.42, can be made into noise reduction Gasket carry out using.

Embodiment 3

50 mass parts glycol phthalates, 26.1 mass parts acrylamides are added in No. 1 reactor to benzene phosphorus Hydrochlorate (being made using being reacted under the catalysis of triethyl group diamines phenylamino based phosphates and acryloyl chloride), 19.3 mass parts propylene 0.01 mass parts KPS, 0.25 mass parts N, N'- methylene-bisacrylamide is added in trimethylammonium trimethyl ammonium chloride, uses nitrogen Then 0.05 mass parts N, N, N', N'- tetramethyl diamines, 0.5 mass parts carbon fiber, ultrasonic wave is added in gas bell deoxygenation 10min It after dispersion, transfers the solution into mold, stands 1h at 40 DEG C, product 1 is made；100 mass parts are added in No. 2 reactors Glycol phthalate, product obtained 1,72 mass parts acrylamides, 15 mass parts 5- vinyl uracils, 0.05 matter Part KPS, 0.35 mass parts N, N'- methylene-bisacrylamide are measured, deoxygenation 10min is bubbled with nitrogen, 0.07 mass is then added Part N, N, N', N'- tetramethyl diamines transfer the solution into mold after mixing, are swollen 12h in the environment of 20 DEG C, take Mold out removes extra solvent, and then mold is put into 40 DEG C of baking ovens and stands 1h, and a kind of dynamic aggregation object plasticizer is made Swell gel.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, carries out stretching survey using cupping machine Examination, rate of extension 50mm/min, measure sample tensile strength be 2.53 ± 0.36MPa, elongation at break be 584.37 ± 59.23.The product has good toughness and intensity, can be used for manufacturing a kind of gel damping fin carry out using.

Embodiment 4

Allyl carbamate -6- the anthanthrene that 0.3 molar equivalent is added in No. 1 reactor (utilizes 6- methylol Anthanthrene and allyl isocyanate reaction be made), the styrene of 1 molar equivalent, 0.005 molar equivalent potassium peroxydisulfate (KPS), 0.005 molar equivalent N, N- dimethyl cyclohexyl amine, enough methylene chloride, be warming up to 50 DEG C be stirred to react 4h after, remove it is molten Product 1 is made in agent；50 mass parts products 1,35 mass parts acrylamides, 0.5 mass parts AIBN, 0.5 mass parts TEMED are mixed Conjunction is dissolved in 100 mass parts toluene, after being warming up to 80 DEG C of reaction 2h, is added 40 mass parts TDI, after the reaction was continued 2h, is removed molten After being washed with deionized water, the 1- ethyl-3-methylimidazole four of 0.5 mass parts nano silica and 50 mass parts is added in agent Borofluoride ion liquid, ultrasonic wave dispersion stand for 24 hours after mixing evenly, then remove solvent, and it is poly- to obtain a kind of dynamic Close object ionic liquid swell gel.The ionic liquid swell gel has good toughness and intensity, can be made into good The material of good cushion performance carry out using.

Embodiment 5

15 mass parts ethyl acrylates are added in No. 1 reactor, 5.1 mass parts acrylamides (utilize benzenephosphonic acid salt Phenylamino based phosphates and acryloyl chloride are reacted under the catalysis of triethyl group diamines and are made), ethyoxyl -1 4- of 5.2 mass parts, The chloro- 3- butene-2 -one of 1,1- tri-, 3- allyl-5- methyl-1 H- pyrrolo- [2,3-b] pyridine of 11 mass parts, 0.12 mass Part methyl ethyl ketone peroxide, the 4-dimethylaminopyridine of 0.12 mass parts, 180 mass parts chloroforms, after being stirred to react 1h at room temperature, add Enter 50 mass parts tetrahydrofurans (THF) to continue to stir 12h, then washes away THF as far as possible with deionized water, obtain product 1；2 10 mass parts products 1,15 mass parts polyethylene glycol (molecular weight is about 2000), 20 mass parts dichloromethanes are added in number reactor After being completely dissolved mixing, 10 mass parts poly methylene poly phenyl poly isocyanates, 5 mass parts glycerol, 0.2 mass parts are added in alkane Triethylamine, 0.5 mass parts glass microballoon are warming up to 80 DEG C after ultrasonic wave dispersion, and after the reaction was continued 2h, 30 mass parts alkane are added The polyethylene glycol oligomer and 1 mass parts copper chloride of base sealing end, remove solvent after mixing, and blend is placed in mold, and 80 12 hours are kept the temperature at DEG C, a kind of dynamic aggregation object oligomer swell gel is obtained after cooling.It is made into 80.0 × 10.0 × The dumbbell shape batten of 2.0mm size carries out extension test using cupping machine, and rate of extension 50mm/min measures sample Tensile strength is 4.21 ± 0.63MPa, and elongation at break is 279.35 ± 46.34, can be made into the progress of gel buffer gasket It uses.

Embodiment 6

1 molar equivalent containing hydrogen silicone oil (average molecular weight about 20000, the repetitive unit of siliceous hydrogen are added in No. 1 reactor Molar ratio with the repetitive unit of not siliceous hydrogen is about 1:2), 50 molar equivalent N- [2- (methylamino) ethyl] carbamic acid alkene Propyl ester and the quaternary ammonium base of silicone oil gross mass 7% are sufficiently mixed and are placed in mold, are warming up to 170 DEG C, keep the temperature 10 minutes, after cooling Product 1 is made；1 molar equivalent containing hydrogen silicone oil (average molecular weight about 20000, the repetition list of siliceous hydrogen are added in No. 1 reactor The molar ratio of first repetitive unit with not siliceous hydrogen is about 1:2), 25 molar equivalent 4-vinylpridines, 25 molar equivalent propylene Sour sodium and the quaternary ammonium base of silicone oil gross mass 7% are sufficiently mixed and are placed in mold, are warming up to 170 DEG C, keep the temperature 10 minutes, after cooling Product 2 is made；By 20 mass parts products 1,10 mass parts products 2,10 mass parts containing hydrogen silicone oils (average molecular weight about 20000, The molar ratio of the repetitive unit of the repetitive unit of siliceous hydrogen and not siliceous hydrogen is about 1:2), 2 mass parts crosslinking agent bi-vinyls seal End silicone oil and the quaternary ammonium base of silicone oil gross mass 7% are sufficiently mixed to be placed in mixer and be kneaded, and 1 mass parts charcoal is added Black, 1 mass parts glass fibre, after being kneaded 6h, taking-up is placed in mold, and a kind of dynamic aggregation object elastomer is made after cooling.Its With good intensity and plasticity, product of different shapes can be prepared into according to die size.Utilize its function Characteristic can be applied to body protection.

Embodiment 7

5.5 mass parts methacryl trimethyl ammonium chlorides, 2.8 mass parts 3- butene-1s-are added in No. 1 reactor Alcohol, 2 mass parts sodium acrylate, 0.1 mass parts azodiisobutyronitrile are warming up to 90 DEG C after mixing evenly, the reaction was continued 4h, so After 2 mass parts TDI and 0.05 mass parts triethylamine are added, after the reaction was continued 2h, product 1 is made；By the product 1,1 of 5 mass parts The diethyl toluene diamines (DETDA) of mass parts, the dibutyl tin dilaurate (DY-12) of 0.5 mass parts, 5 mass parts TDI, 10 mass parts polyether polyol DEP-5631D (hydroxyl value 54-58), 5 mass parts water, 3 parts by mass Methylene chloride, use ultrasonic wave It is put into after dispersion in suitable mold, after mixing with professional blender, is warming up to 80 DEG C, it is made to react and foam, foamed Foam is obtained a kind of dynamic aggregation object foamed material, be made into as curing 6h is continued in 60 DEG C of baking ovens after the completion The bulk sample of 20.0 × 20.0 × 20.0mm size carries out compression performance test using universal testing machine, and compression speed is 2mm/min, measuring 70% compressive strength of sample is 1.34 ± 0.21MPa.Obtained polymer foams light specific gravity and richness It is flexible, can be made into electronic device shockproof cushioning foam carry out using.

Embodiment 8

The allyl isocyanate of 1 molar equivalent, the triethylamine of 0.01 molar equivalent are added in No. 1 reactor, mixing is equal After even, 2- hydroxyl -9-Fluorenone of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；It is reacted at No. 1 It is even that 5.6 mass part compounds 1,8.4 mass parts 3- butene-1-ols, 15 mass parts ethyl acrylates, 0.5 mass parts are added in device Nitrogen bis-isobutyronitrile and 0.1 mass parts TEMED are warming up to 90 DEG C after mixing evenly, the reaction was continued 4h, and 4 mass parts are then added After the reaction was continued 2h, product 1 is made in TDI and 0.05 mass parts triethylamine；It is more that 100 mass parts polyethers are added in No. 2 reactors First alcohol SA-460 (hydroxyl value 445-475), 9 mass parts ethyl isocyanates are warming up to 80 DEG C, after reacting 1h, are warming up to 100 DEG C, reaction Product 2 is made after 2h；By the product 1 of 20 mass parts, 100 mass parts products 2,1 mass parts diethyl toluene diamine (DETDA), the dibutyl tin dilaurate (DY-12) of 0.5 mass parts, the TDI of 55 mass parts, 3 mass parts water, 3 mass parts two Chloromethanes, 3 mass parts glass fibres, are put into suitable mold after being dispersed with ultrasonic wave, after mixing with professional blender, 80 DEG C are warming up to, it is made to react and foam, foam is obtained into one kind as curing 6h is continued in 60 DEG C of baking ovens after the completion of foaming Dynamic aggregation object foamed material, is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, using universal testing machine into The test of row compression performance, compression speed 2mm/min, measuring 10% compressive strength of sample is 7.18 ± 0.44MPa.It obtains Polymer foams light specific gravity, intensity are good, easily molded, can be carried out as the shock resistance shell of electronic device using.

Embodiment 9

3.6g monohydroxy column [5] aromatic hydrocarbons, 150mL anhydrous acetonitrile, 6.8g Anhydrous potassium carbonate are added in No. 1 reactor, Flow back 20min under nitrogen atmosphere, and 1g 4- chloro biphenyl is then added, continues back flow reaction in a nitrogen atmosphere after mixing For 24 hours, it cleans after reaction, product 1 is made；By the product 1 of 5 mass parts, the diethyl toluene diamine of 0.05 mass parts (DETDA), the dibutyl tin dilaurates (DY-12) of 0.01 mass parts, the organic silicone oil of 0.02 mass parts, 1.25 mass parts MDI, 20 mass parts polyether polyol DEP-5631D (hydroxyl value 54-58), 0.5 mass parts water, 0.2 parts by mass Methylene chloride, dispersion It is put into suitable mold after uniformly, after mixing with professional blender, is warming up to 80 DEG C, it is made to react and foam, foamed Foam is obtained a kind of dynamic aggregation object foamed material, be made into as curing 6h is continued in 60 DEG C of baking ovens after the completion The bulk sample of 20.0 × 20.0 × 20.0mm size carries out compression performance test using universal testing machine, and compression speed is 2mm/min, measuring 70% compressive strength of sample is 1.29 ± 0.23MPa.Obtained polymer foams light specific gravity, quality are soft Soft and high resilience, can be made into airborne or air-drop protective materials carry out using.

Embodiment 10

In No. 1 reactor, the sodium alginate of 1 molar equivalent is taken to be dissolved in enough deionized waters, is then added 0.5 and rubs The NaIO of your equivalent₄, after room temperature is protected from light stirring 6h, the ethylene glycol that 0.5 molar equivalent is added continues to stir 1h, rotates by dialysis Afterwards, the sodium alginate of theoretical oxidation degree about 50% is made；In No. 2 reactors, 5.5 mass parts theoretical oxidation degree are added about 50% sodium alginate is dissolved in enough PBS buffer solution, be then added 4.5 mass parts 4- amino -2,6- dimethoxy-pyridines, 3 mass parts, seven fluorine butyryl amidine, 3 mass parts N, N, N- pivaloyl chlorination ammoniums continue after stirring 6h, 0.1 mass parts chlorine are added Change calcium, 10 mass parts deionized waters, after being stirred, mixed liquor is put into after standing 12h in 20 DEG C of insulating boxs, product 1 is made； By 10 mass parts products 1,10 mass parts methyl acrylates, 5 mass parts 1,3- butadiene, 0.1 mass parts potassium peroxydisulfate, 0.2 matter Amount part iron chloride, 0.1 mass parts TEMED mixing are dissolved in 50 mass parts butanone, and mixed liquor is put into 30 DEG C of insulating boxs and is stood After 12h, a kind of dynamic aggregation object organogel is made.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, benefit Extension test is carried out with cupping machine, rate of extension 50mm/min, measuring sample tensile strength is 3.24 ± 0.63 MPa, Elongation at break is 643.25 ± 86.57, which has good toughness and intensity, and the multilayer material of antiknock is made, Applied to anti-explosion building.

Embodiment 11

Allylurea-the 3- that 1 molar equivalent is added in No. 1 reactor is luxuriant and rich with fragrance (with phenanthrene -3- amine and allyl isocyanate reaction Be made), the sodium acrylate of 1 molar equivalent, the acrylamide of 1 molar equivalent, the 3- butene-1-ol of 1 molar equivalent, 0.01 rub That potassium peroxydisulfate of equivalent and the TEMED of 0.01 molar equivalent, and enough toluene is added and is stirred for dissolving, it then heats to 50 DEG C, after reacting 4h, 87 mass parts TDI and 0.1 mass parts triethylamine is added, the reaction was continued 2h removes solvent, product 1 is made； 100 mass parts polyether polyol EP-330N (hydroxyl value 32-36), 20 mass parts products 1,5 mass parts are added in No. 2 reactors Foam microspheres, the N-ethylmorpholine of 0.5 mass parts, the MDI of 8 mass parts, 5 mass parts water, 2 parts by mass Methylene chloride, mixing are equal It is even, 80 DEG C are warming up to, is quickly stirred to react with the blender of profession, it is after foaming that foam is ripe as continuing in 60 DEG C of baking ovens Change 6h, obtains a kind of dynamic aggregation object foamed material after cooling.It is made into the bulk of 20.0 × 20.0 × 20.0mm size Sample carries out compression performance test using universal testing machine, and compression speed 2mm/min, measuring 50% compressive strength of sample is 4.58±0.73MPa.Obtained polymer foams light specific gravity, resilience be good, good mechanical properties, can the army of being made into Alert body protection material carry out using.

Embodiment 12

Polyethers ketone powder, the 0.01 molar equivalent condensing agent that 1 molar equivalent side group contains carboxyl are added in No. 1 reactor I-hydroxybenzotriazole (HOBT) and 0.012 molar equivalent activator 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide salt Hydrochlorate (EDC), is dissolved in enough toluene, and after mixing, the N of 0.5 times of carboxyl molar equivalent, N- bis- is added in stirring to dissolution Picoline -2,6- diimine continues at room temperature after being stirred to react 12h, adds the 4- ammonia of 0.25 times of carboxyl molar equivalent 4- amino -1- the first of base -4'- sulfopropyl amino -3,3', 5,5'- tetramethyl biphenyl sodium salt and 0.25 times of carboxyl molar equivalent Base-pyridine, the reaction was continued 12h remove solvent, and it is spare that product 1 is made；1 molar equivalent side group is added in No. 2 reactors to contain There are the polyethers ketone powder, 0.01 molar equivalent condensing agent I-hydroxybenzotriazole (HOBT) and 0.012 molar equivalent of carboxyl to activate Agent 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC) is dissolved in enough toluene, stirring to dissolution mixing After uniformly, the 1,4-Diaminobutane of 0.5 times of carboxyl molar equivalent is added, continues after being stirred to react 12h at room temperature, removes Product 2 is made in solvent；40 mass parts products 1, the 20 mass parts polyether-ketones of mass parts product 2 and 50 are mixed, and 0.5 matter is added A kind of dynamic aggregation is made after extruding pelletization is molded in amount part Metal Organic Molecular cage (MOC-16), 2 mass parts carbon fibers Object ordinary solid.The dumbbell shape batten for taking 80.0 × 10.0 × 2.0mm size carries out extension test using cupping machine, draws Stretching rate is 10 mm/min, and measuring sample tensile strength is 82.56 ± 6.63MPa, and elongation at break is 72.78 ± 7.92%, Using its surface hardness and high intensity, polymer samples can be made to all kinds of plates with anti-flammability and impact resistance Material, profile shapes are applied to building materials, household field.

Embodiment 13

Be added in No. 1 reactor the end-vinyl of 1 molar equivalent containing viologen compound (with vinyl chloride, 1, 1 '-dialkyl group -4,4'-Bipyridine salt compounded of iodine and 50mL dimethylformamide (DMF), react 4h, and use methylene chloride at 50 DEG C Be made after recrystallization), 4- (trifluoromethyl) styrene of 1 molar equivalent, the potassium peroxydisulfate of 0.01 molar equivalent and 0.01 mole The TEMED of equivalent, and enough toluene is added and is stirred for dissolving, 50 DEG C are then heated to, after reacting 4h, removes solvent, system Obtain product 1；Be added in No. 2 reactors 20 mass parts polyether polyol SA-460 (hydroxyl value 445-475), 10 mass parts products 1, 3 mass parts glass fibres, 3 mass parts nano talcs, 2 mass parts hollow glass microbeads, 0.5 mass parts N- ethyl morpholine, The TDI of 15 mass parts, 4 mass parts water, 2 parts by mass Methylene chloride are uniformly mixed, are warming up to 80 DEG C, and the blender with profession is fast Speed is stirred to react, and foam is obtained a kind of dynamic aggregation after cooling as curing 6h is continued in 60 DEG C of baking ovens after foaming Object foamed material.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, carries out compressibility using universal testing machine It can test, compression speed 2mm/min, measuring 10% compressive strength of sample is 8.33 ± 0.74MPa.Obtained foam of polymers Material proportion is light, intensity is good, and have excellent impact resistance, can be carried out as shock resistance packing box using.

Embodiment 14

The 3- butene-1-ol of 1 molar equivalent, the methacryl trimethyl chlorine of 1 molar equivalent are added in No. 1 reactor Change the AIBN of ammonium, the perfluoropropene of 0.5 molar equivalent, the sodium acrylate of 0.5 molar equivalent, 0.01 molar equivalent, and foot is added The toluene of amount sufficiently dissolves it, then heats to 90 DEG C, removes solvent after reacting 4h, and product 1 is made；By 15 mass parts products 1, the N of 0.5 mass parts, N- dimethyl cyclohexyl amine, the MDI of 10 mass parts, 5 mass parts water, 4 parts by mass Methylene chloride, mixing are equal It is even, 80 DEG C are warming up to, is quickly stirred to react with the blender of profession, it is after foaming that foam is ripe as continuing in 60 DEG C of baking ovens Change 6h, obtains a kind of dynamic aggregation object foamed material after cooling.It is made into the bulk of 20.0 × 20.0 × 20.0mm size Sample carries out compression performance test using universal testing machine, and compression speed 2mm/min, measuring 50% compressive strength of sample is 2.56±0.23MPa.Obtained polymer foams light specific gravity, resilience are good, can be made into insole or matting materials into It exercises and uses.

Embodiment 15

100 mass parts toluene, 30 mass parts polyvinyl alcohol (molecular weight 2000), 0.1 mass parts are added in No. 1 reactor Sodium hydroxide after stirring and dissolving, is warming up to 100 DEG C, 10 mass parts 2,3- epoxypropyltrimethylchloride chloride and 2 mass parts is added Then [2,3,3,3- tetra- fluoro- 2- (trifluoromethyl) propyl] ethylene oxide, the reaction was continued 2h remove solvent, product 1 is made；It will The N of 5 mass parts products 1,0.1 mass parts, N- dimethyl cyclohexyl amine, the MDI of 9 mass parts, 6 mass parts water, 1 mass parts dichloromethane Alkane is uniformly mixed, is warming up to 80 DEG C, is quickly stirred to react with the blender of profession, dries foam as 60 DEG C after foaming Continue to cure 6h in case, obtains a kind of dynamic aggregation object foamed material after cooling.It is made into 20.0 × 20.0 × 20.0 mm The bulk sample of size carries out compression performance test using universal testing machine, and compression speed 2mm/min measures sample 70% Compressive strength is 1.14 ± 0.12MPa.It is obtained polymer foams light specific gravity, soft, damping can be made into and disappeared Sound material carry out using.Synergistic action effect under the action of pulling force, between ion-dipole effect and dipole-dipole effect The tensile strength and elongation at break for making the dynamic aggregation object have obtained certain promotion, and energy-absorbing effect is more preferable.At the material When under higher temperature, dipole-dipole declines, synergistic effect decline, at different temperature, the dynamic aggregation object energy Show orthogonal energy-absorbing effect.

Embodiment 16

The 4-vinylpridine of 1 molar equivalent, the acryloyl-oxyethyl three of 1 molar equivalent are added in No. 1 reactor Ammonio methacrylate, the methyl-allyl ketone of 1 molar equivalent, the acrylamide of 10 molar equivalents, 0.1 molar equivalent potassium peroxydisulfate (KPS), stir evenly, be warming up to 80 DEG C, after reacting 1h, be added the HDI of 5 molar equivalents, the triethylamine of 0.05 molar equivalent and After the reaction was continued after mixing 2h, enough 1,2- dimethyl-are added into product for the carbon nanotube of system gross mass 5% [the 2,3,5,6- tetra- { (diethylamino) of 3- hydroxyethyl imidazole toluenesulfonate ionic liquid and 0.005 molar equivalent Methyl } phenylene-Isosorbide-5-Nitrae-is bis- (trifluoromethanesulfonic acid palladium)], after mixing, places it in and be swollen at room temperature for 24 hours, obtain one kind Dynamic aggregation object ionic liquid swell gel.The dynamic aggregation object has good toughness, and has at various pressures Different resistivity, can be made into a kind of bumper and absorbing shock gel with stress response performance carry out using.

Embodiment 17

100 mass parts polyether polyol EP-560 (hydroxyl value 290-310), 20 mass parts isocyanides are added in No. 1 reactor Isopropyl propionate, 14 mass parts trifluoroacetic acid isocyanates are warming up to 80 DEG C, and after reacting 1h, 30 mass parts 2,3- epoxy third is added Base trimethyl ammonium chloride and 0.1 mass parts sodium hydroxide are warming up to 100 DEG C, and product 1 is made after reacting 2h；In No. 2 reactors It is added the N of obtained product 1,0.5 mass parts, N- dimethyl benzylamine, 3 mass parts trimethylolpropanes, 0.5 mass parts February Dilaurylate (DY-12), 1 mass parts organic silicone oil, the MDI of 50 mass parts, 5 mass parts water, 2 parts by mass Methylene chloride, It is uniformly mixed, is warming up to 80 DEG C, be quickly stirred to react with the blender of profession, by foam as in 60 DEG C of baking ovens after foaming Continue to cure 6h, obtains a kind of dynamic aggregation object foamed material after cooling.It is made into 20.0 × 20.0 × 20.0mm size Bulk sample, using universal testing machine carry out compression performance test, compression speed 2mm/min, measure sample 50% compression Intensity is 2.24 ± 0.13MPa.Polyurethane-based foam material obtained has certain resilience and flexibility, can be as Foamed cushioning pads are applied to sole material or industrial machinery buffer substrate tablet.

Embodiment 18

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, the trans- 4- hydroxyl Stilbene of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；It is anti-at No. 2 It answers and the 1 of 1 molar equivalent is added in device, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent is added 1 after mixing The N-Boc-2- amino-4-hydroxy butyric acid of molar equivalent, is warming up to 80 DEG C, is stirred to react 2h, and compound 2 is made；It is reacted at No. 3 Be added in device 100 mass parts polyether polyol EP-553 (hydroxyl value 54-58), 11.1 mass part compounds 1, be warming up to 80 DEG C, After reacting 1h, 5 mass parts ethyl isocyanates are added, product 1 is made after the reaction was continued 2h；Obtained by being added in No. 4 reactors Product 1,1 mass parts triethanolamine, 3 mass parts 1,4- butanediols (BDO), 17 mass parts cucurbit [7] ureas, 0.1 mass parts three Fluoroacetic acid, 0.1 mass parts hydrochloric acid, 0.5 mass parts organo-bismuth (DY-20), 0.5 mass parts organic silicone oil, 5 mass parts water, 4 mass Part methylene chloride, 5 mass parts MDI, are uniformly mixed, are warming up to 80 DEG C, are quickly stirred to react with the blender of profession, foaming Foam is obtained into a kind of dynamic aggregation object foamed material after cooling as curing 6h is continued in 60 DEG C of baking ovens afterwards.It is made into The bulk sample of 20.0 × 20.0 × 20.0mm size carries out compression performance test using universal testing machine, and compression speed is 2mm/min, measuring 50% compressive strength of sample is 1.89 ± 0.15MPa.Obtained polymer foams light specific gravity, quality compared with It is soft, resilience is good, can using polymer foams obtained as sound insulation, yielding rubber packing material carry out using.

Embodiment 19

100 mass parts deionized waters, 36 mass parts acrylamides, 19.3 mass parts acryloyls are added in No. 1 reactor Oxygroup ethyl-trimethyl salmiac, 13.6 mass parts sodium acetates, 0.1 mass parts thermal initiator potassium peroxydisulfate (KPS) and 0.77 matter Part N is measured, then N'- methylene-bisacrylamide is bubbled 10min with nitrogen and removes oxygen, is subsequently added into 0.1 mass parts N, N, N', N'- tetramethyl diamines, 0.2 mass parts nano silica, 0.5 mass parts graphene are dispersed with ultrasonic wave and are stirred Solution is transferred in mold after even, stands 1h at 40 DEG C, a kind of dynamic aggregation object hydrogel is made.It is made into 80.0 × The dumbbell shape batten of 10.0 × 2.0mm size carries out extension test using cupping machine, and rate of extension 50mm/min is surveyed Obtaining sample tensile strength is 2.35 ± 0.35MPa, and elongation at break is 364.15 ± 37.58, dynamic aggregation object hydrogel tool There are good toughness and resilience, can be by the deformation of itself come dissipative stress, while the conductivity of material can be with material Stretch or compressive state and change, embody stress response；Obtained polymeric material can be resisted at antistatic Surge guard pad.

Embodiment 20

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, the bromo- 1- propyl alcohol of 2,3- bis- of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；4 100 mass parts polyether polyol ED-28 (hydroxyl value 26.5-29.5), 15 mass part compounds 1 are added in number reactor, are warming up to 80 DEG C, after reacting 1h, product 1 is made；Obtained product 1,1 mass parts N, N- dimethyleyelohexane are added in No. 5 reactors Amine, 2 mass parts ethylenediamines (DA), 0.5 mass parts DY-215,1 mass parts organic silicone oil, 5 mass parts water, 3 mass parts dichloromethanes Alkane, 4 mass parts MDI are uniformly mixed, are warming up to 80 DEG C, are quickly stirred to react with the blender of profession, by foam after foaming As for curing 6h is continued in 60 DEG C of baking ovens, a kind of dynamic aggregation object foamed material is obtained after cooling.It is made into 20.0 × The bulk sample of 20.0 × 20.0mm size, using universal testing machine carry out compression performance test, compression speed 2mm/min, Measuring 50% compressive strength of sample is 2.49 ± 0.55MPa.Obtained polymer foams light specific gravity, good mechanical properties, Can be made into automobile impacting padded coaming carry out using.

Embodiment 21

1 molar equivalent [6- phenyl -2,2'- bipyridyl] -4- carboxylic acid, 1 molar equivalent allyl is added in No. 1 reactor Isocyanates, 0.01 molar equivalent triethylamine after being substantially soluble in sufficient toluene, are warming up to 80 DEG C, react 2h, then remove molten Compound 1 is made in agent；Be added in No. 2 reactors 1 molar equivalent 1- methylol pyrene, 1 molar equivalent allyl iso cyanurate, 0.01 molar equivalent triethylamine after being substantially soluble in sufficient toluene, is warming up to 80 DEG C, reacts 2h, then remove solvent, obtainedization Close object 2；7 mass part compounds 1,9 mass part compounds 2,0.2 mass parts NaOH are mixed and are dissolved in 10 mass parts DMSO, 30 mass parts ethyl acrylates are added under ice bath, after leading to nitrogen deoxygenation, 0.02 mass parts potassium peroxydisulfate, 0.01 mass parts is added TEMED, 0.01 mass parts platinum chloride, 1 mass parts glass fibre after being quickly stirred, are warming up to 60 DEG C, remove after reacting 4h A kind of dynamic aggregation object elastomer is made in solvent.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, is utilized Cupping machine carries out extension test, and rate of extension 50mm/min, measuring sample tensile strength is 4.78 ± 0.89MPa, breaks Splitting elongation is 452.67 ± 64.23%.The product has good resilience and mechanical property, can be prepared into a kind of suction Energy buffering spacer, for precision instrument or the shock-absorbing protecting of electronic product.

Embodiment 22

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, the pyridazine -3- methanol of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；It is anti-at No. 2 It answers and 100 mass parts polyether polyol EP-455S (hydroxyl value 43.5-46.5), 2.8 mass part compounds 1,3.2 mass is added in device Part isopropyl isocyanate, is warming up to 80 DEG C, and after reacting 1h, 1.9 mass parts 2,3- glycidyl phosphonic acids disodium salt and 0.01 is added Mass parts sodium hydroxide is warming up to 100 DEG C, and product 1 is made after reacting 2h；Be added in No. 5 reactors obtained product 1, 0.5 mass parts triethylamine, 3 mass parts diethylaminoethanols (DEAE), 0.5 mass parts organo-bismuth (DY-20), 0.5 mass parts have Machine silicone oil, 3 mass parts water, 1 parts by mass Methylene chloride, 6 mass parts isophorone diisocyanate (IPDI) are uniformly mixed, and are risen Temperature to 80 DEG C, with profession blender be quickly stirred to react, after foaming by foam as continue in 60 DEG C of baking ovens cure 6h, A kind of dynamic aggregation object foamed material is obtained after cooling.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, Using universal testing machine carry out compression performance test, compression speed 2mm/min, measure 70% compressive strength of sample be 1.32 ± 0.25MPa.Light-weight, good mechanical properties that obtained polymer foams have, the features such as energy-absorbing effect is prominent, can will It is as with stress buffer bubble wrap material.

Embodiment 23

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, 2,4,6- trimethyl benzylalcohols of 1 molar equivalent are added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；? 100 mass parts polyether polyol HPOP40 (hydroxyl value 20-23), 3.2 mass part compounds 1,3.5 mass are added in No. 3 reactors Part isopropyl isocyanate, is warming up to 80 DEG C, and after reacting 1h, 1.9 mass parts N- (2,3- glycidyl)-N-methylmorpholine is added Chloride and 0.01 mass parts sodium hydroxide are warming up to 100 DEG C, and product 1 is made after reacting 2h；Institute is added in No. 4 reactors Product 1 obtained, 1 mass parts N, N- dimethyl benzylamine, 3 mass parts trimethylolpropanes, 0.5 mass parts di lauric dibutyl Tin (DY-12), 1 mass parts organic silicone oil, 5 mass parts water, 2 parts by mass Methylene chloride, 7 mass parts MDI are uniformly mixed, heating To 80 DEG C, with profession blender be quickly stirred to react, after foaming by foam as continue in 60 DEG C of baking ovens cure 6h, it is cold But a kind of dynamic aggregation object foamed material is obtained afterwards.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, benefit Carry out compression performance test with universal testing machine, compression speed 2mm/min, measure 50% compressive strength of sample be 3.45 ± 0.33MPa.Obtained polymer foams light specific gravity, resilience are good, can be made into the body protections material such as wrist guard or knee-pad Material carry out using.

Embodiment 24

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, 2,3,4,5,6- five fluoro benzyl alcohols of 1 molar equivalent are added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made； The 1 of 1 molar equivalent is added in No. 2 reactors, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent is uniformly mixed Afterwards, the benzyl alcohol of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 2 is made；1 is added in No. 3 reactors The 1 of molar equivalent, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent, after mixing, 1 molar equivalent of addition (1, 1'- biphenyl) -4- methanol, 80 DEG C are warming up to, 2h is stirred to react, compound 3 is made；100 mass parts are added in No. 4 reactors Polyether polyol EP-3600 (hydroxyl value 26-30), 3.7 mass part compounds 1,2.7 mass part compounds 2,3.5 mass parts chemical combination Object 3 is warming up to 80 DEG C, and product 1 is made after reacting 2h；Obtained product 1,1 mass parts, three second are added in No. 5 reactors Amine, 3 mass parts ethylenediamines (DA), 0.5 mass parts modified triethylene diamine solution (DY-8154), 1 mass parts organic silicone oil, 2 matter Part water, 1 parts by mass Methylene chloride, 3 mass parts glass fibres, 5 mass parts TDI are measured, is uniformly mixed, 80 DEG C is warming up to, with profession Blender be quickly stirred to react, foam is obtained one after cooling as continuing to cure 6 h in 60 DEG C of baking ovens after foaming Kind dynamic aggregation object foamed material.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, utilizes universal testing machine Compression performance test is carried out, compression speed 2mm/min, measuring 10% compressive strength of sample is 4.53 ± 0.67MPa.It obtains Polymer foams light specific gravity, intensity it is good, can be made into residential block on both sides of the road acoustic material carry out using.

Embodiment 25

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, the 1- amino that 1 molar equivalent is added is cool (restore the cool nitro of 1- nitro and be made), is warming up to 80 DEG C, stirring 2h is reacted, compound 1 is made；Hexamethylene diisocyanate, 0.01 molar equivalent of 1 molar equivalent are added in No. 2 reactors Triethylamine, after mixing, be added 1 molar equivalent 6- amino-alpha-cyclodextrin, be warming up to 80 DEG C, be stirred to react 2h, be made Compound 2；The 1 of 1 molar equivalent is added in No. 3 reactors, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, the 4- azido -1- butylamine of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 3 is made；? 100 mass parts polyether polyol DD-380A (hydroxyl value 360-400), 35 mass part compounds 1,11.7 are added in No. 4 reactors Mass part compound 2,11.7 mass part compounds 2,2.8 mass part compounds 3 are warming up to 80 DEG C, and product is made after reacting 2h 1；Obtained product 1,3 mass parts AC foaming agents, 7 mass parts sorbierites, 57 mass parts MDI, 1 are added in No. 3 reactors Mass parts carbon fiber, the miscellaneous furans particle of 1 mass parts osmium, are warming up to 80 DEG C, after abundant cross-linking reaction, by cross-linking products take out as In mold, foaming is carried out using vulcanizing press, wherein molding temperature is 140-150 DEG C, clamp time 10- 15min, pressure 10MPa finally obtain dynamic aggregation object foamed material, with good rigidity and intensity.It is made into The bulk sample of 20.0 × 20.0 × 20.0mm size carries out compression performance test using universal testing machine, and compression speed is 2mm/min, measuring 10% compressive strength of sample is 9.27 ± 1.33MPa.Obtained polymer foams light specific gravity, size are steady It is qualitative good, can be carried out as the shock resistance antistatic guard shield of electronic device using.

Embodiment 26

3- methyl -2- propylene tetrazole radical-pyridine (3- methyl -2- cyanopyridine of 24 mass parts is added in No. 1 reactor Carry out click-reaction under triethylamine hydrochloride and toluene catalytically with 3- azido -1- propylene and be made), 40 mass parts acrylic acid Methyl esters, 15 mass parts 1,2- butadiene monoxides, 29.5 mass parts 2- methacryloxyethyl phosphocholines, 100 mass parts first Benzene, 0.1 mass parts potassium peroxydisulfate, are uniformly mixed, and be warming up to 80 DEG C, after reacting 4h, remove excess of solvent, product is made 1；By product 1, the diethyl toluene diamine (DETDA) of 10 mass parts, 0.5 mass parts dibutyl tin dilaurate (DY-12), 6 Mass parts diethyl azodiformate, 20 mass parts TDI, 5 mass parts palladium (II) propionates, 10 mass parts water, after mixing It is put into suitable mold, carries out foaming using vulcanizing press, wherein molding temperature is 110-120 DEG C, clamp time For 10-15min, pressure 10MPa, foam is placed in 60 DEG C of baking ovens after molding and continues to cure 4h, it is poly- that dynamic is obtained after cooling Polymer foam.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, is compressed using universal testing machine Performance test, compression speed 2mm/min, measuring 50% compressive strength of sample is 2.84 ± 0.35MPa.Obtained polymer bubble Foam material proportion is light, toughness is good, can be automatically repaired after cracking, can be made as airborne or air-drop protective materials With.

Embodiment 27

100 mass parts deionized waters, 20 mass parts methyl acrylates, 10 mass parts acryloyls are added in No. 1 reactor Amine, 10.5 mass parts acrylamides-beta-cyclodextrin (reacted and be made with acryloyl chloride using 6- amino-beta-cyclodextrin), 3 mass Part acrylamide -1- adamantane (reacted and be made with acryloyl chloride using 1- aminoadamantan), 1 mass parts polyvinyl alcohol, 10 matter Measure part (perfluoro butyl) ethylene, then be added 2.0 mass parts carbon nanotubes, 1.5 mass parts of carbon black, 1.5 mass parts nano-silver powders, 10 mass parts 1- allyl pyridines, 1 mass parts azodiisobutyronitrile are uniformly mixed after ultrasonic wave dispersion, are warming up to 90 DEG C, after reacting 4h, 15 mass parts MDI and 0.1 mass parts triethylamine is added, after the reaction was continued 2h, removes solvent, place the product in After dibutyl phthalate (DBP) stands swelling for 24 hours, takes out, dry surface DBP, a kind of dynamic aggregation object plasticizer is made Swell gel.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, carries out stretching survey using cupping machine Examination, rate of extension 50mm/min, measure sample tensile strength be 2.33 ± 0.45MPa, elongation at break be 627.34 ± 69.18%.Polymer material has good flexibility and tensile toughness, can be by the deformation of itself come dissipative stress, simultaneously Material has good electric conductivity；It can be by obtained polymeric material at the supercapacitor with excellent impact resistance energy Carry out using.

Embodiment 28

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, 4- amino-cup [4] aromatic hydrocarbons of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；? The 1 of 1 molar equivalent is added in No. 2 reactors, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent adds after mixing The dodecanol for entering 1 molar equivalent is warming up to 80 DEG C, is stirred to react 2h, and compound 2 is made；1 is added in No. 3 reactors to rub The left-handed of 1 molar equivalent is added after mixing in the 1 of that equivalent, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent Carnitine is warming up to 80 DEG C, is stirred to react 2h, and compound 3 is made；100 mass parts polyether polyol are added in No. 4 reactors EP-8000 (hydroxyl value 22-26) and 0.5 mass parts triethylamine, are added 11.4 mass part compounds 1,3.6 mass after mixing Part compound 2,3.3 mass part compounds 3, are warming up to 80 DEG C, and after the reaction was continued 2h, product 1 is made；Add in No. 5 reactors Enter obtained product 1,1 mass parts N, N- dimethyl cyclohexyl amine, 2 mass parts triethylene glycols, 4 mass parts TDI, be uniformly mixed, rises Temperature is to 80 DEG C, after reacting 2h, reaction solution taking-up is placed in mold, 100 mass parts diisooctyl phthalates are added (DIOP), after standing swelling for 24 hours in 30 DEG C of baking ovens, a kind of dynamic aggregation object plasticizer swell gel had both been made.Gel tool Have good toughness and anti-pressure ability, can be used as one kind can selfreparing buffering spacer, the damping for precision instrument structure disappears Sound.

Embodiment 29

1 molar equivalent [6- phenyl -2,2'- bipyridyl] -4- carboxylic acid, 1 molar equivalent allyl is added in No. 1 reactor Isocyanates, 0.01 molar equivalent triethylamine after being substantially soluble in sufficient toluene, are warming up to 80 DEG C, react 2h, then remove molten Product 1 is made in agent；5 mass parts products 1,0.2 mass parts NaOH are mixed and are dissolved in 10 mass parts DMSO, and 1.6 mass are added Part 1- allyl -3- methylimidazole chlorine, 1.9 mass parts acryloyloxyethyl trimethyl ammonium chlorides and 2 mass parts 1,4- fourths two After stirring and dissolving, 2.7 mass parts sodium acrylate are added in alkene under ice bath, and after leading to nitrogen deoxygenation, 0.02 mass parts persulfuric acid is added Potassium, 0.01 mass parts TEMED, 0.02 mass parts palladium chloride, 0.8 mass parts glass fibre, after being quickly stirred, are warming up to 60 DEG C, solvent is removed after reacting 4h, a kind of dynamic aggregation object elastomer is made.It is made into 80.0 × 10.0 × 2.0mm size Dumbbell shape batten, using cupping machine carry out extension test, rate of extension 50mm/min, measuring sample tensile strength is 4.67 ± 0.82MPa, elongation at break are 378.56 ± 53.25%.Obtained dynamic aggregation object elastomer after tension failure, By section fit together can self-heal, can a kind of system as energy-absorbing damping property gasket for footwear material or sports goods Make.

Embodiment 30

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, the bromo- 1- propyl alcohol of 2,3- bis- of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；4 100 mass parts polyether polyol ED-28 (hydroxyl value 26.5-29.5), 3.9 mass part compounds 1 are added in number reactor, are warming up to 80 DEG C, react 1h after, be added 5.6 mass parts 2,3- epoxypropyltrimethylchloride chloride, 4.5 mass parts oxygen acetyl formic acid sylvite and 0.1 mass parts sodium hydroxide, is warming up to 100 DEG C, the reaction was continued 2h, and product 1 is made；Obtained by being added in No. 5 reactors Product 1,1 mass parts N, N- dimethyl cyclohexyl amine, 2 mass parts ethylenediamines (DA), 0.5 mass parts DY-215,1 mass parts are organic Silicone oil, 5 mass parts water, 3 parts by mass Methylene chloride, 6 mass parts MDI are uniformly mixed, are warming up to 80 DEG C, with the blender of profession It is quickly stirred to react, after foaming it is poly- to be obtained into a kind of dynamic as curing 6h is continued in 60 DEG C of baking ovens for foam after cooling Polymer foam.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, is compressed using universal testing machine Performance test, compression speed 2mm/min, measuring 50% compressive strength of sample is 3.25 ± 0.63MPa.Obtained polymer bubble Foam material proportion is light, resilience is good, and the energy self-healing after cracking, movement can be made in this dynamic aggregation object foamed material Shoes insole plays the role of good buffering and protection sole.

Embodiment 31

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, 4- amino -2,3 of 1 molar equivalent is added, 5,6- ptfe pyridines are warming up to 80 DEG C, are stirred to react 2h, obtainedization Close object 1；The 1 of 1 molar equivalent is added in No. 2 reactors, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After uniformly, the benzyl alcohol of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 2 is made；In No. 3 reactors It is added the 1 of 1 molar equivalent, 1 molar equivalent is added after mixing in the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent 4'- amino -2,2':6', 2 "-terpyridyls are warming up to 80 DEG C, are stirred to react 2h, and compound 3 is made；In No. 4 reactors 100 mass parts polyether polyol DL-400 (hydroxyl value 270-290) and 0.5 mass parts triethylamine are added, 23 are added after mixing Mass part compound 1,42 mass part compounds 2,28 mass part compounds 3, are warming up to 80 DEG C, after the reaction was continued 2h, are made and produce Object 1；Obtained product 1,100 mass parts polyether polyol MN-3050DF (hydroxyl value 54-57), 4 are added in No. 5 reactors Mass parts 3- amido-1,2-propanediol, 10 mass parts epoxidized soybean oils, 0.5 mass parts KH550,60 mass parts kaolin, 3 matter Part UV-531,10 mass parts pentachlorophenols, 1 mass parts trifluoromethanesulfonic acid europium, 1.5 mass parts dibutyl tin dilaurates are measured, is mixed After closing uniformly, 50 mass parts TDI are added, stirs evenly, mixed liquor is placed in mold, stand 4h in 50 DEG C of baking ovens, takes out A kind of dynamic aggregation object elastomeric material is made after cooling.It is made into the dumbbell pattern of 80.0 × 10.0 × 2.0 mm sizes Item, using cupping machine carry out extension test, rate of extension 50mm/min, measure sample tensile strength be 4.13 ± 0.95MPa, elongation at break are 359.27 ± 77.35%.The product can be prepared into a kind of damping, buffering race of good performance Road material is carried out using can be realized the effect being automatically repaired in impaired cracking.

Embodiment 32

N-Methyl pyrrolidone, the 3g graphene oxide of 150mL are added in No. 1 reactor, after ultrasonic wave is uniformly dispersed, Be added the 4,4- diamino-diphenyl ether (ODA) of 4.6g, 3.7g 1- (2- diazanyl -2- oxoethyl)-pyridinium chloride, 1.3g (2- amino-ethyl) phosphonic acids disodium, and 80 DEG C, after being uniformly mixed are warming up to, reactant is moved into hydro-thermal reaction container In, it is placed under 80 DEG C of baking ovens and reacts for 24 hours, after the reaction was completed disperse modified graphene oxide obtained in using ultrasonic wave N-Methyl pyrrolidone is configured to the solution of 3.5mg/mL, spare；The N- crassitude of 72mL is added in No. 2 reactors Ketone, 4, the 4- diamino-diphenyl ether (ODA) of 3.2g, 6.3mL modified graphene oxide solution, be uniformly dispersed using ultrasonic wave Afterwards, 3,3', 4, the 4'- biphenyltetracarboxylic dianhydrides (BPDA) of 4.8g are added in a nitrogen atmosphere, stir to after being completely dissolved, are added Reactant is transferred in the mold of production film by 13mL acetic anhydride, 10.5mL pyridine immediately after mixing, and reaction is for 24 hours Afterwards, a kind of dynamic aggregation object film is obtained.It is cut into the dumbbell pattern of 80.0 × 10.0 × (0.08 ± 0.02) mm sizes Item, using cupping machine carry out extension test, rate of extension 50mm/min, measure sample tensile strength be 4.42 ± 0.34MPa, elongation at break are 435 ± 63%.Sample recycles after breaking, and places it in mold and is bonded after 1-3h, can Again it forms a film, is reused, thin polymer film is pressed together on tent cloth, explosion-proof tent can be prepared.

Embodiment 33

With 1 molar equivalent 4,4'- azo bis- (4- cyano amylalcohols) is initiator, using 4- amylene-1-ol as chain-transferring agent, with Stannous octoate is catalyst, causes 50 molar equivalent α-ring-opening polymerisation of the chloro- 6-caprolactone at 110 DEG C, obtains product 1.It will Resulting product 1 is dissolved in dimethylformamide, and the sodium azide of 2 molar equivalent of chlorine atom is added, and reaction obtains product 2, is added One end of 0.6 times of molar equivalent of azido is the 1,4- fourth two of 0.2 times of molar equivalent of bipyridyl salt compounded of iodine and azido of alkynyl Alkynes is dissolved in tetrahydrofuran, and under the catalysis of cuprous iodide and pyridine, reaction obtains product 3 at 35 DEG C.It will be obtained by 100 mass parts Product 3 is blended with a certain amount of cucurbit [8] urea, keeps bipyridyl and the molar ratio of cucurbit [8] urea is 4:1,2-5 is added The antioxidant sodium dithionite of mass parts is sufficiently blended and is placed in mold, is pressed and molded, obtains a kind of dynamic aggregation object Elastomer.The elastomer has good resilience, intensity, toughness and good plasticity, can be prepared into according to die size Product of different shapes, can be made into buffering spacer carry out using.

The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks Domain is included within the scope of the present invention.

Claims

1. a kind of energy-absorbing method based on hybrid cross-linked dynamic aggregation object, which is characterized in that it is poly- to provide a kind of hybrid cross-linked dynamic Object or its composition are closed, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object, contains The covalent cross-linking and at least one second group of supermolecular mechanism that formed by covalent bond and optional first group of supermolecular mechanism；Its In, it is more than the gel point that covalent cross-linking reaches covalent cross-linking at least one cross-linked network；Wherein, second group of oversubscription Son acts on and includes at least ionization, ion-dipole acts on, Host-guest acts on, close metal function, dipole-dipole act on, Halogen bond effect, cation-π effect, anion-π effect, benzene-fluorobenzene effect, the effect of π-π stacking, ion hydrogen bond action, freedom Base cation dimerization, first group of supermolecular mechanism include hydrogen bond action, metal-ligand effect.

2. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object is only Make simultaneously containing covalent cross-linking and at least one second group of supermolecule containing a cross-linked network, and in this cross-linked network With crosslinking, wherein the degree of cross linking of covalent cross-linking is more than its gel point, the crosslinking of supermolecule provided by second group of supermolecular mechanism The degree of cross linking in its gel point above and below.

3. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object is only Make simultaneously containing covalent cross-linking and at least one second group of supermolecule containing a cross-linked network, and in this cross-linked network With crosslinking and at least one first group of supermolecular mechanism crosslinking, wherein the degree of cross linking of covalent cross-linking is more than its gel point, and second The degree of cross linking of supermolecule crosslinking is in its gel point above and below, first group of supermolecular mechanism institute provided by group supermolecular mechanism The degree of cross linking of the supermolecular mechanism crosslinking of offer is in its gel point above and below.

4. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, one of cross-linked network contains covalent cross-linking simultaneously and at least one second group of supermolecular mechanism is handed over Connection, wherein the degree of cross linking of covalent cross-linking is more than its gel point, the friendship of the crosslinking of supermolecule provided by second group of supermolecular mechanism Connection degree is in its gel point above and below；Another cross-linked network only contains at least one first group of supermolecular mechanism, wherein The degree of cross linking of the crosslinking of supermolecule provided by least one first group of supermolecular mechanism is more than its gel point.

5. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking its gel point with On；Another cross-linked network contains at least one second group of supermolecular mechanism, wherein at least one second group of supermolecular mechanism The degree of cross linking of provided supermolecule crosslinking is more than its gel point.

6. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, one of cross-linked network contains the degree of cross linking of covalent cross-linking and covalent cross-linking more than its gel point； Another cross-linked network contains at least one second group of supermolecular mechanism, wherein at least one second group of supermolecular mechanism institute The degree of cross linking of the supermolecule crosslinking of offer is more than its gel point；Simultaneously also containing at least one at least one cross-linked network First group of supermolecular mechanism, wherein supermolecule provided by first group of supermolecular mechanism crosslinking the degree of cross linking its gel point with It is upper or following.

7. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are three cross-linked network, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking its gel point with On；Another cross-linked network only contains at least one second group of supermolecular mechanism crosslinking, wherein at least one second group of oversubscription Son acts on the degree of cross linking of provided supermolecule crosslinking more than its gel point；Third cross-linked network only contains at least one the One group of supermolecular mechanism crosslinking, wherein the degree of cross linking of the crosslinking of supermolecule provided by least one first group of supermolecular mechanism exists It is more than its gel point.

8. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking its gel point with On；Another cross-linked network is simultaneously containing covalent cross-linking and the crosslinking of at least one second group of supermolecular mechanism and covalent cross-linking The degree of cross linking is more than its gel point, wherein the degree of cross linking of the crosslinking of supermolecule provided by second group of supermolecular mechanism is in its gel Point above and below.

9. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object contains There are two cross-linked network, one of cross-linked network contains the degree of cross linking of covalent cross-linking and covalent cross-linking more than its gel point； Another cross-linked network is simultaneously containing covalent cross-linking and the crosslinking of at least one second group of supermolecular mechanism and the friendship of covalent cross-linking Connection degree is more than its gel point, wherein the degree of cross linking of the crosslinking of supermolecule provided by second group of supermolecular mechanism is in its gel point Above and below；Simultaneously also containing at least one first group of supermolecular mechanism at least one cross-linked network, wherein first group The degree of cross linking of the crosslinking of supermolecular mechanism provided by supermolecular mechanism is in its gel point above and below.

10. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one friendship Networking network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and divide in wherein at least one network Dissipate the noncrosslinking supermolecule polymer containing at least one second group of supermolecular mechanism.

11. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one friendship Networking network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and divide in wherein at least one network It is poly- to dissipate the noncrosslinking supermolecule containing at least one second group of supermolecular mechanism and at least one first group of supermolecular mechanism Close object.

12. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one friendship Networking network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and divide in wherein at least one network Dissipate the existing cross-linked polymer for containing at least one second group of supermolecular mechanism in granular form.

13. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one friendship Networking network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and divide in wherein at least one network It dissipates existing containing at least one second group of supermolecular mechanism and at least one first group of supermolecular mechanism in granular form Cross-linked polymer.

14. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and acted on simultaneously containing covalent cross-linking and ion-dipole in this cross-linked network, wherein covalently For the degree of cross linking of crosslinking more than its gel point, ion-dipole acts on the degree of cross linking of provided supermolecule crosslinking in its gel point Above and below.

15. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and contain covalent cross-linking and ionization simultaneously in this cross-linked network, wherein covalent cross-linking The degree of cross linking more than its gel point, supermolecular mechanism provided by ionization crosslinking the degree of cross linking more than its gel point or with Under.

16. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and contain covalent cross-linking and ion-dipole effect and ionization simultaneously in this cross-linked network, Wherein, more than its gel point, the degree of cross linking that ion-dipole acts on provided supermolecule crosslinking exists the degree of cross linking of covalent cross-linking Its gel point above and below, the degree of cross linking of the crosslinking of supermolecular mechanism provided by ionization more than its gel point or with Under.

17. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and acted on simultaneously containing covalent cross-linking and dipole-dipole in this cross-linked network, wherein covalently For the degree of cross linking of crosslinking more than its gel point, the degree of cross linking that dipole-dipole acts on provided supermolecular mechanism crosslinking is solidifying at it Glue point above and below.

18. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and simultaneously containing covalent cross-linking and ion-dipole effect and dipole-dipole in this cross-linked network Effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, ion-dipole acts on the friendship of provided supermolecule crosslinking For connection degree in its gel point above and below, dipole-dipole acts on the degree of cross linking of provided supermolecular mechanism crosslinking in its gel Point above and below.

19. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and simultaneously containing covalent cross-linking and ion-dipole effect and metal-ligand in this cross-linked network Effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, ion-dipole acts on the friendship of provided supermolecule crosslinking For connection degree in its gel point above and below, metal-ligand acts on the degree of cross linking of provided supermolecular mechanism crosslinking in its gel Point above and below.

20. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and contain covalent cross-linking and ion-dipole effect and hydrogen bond action simultaneously in this cross-linked network, Wherein, more than its gel point, the degree of cross linking that ion-dipole acts on provided supermolecule crosslinking exists the degree of cross linking of covalent cross-linking Its gel point above and below, the degree of cross linking of the crosslinking of supermolecular mechanism provided by hydrogen bond action more than its gel point or with Under.

21. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and acted on simultaneously containing covalent cross-linking and Host-guest in this cross-linked network, wherein covalently For the degree of cross linking of crosslinking more than its gel point, Host-guest acts on the degree of cross linking of provided supermolecule crosslinking in its gel point Above and below.

22. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and simultaneously containing covalent cross-linking and ion-dipole effect and Host-guest in this cross-linked network Effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, ion-dipole acts on the friendship of provided supermolecule crosslinking For connection degree in its gel point above and below, Host-guest acts on the degree of cross linking of provided supermolecular mechanism crosslinking in its gel Point above and below.

23. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and contain covalent cross-linking and Host-guest effect and hydrogen bond action simultaneously in this cross-linked network, Wherein, more than its gel point, the degree of cross linking that Host-guest acts on provided supermolecule crosslinking exists the degree of cross linking of covalent cross-linking Its gel point above and below, the degree of cross linking of the crosslinking of supermolecular mechanism provided by hydrogen bond action more than its gel point or with Under.

24. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and simultaneously containing covalent cross-linking and Host-guest effect and metal-ligand in this cross-linked network Effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, Host-guest acts on the friendship of provided supermolecule crosslinking For connection degree in its gel point above and below, metal-ligand acts on the degree of cross linking of provided supermolecular mechanism crosslinking in its gel Point above and below.

25. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and simultaneously containing covalent cross-linking and Host-guest effect and ion hydrogen bond in this cross-linked network Effect, wherein for the degree of cross linking of covalent cross-linking more than its gel point, Host-guest acts on the friendship of provided supermolecule crosslinking Connection degree is in its gel point above and below, and the degree of cross linking of the crosslinking of supermolecular mechanism provided by ion hydrogen bond action is in its gel point Above and below.

26. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and acted on simultaneously containing covalent cross-linking and π-π stacking in this cross-linked network, wherein is covalently handed over For the degree of cross linking of connection more than its gel point, π-π stacking acts on the degree of cross linking of provided supermolecule crosslinking more than its gel point Or it is following.

27. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and makees simultaneously containing covalent cross-linking and the effect of π-π stacking and ion-dipole in this cross-linked network With, wherein for the degree of cross linking of covalent cross-linking more than its gel point, π-π stacking acts on the degree of cross linking of provided supermolecule crosslinking In its gel point above and below, ion-dipole act on provided by supermolecule crosslinking the degree of cross linking more than its gel point or Below.

28. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and makees simultaneously containing covalent cross-linking and the effect of π-π stacking and Host-guest in this cross-linked network With, wherein for the degree of cross linking of covalent cross-linking more than its gel point, π-π stacking acts on the degree of cross linking of provided supermolecule crosslinking In its gel point above and below, Host-guest act on provided by supermolecule crosslinking the degree of cross linking more than its gel point or Below.

29. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and simultaneously containing covalent cross-linking and the effect of π-π stacking and hydrogen bond action in this cross-linked network, and The effect of π-π stacking and hydrogen bond action are mutually indepedent；Wherein, the degree of cross linking of covalent cross-linking is more than its gel point, the effect of π-π stacking The degree of cross linking of provided supermolecule crosslinking is in its gel point above and below, the friendship of supermolecule crosslinking provided by hydrogen bond action Connection degree is in its gel point above and below.

30. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and makees simultaneously containing covalent cross-linking and the effect of π-π stacking and metal-ligand in this cross-linked network With, and the effect of π-π stacking and metal-ligand effect are mutually indepedent；Wherein, the degree of cross linking of covalent cross-linking is more than its gel point, π-π stacking acts on the degree of cross linking of provided supermolecule crosslinking in its gel point above and below, and metal-ligand effect is provided Supermolecule crosslinking the degree of cross linking in its gel point above and below.

31. the energy-absorbing method of hydridization dynamic aggregation object according to claim 1, which is characterized in that provide a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object contains only There is a cross-linked network, and makees simultaneously containing covalent cross-linking and the effect of π-π stacking and ion hydrogen bond in this cross-linked network With, and the effect of π-π stacking and ion hydrogen bond action are mutually indepedent；Wherein, the degree of cross linking of covalent cross-linking is more than its gel point, π- π stacking act on provided by supermolecule crosslinking the degree of cross linking in its gel point above and below, provided by ion hydrogen bond action The degree of cross linking of supermolecule crosslinking is in its gel point above and below.

32. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that constitute dynamic The recipe ingredient of state polymer further include it is following any or appoint it is several can additive: other polymers, auxiliary agent, filler；

Wherein, addible other polymers be selected from it is following any or appoint it is several: natural polymer, synthetic resin, Synthetic rubber, synthetic fibers；

Wherein, addible auxiliary agent is selected from following any or appoints several: catalyst, initiator, antioxidant, light stabilizer, heat Stabilizer, chain extender, toughener, coupling agent, lubricant, release agent, plasticizer, foaming agent, dynamic regulation agent, antistatic agent, Emulsifier, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickener, levelling agent, resists dispersing agent Microbial inoculum；

Wherein, addible filler is selected from following any or appoints several: inorganic non-metallic filler, metal packing, organic filler.

33. according to claim 1 to the energy-absorbing method based on hybrid cross-linked dynamic aggregation object described in any one of 32, feature It is, the form of the dynamic aggregation object or its composition has following any: ordinary solid, elastomer, gel, foam material Material.

34. according to claim 1 to the energy-absorbing method based on hybrid cross-linked dynamic aggregation object described in any one of 32, feature It is, is applied to explosion-proof, defense of resistance to impact, sound insulation, noise elimination, damping, vibration damping, damping, buffering.