CN109206824A - A kind of physics split-phase supermolecule dynamic aggregation object and its application - Google Patents

A kind of physics split-phase supermolecule dynamic aggregation object and its application Download PDF

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CN109206824A
CN109206824A CN201710522388.5A CN201710522388A CN109206824A CN 109206824 A CN109206824 A CN 109206824A CN 201710522388 A CN201710522388 A CN 201710522388A CN 109206824 A CN109206824 A CN 109206824A
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polymer
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不公告发明人
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Xiamen Iron Cloth Mstar Technology Ltd
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Weng Qiumei
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Abstract

The invention discloses a kind of physics split-phase supermolecule dynamic aggregation objects, wherein containing while having the block polymer molecules of hard section and soft segment；Crystalline phase and/or the phase incompatible with soft segment are mutually mixed and/or can formed each independently between each hard section of the block polymer molecules, to form split-phase physical crosslinking and/or the polymerization based on hard section, each soft segment of the block polymer molecules is unformed shape；Contain at least one group/unit for forming dynamic supermolecular mechanism at least one soft segment of the block polymer molecules；The dynamic aggregation object has shape memory function, self-repair function and ultra-tough, and in fields such as bio-medical material, military affairs, aerospace, the energy, buildings, tool has been widely used.

Description

Physical split-phase supermolecule dynamic polymer and application thereof
Technical Field
The invention relates to an intelligent material, in particular to a dynamic polymer containing physical split-phase crosslinking and dynamic supermolecular action.
Background
Crosslinking is a general method by which polymers form three-dimensional network structures to achieve the effects of improving the elasticity, thermal stability, mechanical properties and the like of the polymers. The cross-linking may be chemical (covalent) cross-linking or physical (non-covalent/supramolecular) cross-linking. Physical crosslinking is one direction in the development of polymers, since it is particularly useful for improving the processability and the like of the polymers. However, when only conventional physical crosslinking such as phase separation or crystallization is employed, if the crosslinking density is low (longer chains between crosslinking points/lower functionality of crosslinking points), the crosslinked polymer tends to be softer and has poor mechanical properties; whereas if the crosslink density is high (longer chains between crosslinks/higher functionality at crosslinks), the crosslinked polymer tends to be hard and brittle, to break easily, resulting in material failure, and at the material operating temperature, once failed, must be replaced and cannot be reused; furthermore, in order to maintain the stability of the material, the de-crosslinking temperature of the physical crosslinking needs to be higher than the working temperature of the material, so that the physical crosslinking lacks the dynamic property at the working temperature of the material. Meanwhile, due to the fact that the requirements of various new technologies in various industries such as military affairs, electronics, machinery and medical treatment on intelligent materials are more and more extensive and diversified, a novel dynamic polymer needs to be developed, so that the system can have dimensional stability, good mechanical property, self-repairability and excellent dynamics, and meanwhile, other properties can be considered, and the requirements of modern scientific technologies on the intelligent materials are met.
Disclosure of Invention
Aiming at the background, the invention provides a physical phase-splitting supermolecule dynamic polymer in order to ensure that the polymer has enough toughness, self-repairability and dynamic property and also has other properties. For this purpose, we include block polymer molecules with hard and soft segment structures in dynamic polymers and introduce dynamic supramolecular interactions. The split-phase physical crosslinking formed by the hard segments of the block polymer molecules can maintain the thermal stability, the mechanical property, the dimensional stability and the like of the dynamic polymer, and the introduced dynamic supermolecule effect can further improve the crosslinking density and enhance the stability and the mechanical property of the dynamic polymer.
A physically phase-separated supramolecular dynamic polymer comprises block polymer molecules with hard blocks and soft blocks; the hard segments of the block polymer molecules are mutually mixed or are respectively independent or are partially mixed with each other and partially respectively independent to form a crystalline phase or a phase incompatible with the soft segments or both the crystalline phase and the phase incompatible with the soft segments so as to form phase-separated physical crosslinking or crosslinking and polymerization based on the hard segments; each soft segment of the block polymer molecule is in an amorphous state; at least one soft segment of the block polymer molecule contains at least one group/unit capable of forming supramolecular interaction, and the group/unit forms dynamic supramolecular interaction; the supramolecular interaction is selected from the group consisting of halogen bond interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic interaction, ion-dipole interaction, ionic hydrogen bonding interaction, metallophilic interaction, free radical cation dimerization, host-guest interaction.
In one embodiment of the present invention, the dynamic polymer contains block polymer molecules having both hard segment a and soft segment B, and has at least one or a combination of any of the structures described in the following formulas:
wherein, the formula (1A) is a straight chain structure, n is the number of hard segment-soft segment alternating units and is more than or equal to 0;
the formula (1B) is a straight chain structure, two end sections are hard sections, n is the number of hard section-soft section alternating units and is more than or equal to 0;
the formula (1C) is a straight chain structure, two end sections are soft sections, n is the number of hard section-soft section alternating units and is more than or equal to 0;
the formula (1D) is a branched structure, and x is the number of hard segment branched chain units connected to the soft segment B; n is the number of hard segment-soft segment alternating units and is more than or equal to 0; y is the number of hard segment-soft segment branch chain units connected to the soft segment B; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3;
the formula (1E) is a branched structure, and x is the number of hard segment branched chain units connected to the soft segment B; n is the number of hard segment-soft segment alternating units and is more than or equal to 0; y is the number of branch chain units which are connected to the soft segment B and have hard segment-soft segment alternation and take the hard segment as an end segment; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3;
the formula (1F) is a branched structure, and x is the number of soft segment branched chain units connected to the hard segment A; n is the number of soft segment-hard segment alternating units and is more than or equal to 0; y is the number of soft segment-hard segment branch chain units connected to the hard segment A; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3;
the formula (1G) is a branched structure, and x is the number of soft segment branched chain units connected to the hard segment A; n is the number of soft segment-hard segment alternating units and is more than or equal to 0; y is the number of branch chain units which are connected to the hard segment A and have soft segment-hard segment alternation and soft segment as an end segment; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3;
the formula (1H) is a ring structure, n is the number of hard segment-soft segment alternating units, and is more than or equal to 1.
In one embodiment of the present invention, the main chain of the soft segment of the block polymer molecule is selected from the group consisting of a carbon chain structure, a carbon hetero chain structure, a carbon element chain structure, an element hetero chain structure, and a carbon hetero element chain structure; the main chain of the hard segment of the block polymer molecule is selected from a carbon chain structure, a carbon-mixed chain structure, a carbon element chain structure, an element-mixed chain structure and a carbon-mixed element chain structure.
In one embodiment of the present invention, each of the soft segments in the block polymer molecule has a glass transition temperature of no more than 25 ℃.
In one embodiment of the present invention, the hard segment of the block polymer molecule is selected from the group consisting of an amorphous polymer segment with a high glass transition temperature, a polymer segment or group rich in hydrogen bonding groups, a polymer segment or group rich in crystalline phases, a polymer segment rich in conjugated structures.
In one embodiment of the present invention, the block polymer molecule optionally further comprises any one or more of hydrogen bonding, metal-ligand bonding, and dipole-dipole bonding.
In one embodiment of the present invention, the block polymer molecule further comprises a structural supramolecular interaction.
In one embodiment of the invention, the block polymer molecule comprises at least two dynamic supramolecular interactions selected from the group consisting of: pi-pi stacking interactions and metallophilic interactions, host-guest interactions and ionic interactions, host-guest interactions and ion-dipole interactions, host-guest interactions and ionic hydrogen bonding interactions, ionic interactions and ionic dipole interactions, ionic interactions, ion-dipole interactions and ionic hydrogen bonding interactions.
In one embodiment of the invention, the block polymer molecule comprises at least two dynamic supramolecular interactions selected from the group consisting of: pi-pi stacking interactions and metal-ligand interactions, host-guest interactions and hydrogen bonding interactions, host-guest interactions and metal-ligand interactions, host-guest interactions and dipole-dipole interactions, ionic interactions and metal-ligand interactions, ion-dipole interactions and metal-ligand interactions, ion hydrogen bonding interactions and metal-ligand interactions, ionic interactions and hydrogen bonding interactions, ion-dipole interactions and hydrogen bonding interactions, pi-pi stacking interactions and hydrogen bonding interactions, halogen bonding interactions and metal-ligand interactions, ion-dipole interactions and dipole-dipole interactions, ionic interactions, ion-dipole interactions and dipole-dipole interactions.
In one embodiment of the present invention, the dynamic polymer has any one of the following properties: common solids, elastomers, gels, foams.
In one embodiment of the present invention, the formulation components comprising the dynamic polymer further comprise any one or more of the following additives or utilizable materials: other polymers, auxiliaries, fillers, swelling agents. Wherein, the other polymer is selected from any one or more of the following polymers: natural polymer compounds and synthetic polymer compounds; the auxiliary agent is selected from any one or more of the following components: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants, toughening agents, coupling agents, solvents, lubricants, mold release agents, plasticizers, thickeners, thixotropic agents, leveling agents, colorants, optical brighteners, delustering agents, antistatic agents, dehydrating agents, sterilization and mold inhibitors, foaming agents, co-foaming agents, nucleating agents, and rheological agents; the filler is selected from any one or more of the following materials: inorganic non-metallic fillers, organic fillers; the swelling agent is selected from any one or more of the following components: water, organic solvent, ionic liquid, oligomer and plasticizer.
In one embodiment of the invention, the dynamic polymer is applied to the following materials or articles: self-repairing coating, self-repairing plate, self-repairing sealing material, self-repairing plugging glue, self-repairing conductive glue, tough material, tough elastomer material, flexible material, heat insulation material, shape memory material, force sensor, toy and toy filler.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the present invention, the dynamic polymer of the present invention comprises dynamic polymer molecules having hard and soft segments, and simultaneously contains physical phase separation and at least one dynamic supramolecular effect, and the organic combination of the two can obtain rich synergistic and orthogonal material properties. Physical phase separation is convenient to be used as a more stable polymerization/crosslinking connection point, a strong and stable network structure is provided for the dynamic polymer, and the polymer can keep a balanced structure, namely dimensional stability; dynamic supramolecular action can change spontaneously or reversibly under the external action, and dynamic elastomers/gels and the like can be obtained. Since the physical phase separation can be dissociated by heating and/or a solvent, the material has good processing performance even though physical crosslinking based on the physical phase separation is formed, so that self-repairing, shaping, recycling and reprocessing utilization are realized to a greater extent, and the polymer material has a wider application range and longer service life, which cannot be realized in the existing polymer system.
(2) Besides the general dynamic, self-repairing and re-processibility of the polymers usually containing supramolecular interactions, the dynamic polymers of the invention have a variety of other properties: such as directionality of halogen bond action, cation-pi action, anion-pi action, controllable selectivity and controllable identification to small molecules/ions/groups in host-guest action, orderliness of benzene-fluorobenzene action, pi-pi stacking action, pH, concentration sensitivity and conductivity of ion action (positive and negative ion pair action), ion-dipole action, special photoelectricity of ion hydrogen bond action, metallophilic interaction, radical cation dimerization and the like, and supermolecule acting groups/units can be reasonably selected according to requirements for molecular design.
(3) The dynamic polymer has the advantages of rich component structure, various performances and strong controllability. By controlling the parameters of molecular structure, functional group number, molecular weight, etc. of the compound as material, dynamic polymer with different appearance characteristics, adjustable performance and wide use may be prepared. For example, by controlling the number of functional groups and the number of other reactive groups of the compound as a raw material, dynamic polymers having different topologies can be prepared, thereby preparing polymer materials having different properties; two or more mutually synergistic or orthogonal supramolecular interactions are selected to provide rich dynamics.
(4) The dynamic polymer of the invention can simultaneously contain two or more than two supermolecule actions, and can obtain rich performance through reasonable selection design. The controllable selectivity and controllable identification of small molecules/ions/groups can be enhanced by combining the host-guest action with other supermolecule actions; the electric conductivity of the dynamic polymer can be enhanced by combining the supermolecule effects containing ionic groups; the dynamic polymer with rich dynamic layers can be obtained by combining the supermolecule effects with different strengths; the mutually orthogonal supermolecule actions are combined to obtain dynamic polymers which respond to different external stimuli in different ways; the mutual synergistic supermolecule effect is combined, and the dynamic polymer with more stable mechanical property can be obtained.
These and other features and advantages of the present invention will become apparent with reference to the following description of embodiments, examples and appended claims.
Detailed Description
The invention relates to a physical phase-splitting supermolecular dynamic polymer, which contains block polymer molecules with hard segments and soft segments simultaneously; the hard segments of the block polymer molecules are mixed with each other and/or independently can form a crystalline phase and/or a phase incompatible with the soft segments to form phase-separated physical crosslinking and/or polymerization based on the hard segments; each soft segment of the block polymer molecule is in an amorphous state; at least one soft segment of the block polymer molecule contains at least one group/unit capable of forming a supramolecular interaction, which forms a dynamic supramolecular interaction selected from at least halogen bond interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic interaction (positive and negative ion pair interaction), ion-dipole interaction, ionic hydrogen bonding interaction, metallophilic interaction, radical cation dimerization, host-guest interaction.
For simplicity of description, in the description of the present invention, the term "and/or" is used to indicate that the term may include three cases selected from the options described before the conjunction "and/or," or selected from the options described after the conjunction "and/or," or selected from the options described before and after the conjunction "and/or.
In the present invention, the range of series in the terms "species", "class" and "series" used to describe different structures is larger than that of the class, and the range of the class is larger than that of the species, that is, one series can have many kinds, and one class can have many kinds. Even if the supramolecular interaction has the same motif structure, differences in properties may result due to differences in linkers, substituents, isomers, etc. In the present invention, supramolecules having the same motif structure are generally regarded as the same structure; if the difference in properties is caused by the difference in the linking group, substituent, isomer, etc., the same structure is considered. The invention can be reasonably designed, selected and regulated according to the needs to obtain the best performance, which is also the advantage of the invention. In the present invention, it is preferred to use different series of structures in order to better regulate orthogonality.
The "polymerization" reaction/action referred to in the present invention is a chain extension process/action, i.e., a polymer forming a linear, branched, cyclic, two-dimensional/three-dimensional cluster, three-dimensional infinite network structure by intermolecular reaction/action (including covalent chemical reaction and supramolecular action).
The term "crosslinking" reaction/action as used in the present invention refers to the process of intermolecular and/or intramolecular formation of a product having a three-dimensional infinite network type by covalent bond and/or supramolecular action. During the crosslinking process, the polymer chains generally grow continuously in two/three dimensions, gradually form clusters (which may be two-dimensional or three-dimensional), and then develop into a three-dimensional infinite network. Thus, crosslinking can be considered a special form of polymerization. The degree of crosslinking, just before a three-dimensional infinite network is reached during crosslinking, is called the gel point, also called the percolation threshold. A crosslinked product above the gel point (inclusive, the same applies hereinafter) having a three-dimensional infinite network structure, the crosslinked network constituting a whole and spanning the entire polymer structure; the crosslinked product below the gel point, which is only a loose inter-chain linking structure, does not form a three-dimensional infinite network structure, and does not belong to a crosslinked network that can constitute a whole across the entire polymer structure. Unless otherwise specified, the crosslinked structure in the present invention includes only a three-dimensional infinite network structure above the gel point, and the non-crosslinked structure includes a two-dimensional/three-dimensional cluster structure below the gel point and linear and nonlinear structures with a zero degree of crosslinking.
In the present invention, the term "polymer main chain" refers to a chain having the largest number of links in a polymer structure, unless otherwise specified. The side chain refers to a chain structure which is connected with a polymer main chain skeleton/a crosslinking network chain skeleton in a polymer structure and is distributed beside the skeleton, and the molecular weight of the chain structure exceeds 1000 Da; wherein the branched chain and the branched chain refer to chain structures which are branched from a polymer main chain skeleton/a crosslinking network chain skeleton or any other chains and have the molecular weight of more than 1000 Da; for simplicity, side chains, branches, and branched chains are collectively referred to as side chains unless otherwise specified, when the molecular weight exceeds 1000 Da. Wherein, the side group refers to a chemical group with molecular weight not higher than 1000Da and a short side chain with molecular weight not higher than 1000Da which are connected with the polymer main chain skeleton/crosslinking network chain skeleton and distributed beside the main chain skeleton in the polymer structure. For the side chain and the side group, the side chain and the side group can have a multi-stage structure, that is, the side chain can be continuously provided with the side group and the side chain, the side chain of the side chain can be continuously provided with the side group and the side chain, and the side chain also comprises chain structures such as branched chain and branched chain. Wherein, the "terminal group" refers to a chemical group which is linked to the polymer chain skeleton in the polymer structure and is located at the terminal of the chain skeleton; in the present invention, the side groups may have terminal groups in specific cases.
In an embodiment of the present invention, the block polymer molecule having both hard blocks and soft blocks contains at least one hard block and at least one soft block, wherein the total number of hard blocks and soft blocks is 2 or more. The hard segments intermix with each other and/or, independently of each other, can form a crystalline phase and/or a phase incompatible with the soft segments to form phase-separated physical crosslinks and/or polymerizations based on the hard segments. Said physical polymerization causes polymer chain extension (including crosslinking); the physical crosslinking provides the polymer with crosslinking physical properties similar to those of covalent crosslinking, including but not limited to, apparent molecular weight increase, elasticity, dimensional stability, mechanical strength, and the hard segment phase-separated physical crosslinking is particularly suitable for providing the equilibrium structure, i.e., dimensional stability, of the dynamic polymer of the present invention. When the number of hard segments is 2 or more and the hard segments are connected with each other by the soft segments, the crystallization/phase separation of the hard segments will more effectively form inter-chain phase-separated physical cross-linking, which can effectively provide the strength of the phase-separated physical cross-linking, the equilibrium structure of the polymer and the mechanical properties of the physically phase-separated polymer, so that it is preferable to form an alternating hard segment-soft segment structure comprising at least two hard segments and at least one soft segment.
In the present invention, the hard and soft segments of the same molecule may be linked by covalent bonds and optionally by structural supramolecular interactions. The covalent bond refers to a conventional covalent bond, which is difficult to break at normal temperature (generally not higher than 100 ℃) and normal time (generally less than 1 day), and includes, but is not limited to, normal carbon-carbon bond, carbon-oxygen bond, carbon-hydrogen bond, carbon-nitrogen bond, carbon-sulfur bond, nitrogen-hydrogen bond, nitrogen-oxygen bond, hydrogen-oxygen bond, nitrogen-nitrogen bond, etc. The structural supramolecular action refers to a strong supramolecular action which is not dissociated/broken in the normal use process of the dynamic polymer, the dynamic property of the dynamic supramolecular action is weaker than that of the dynamic supramolecular action which can be dissociated in the normal use process, the stability of the dynamic supramolecular action can be higher or lower than that of a hard phase formed by crystal and phase separation, and preferably higher than that of the hard phase formed by the crystal and the phase separation, so that a stable block polymer molecule with a required hard segment-soft segment structure can be obtained, but the structural supramolecular action which selectively exists under the extreme conditions, such as high temperature, strong competitive ligand, strong mechanical force and the like, can also be dissociated/broken. In the process of processing and forming materials, the selective structural supramolecular function which can be broken/dissociated under the conditions of proper temperature or solvent existence is beneficial to processing, forming, recycling and reusing of the materials. Wherein, the term "does not dissociate/break" also includes the crystal formed by the structural supramolecular interaction and the hard phase formed by phase separation. In the present invention, the mutually orthogonal supramolecular interactions refer to the formation, dissociation and other responses of these supramolecular interactions without affecting each other when two or more supramolecular interactions are present (preferably of different types, more preferably of different series); by mutually synergistic supramolecular interactions is meant that when two or more supramolecular interactions are present, the formation and/or dissociation and/or other response of one of these supramolecular interactions triggers the formation and/or dissociation and/or other response of the other supramolecular interaction or occurs simultaneously with the formation and/or dissociation and/or other response of the other supramolecular interaction and produces an effect greater than the linear superposition of the various supramolecular interactions.
In the embodiment of the present invention, the chain topology of the block polymer molecule having both hard segment and soft segment is not particularly limited, and includes but is not limited to linear structure, branched structure (including but not limited to star, H, dendritic, comb, hyperbranched), cyclic structure (including but not limited to single ring, multiple ring, bridge ring, grommet, wheel ring), two-dimensional/three-dimensional cluster structure and combination of two or any several thereof, preferably linear and branched structure. When a branched structure is present, part of the hard/soft segments may be on the main chain and part of the hard/soft segments may be on the side chains/branches/bifurcations. In the embodiment of the present invention, the dynamic polymer may contain only one topological form of the block polymer, or may be a mixture of several topological forms of the block polymer; other polymers and raw material components in the composition may be polymers having only one topological form, or may be a mixture of polymers having a plurality of topological forms.
In the embodiment of the present invention, in the block polymer molecule having both hard blocks and soft blocks, each hard block may be the same or different, and each soft block may be the same or different; wherein, the hard segment and the soft segment can respectively and independently comprise two or more than two same or different sub-segments; the sub-strands can be connected by covalent bonds and optionally by structural supramolecular interactions; the sub-chain segments can be smaller chain segments on the same main chain or smaller chain segments on side chains, branched chains and branched chains; such differences include, but are not limited to, differences in chemical composition, molecular weight, topology, and spatial configuration; the individual sub-strands may be compatible or phase separated. In the embodiment of the present invention, each of the hard segment, the soft segment and the sub-segment thereof may be a homopolymer segment, a copolymer segment, a homopolymeric cluster or a copolymeric cluster, a crosslinked particle having a gel point of homo-polymerization or copolymerization or a functional group, or any combination of the foregoing.
In the embodiment of the present invention, the topology structure of any segment in the hard segment is not particularly limited, and may be a linear structure, a branched structure (including but not limited to star, H, dendritic, comb, and hyperbranched), a cyclic structure (including but not limited to single ring, multiple ring, bridged ring, grommet, and torus), a two-dimensional/three-dimensional cluster structure, a particle crosslinked above the gel point, and a combination of two or any several thereof, but the present invention is not limited thereto, and is preferably a linear structure and a branched structure. The topology of any segment in the soft segment is not particularly limited, and may be a linear structure, a branched structure (including but not limited to star, H, dendritic, comb, hyperbranched), a cyclic structure (including but not limited to single ring, multiple ring, bridge ring, grommet, and wheel ring), a two-dimensional/three-dimensional cluster structure, a particle crosslinked above the gel point, and a combination of two or any of them, but the present invention is not limited thereto, and is preferably a linear structure, a branched structure, and a cluster structure.
Some preferred structures of the block polymer molecule of the present invention are shown by the following formulas (1A) to (1H), but the present invention is not limited thereto, wherein A is a hard segment and B is a soft segment, and hard segments A at different positions in the same block polymer molecule may be the same or different, and may be compatible or phase-separated; the soft segments B at different positions in the same molecule may be the same or different, and may be compatible or phase separated:
wherein, the formula (1A) is a straight chain structure, n is the number of hard segment-soft segment alternating units and is more than or equal to 0; preferably n is greater than or equal to 1;
the formula (1B) is a straight chain structure, two end sections are hard sections, n is the number of hard section-soft section alternating units and is more than or equal to 0;
the formula (1C) is a straight chain structure, two end sections are soft sections, n is the number of hard section-soft section alternating units and is more than or equal to 0; preferably n is greater than or equal to 1;
the formula (1D) is a branched structure, and x is the number of hard segment branched chain units connected to the soft segment B; n is the number of hard segment-soft segment alternating units and is more than or equal to 0; y is the number of hard segment-soft segment branch chain units connected to the soft segment B; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3;
the formula (1E) is a branched structure, and x is the number of hard segment branched chain units connected to the soft segment B; n is the number of hard segment-soft segment alternating units and is more than or equal to 0; y is the number of branch chain units which are connected to the soft segment B and have hard segment-soft segment alternation and take the hard segment as an end segment; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3;
the formula (1F) is a branched structure, and x is the number of soft segment branched chain units connected to the hard segment A; n is the number of soft segment-hard segment alternating units and is more than or equal to 0; y is the number of soft segment-hard segment branch chain units connected to the hard segment A; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3; preferably, y is 1 or more and the sum of x and y is 3 or more;
the formula (1G) is a branched structure, and x is the number of soft segment branched chain units connected to the hard segment A; n is the number of soft segment-hard segment alternating units and is more than or equal to 0; y is the number of branch chain units which are connected to the hard segment A and have soft segment-hard segment alternation and soft segment as an end segment; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3; preferably, y is 1 or more and the sum of x and y is 3 or more;
the formula (1H) is a ring structure, n is the number of hard segment-soft segment alternating units and is more than or equal to 1; preferably, n is 2 or more.
Furthermore, the structure of the block polymer molecule having both hard and soft segments of the present invention can also be any combination of the preferred structures listed above and any other suitable structure, which can be reasonably realized by those skilled in the art according to the logic and context of the present invention.
In an embodiment of the present invention, the group/unit capable of forming supramolecular interactions includes skeletal supramolecular interacting groups/units, side-group supramolecular interacting groups/units and terminal supramolecular interacting groups/units located at different positions. The skeleton supramolecular interaction group/unit means that at least one atom in the group/unit directly participates in the construction of a continuous polymer main chain (including crosslinking and non-crosslinking)/side chain (including branched chain/branched chain); the side group supermolecule interaction group/unit means that all atoms on the group/unit are on the side group; the terminal supramolecular interacting group/unit refers to the group/unit with all atoms on the terminal group. In some cases, the terminal supramolecular interacting group/unit is also a skeletal supramolecular interacting group/unit or a side-group supramolecular interacting group/unit. The skeletal supramolecular interacting groups/units may be generated during polymerization/cross-linking of the polymer, i.e. by formation of the supramolecular interacting groups/units; or may be previously formed and then polymerized/crosslinked; preferably generated in advance. The side group supramolecular interacting group/unit may be generated before, after or during polymerization/crosslinking, the amount generated before or after being relatively freely controllable.
In the embodiment of the invention, one or more same or different dynamic supramolecular groups/units can exist on the same block polymer molecular chain to form same or different dynamic supramolecular action, and do not form phase separation with a soft phase when the dynamic supramolecular groups/units exist in the soft phase; different block polymer molecular chains can have the same or different dynamic supermolecular groups/units to form the same or different dynamic supermolecular functions. Any one or more dynamic supramolecular groups positioned at any position and the introduced supramolecular groups can form interchain and/or intrachain supramolecular interaction; the intermolecular supramolecular interaction produces polymerization and/or crosslinking; the intrachain supramolecular interactions generally produce intrachain rings without cross-linking, but if grommets and/or annuli are produced, cross-linking can occur; preferably, interchain and/or intrachain crosslinking occurs. In the embodiment of the present invention, suitable groups in other polymers or small molecule compounds selectively existing in the dynamic polymer system can form dynamic supramolecular interaction together with dynamic supramolecular groups in the block polymer molecules with hard-segment-soft-segment structure. In the present invention, the dynamic supramolecular interaction may be any degree of crosslinking. It is to be noted that the invention does not exclude that part of the dynamic supramolecular interactions formed do not form interchain interactions nor intrachain rings, but only interactions including but not limited to grafting, etc.
In the embodiment of the present invention, the group/unit constituting the dynamic supramolecular interaction in the block polymer molecule having the soft segment-hard segment structure may be a soft segment main chain skeleton supramolecular interaction group/unit, a soft segment main chain end group supramolecular interaction group/unit, a soft segment main chain side group supramolecular interaction group/unit, the combination of any one or more of the soft segment side chain/branched chain side group supramolecular interacting group/unit, soft segment side chain/branched chain skeleton supramolecular interacting group/unit, soft segment side chain/branched chain end group supramolecular interacting group/unit, and optionally any one or more of the following forms may be present at other positions in the block polymer molecule (but the present invention is not limited thereto): the system comprises a hard segment main chain skeleton supramolecular interaction group/unit, a hard segment side chain/branched chain skeleton supramolecular interaction group/unit, a hard segment main chain side group supramolecular interaction group/unit, a hard segment main chain end group supramolecular interaction group/unit, a hard segment side chain/branched chain side group supramolecular interaction group/unit and a hard segment side chain/branched chain end group supramolecular interaction group/unit. Preferably, the supermolecule functional group/unit is in the form of any one or combination of a soft segment main chain skeleton supermolecule functional group/unit, a soft segment side chain/branched chain side group supermolecule functional group/unit, a soft segment side chain/branched chain skeleton supermolecule functional group/unit and a soft segment side chain/branched chain end group supermolecule functional group/unit, more preferably in the form of a soft segment main chain side group supermolecule functional group/unit and/or a soft segment side chain/branched chain side group supermolecule functional group/unit, and can fully play the dynamic property of the supermolecule function without damaging the topological structure and the phase-splitting physical crosslinking network structure of the block polymer molecule.
In the embodiment of the present invention, when there is more than one dynamic supramolecular function, the groups capable of forming the dynamic supramolecular function may be distributed on the same soft segment of the same block polymer molecule, may be distributed on different soft segments of the same block polymer molecule, or may be distributed on soft segments of different block polymer molecules, and preferably, the groups are connected with each other by a flexible linker or chain segment containing at least six skeleton atoms, so as to better exert the synergistic effect of different supramolecular functions. In the present invention, when a plurality of polymer components are present, the components may be compatible or incompatible with each other; when at least one cross-linked component is present, the different components may be dispersed, interspersed or partially interspersed with each other, although the invention is not limited in this respect.
In the embodiment of the present invention, one or more same or different groups/units constituting the structural supramolecular interaction may be optionally present on the same molecular chain of the block polymer to form the structural supramolecular interaction. The groups/units constituting structural supramolecular interactions may optionally be present in any one or more of any suitable combination in the soft and/or hard segments of the polymer molecule and do not form phase separation with the soft phase when the groups/units constituting structural supramolecular interactions are present in the soft segments. Since partial supramolecular interactions are not directional and selective, the groups/units constituting the structural supramolecular interactions are preferably located at the soft and hard end groups and are directional and selective groups/units, producing only interchain polymerization. In the present invention, the structural supramolecular interaction may be any degree of crosslinking. It is to be noted that the invention does not exclude that some of the formed intrachain structural supramolecules do not form interchain interactions or intrachain rings, but only form interactions including but not limited to grafting, etc.
In the present invention, in addition to the split-phase physical crosslinking/polymerization based on the crystalline phase of the hard segment and/or the formation of a phase incompatible with the soft segment being a physical crosslinking/polymerization, the crosslinking/polymerization by dynamic supramolecular action is also a physical crosslinking/polymerization, and the crosslinking/polymerization by structural supramolecular action is also a physical crosslinking/polymerization. The physical crosslinking/polymerization related by the invention has reversibility, namely, the physical crosslinking/polymerization can be subjected to decrosslinking/depolymerization under the condition of heating or in a good solvent or under other proper stimulation; physical crosslinks/polymerizations can be reformed under cooling conditions or in poor solvents or after release of the stimulus.
In the present invention, the hard segment generally has a higher glass transition temperature and/or forms a crystalline phase and/or forms a phase which is more thermally stable and/or has a higher mechanical strength and/or is less soluble than the soft segment does. In an embodiment of the invention, a soft phase of soft segments and a hard phase of hard segments are generally present in the dynamic polymer; however, the different hard phases formed by the different hard segments may or may not be compatible, and the different soft phases formed by the different soft segments may or may not be compatible, i.e. two or even three or more incompatible phases may be present in the dynamic polymer. In the embodiment of the present invention, the phase topology (phase morphology) formed by the soft phase composed of soft segments and the hard phase composed of hard segments is not limited, and includes, but is not limited to, a sphere, a cylinder, a spiral, a layer, and a combination thereof. Any phase, including different soft phases and different hard phases, can be dispersed in another phase, can form interpenetrating double/multiple continuous phases with other phases, can be mutually independent continuous phases, and can also be in a mixed form. In the embodiment of the present invention, it is preferable that the soft phase is a continuous phase, the hard phase is a discontinuous phase dispersed in the soft phase, and it is more preferable that the hard phase is dispersed in the soft phase in a spherical shape as phase-separated physical crosslinks, so that the polymer can more conveniently have better flexibility and elasticity and be more suitable for exerting the dynamic property of dynamic covalent bonds. The size of the discontinuous hard phase is typically no greater than 100 microns, more preferably no greater than 10 microns, more preferably no greater than 1 micron, and most preferably no greater than 100 nanometers. The total amount of hard segments in the dynamic polymer system is not particularly limited, and preferably is between 1% and 50% of the total weight, more preferably between 5% and 35% of the total weight, to facilitate the formation of effective phase-separated physical crosslinks.
In the embodiment of the invention, the crosslinking degree of the phase-separated physical crosslinking formed by the hard segment can be above and below the gel point, the dynamic supramolecular crosslinking formed by the dynamic supramolecular action can be above and below the gel point, and the structural supramolecular crosslinking formed by the structural supramolecular action can also be above and below the gel point; preferably the sum of the phase-separated physical cross-links formed by the hard segments and the supramolecular cross-links formed by the structural supramolecular interactions is above the total gel point of the polymer; more preferably, the degree of crosslinking of the phase-separated physical crosslinks formed by the hard segments is at the gel point (including the gel point, the same applies hereinafter) thereof, so as to obtain a three-dimensional infinite network based entirely on the phase-separated physical crosslinks of the hard segments, and the dynamic polymer can also maintain an equilibrium structure, i.e., dimensional stability, in the case of complete dissociation by reversible supramolecular action.
In embodiments of the present invention, the soft phase of the dynamic polymer may have no glass transition temperature, or one or more glass transition temperatures, preferably at least one of which is not higher than the lower limit of the operating temperature range; the hard phase may also have no glass transition temperature, or one or more glass transition temperatures, and may also have one or more temperatures for physical crosslinking/polymerization of the split phase, preferably any hard segment having a split phase physical crosslinking/polymerization temperature above the upper limit of the operating temperature range. When the dynamic polymer contains an auxiliary agent or a filler such as a plasticizer and the like so that at least one glass transition temperature of a soft segment is not higher than the lower limit of the working temperature range, and the uncrosslinking/polymerization temperature of a hard segment is higher than the upper limit of the working temperature range, the composition also belongs to the dynamic polymer. Among these, it is preferred that the glass transition temperatures of the individual components of the entire soft segment are all below the lower limit of the working temperature range, which is advantageous for obtaining polymers with high softness, in particular elastomers with a wide range of uses. The elastomer obtained by the method not only has dynamic property, but also has thermoplasticity, so that the elastomer is convenient to form and reprocess, and the thermoplastic dynamic elastomer has very important application in the aspects of sealing, force sensing and the like. The glass transition temperature of each soft segment of the thermoplastic dynamic elastomer is preferably not higher than 25 ℃, and the thermoplastic dynamic elastomer can be used as an elastomer at room temperature.
In the embodiment of the present invention, the dynamic property of the hard segment reversible phase-separated physical crosslinking/polymerization is lower than that of the dynamic supramolecular action, and more preferably, the decrosslinking/polymerization temperature and the mechanical stability of the hard segment reversible phase-separated physical crosslinking/polymerization are also higher than the dissociation temperature and the mechanical stability of the dynamic supramolecular action, respectively. Dynamic supramolecular action is generally dynamic at lower temperatures, preferably not higher than room temperature; or are susceptible to dissociation/fracture under external forces.
In the embodiment of the present invention, the chemical composition of the hard segment is not particularly limited, and may be selected from, but not limited to, polymer segments whose main chain is a carbon chain structure, a carbon hetero chain structure, a carbon element chain structure, an element hetero chain structure, and a carbon hetero element chain structure. The carbon chain structure is a structure of which the main chain skeleton only contains carbon atoms; the carbon heterochain structure is a structure of which a main chain skeleton simultaneously contains carbon atoms and any one or more heteroatoms, wherein the heteroatoms comprise but are not limited to sulfur, oxygen and nitrogen; the carbon element chain structure is a structure that a main chain skeleton simultaneously contains carbon atoms and any one or more element atoms, wherein the element atoms comprise but are not limited to silicon, boron and aluminum; the element chain structure is a structure that a main chain skeleton only contains element atoms; the element heterochain structure is a structure which has a main chain skeleton and only contains at least one heteroatom and at least one element atom; the carbon-heteroatom chain structure is a structure of which a main chain skeleton simultaneously contains carbon atoms, heteroatoms and element atoms. Among them, a carbon chain structure and a carbon hetero chain structure are preferable because of their rich structure and excellent performance. By way of example, the hard segment of the dynamic polymer may be a segment based on, but not limited to, the following polymer segments, groups, or any combination thereof: amorphous polymer segments with high glass transition temperatures (i.e., glass transition temperatures above the upper limit of the material's operating temperature, typically above 40 ℃, preferably not less than 100 ℃), such as polystyrene, polymethylmethacrylate, polyvinylpyridine, hydrogenated polynorbornene, polyether, polyester, polyetheretherketone, polyaromatic carbonate, polysulfone, and the like; hydrogen bond group-rich polymer segments, groups such as polyamides, polypeptides, urea bond-rich segments, urethane bond-rich segments, ureido pyrimidinone-based segments, and the like; polymer segments, groups rich in crystalline phases, such as crystalline polyethylene, crystalline polypropylene, crystalline polyester, crystalline polyether, liquid crystal polymer, liquid crystal groups, and the like; ionic polymer segments such as polyacrylate, polymethacrylate, polyacrylamide, polystyrene sulfonate, and the like; polymer chain segments rich in conjugated structures, such as polyacetylene, polyphenylacetylene, polyphenyl, polyfluorene, polythiophene and the like. Among them, amorphous polymer segment with high glass transition temperature, polymer segment/group rich in hydrogen bonding group, and polymer segment/group rich in crystalline phase are preferable, so as to design and regulate the molecular structure and phase-separated physical crosslinking of the block polymer to obtain the best performance.
In the embodiment of the present invention, the soft segment polymer chain skeleton may be selected from, but not limited to, polymer chain segments whose main chains are a carbon chain structure, a carbon hetero chain structure, a carbon element chain structure, an element hetero chain structure, and a carbon hetero element chain structure, and the carbon chain structure, the carbon hetero chain structure, the element hetero chain structure, and the carbon hetero element chain structure are preferable because of their abundant structure and excellent performance. The soft segment can be obtained by the continuous reaction of synthetic macromolecule and/or natural macromolecule precursors (including the introduction of end group and/or side group active points, the introduction of side group and/or side chain, grafting, chain extension, etc.), or can be obtained by the polymerization of monomers and/or prepolymer/oligomer, or by the combination of the above different methods. By way of example, the soft segment polymer chain backbone may be a segment based on the following polymers, but the invention is not limited thereto: homopolymers, copolymers, modified products and derivatives of acrylate polymers, saturated olefin polymers, unsaturated olefin polymers, halogen-containing olefin polymers, polyacrylonitrile polymers, polyvinyl alcohol polymers, silicone polymers, polyether polymers, polyester polymers, and biological polyester polymers.
In an embodiment of the present invention, the halogen bonding is a non-covalent interaction between a halogen atom and a neutral or negatively charged lewis base, and is essentially an interaction between the sigma-bar orbital of the halogen atom in the halogen bond donor group and an atom or pi-electron system with a lone electron pair in the halogen bond acceptor group. Wherein, the halogen bond donor group can be selected from Cl, Br and I, preferably Br and I; the halogen bond acceptor group may be selected from F, Cl, Br, I, N, O, S, π bonds, preferably Br, I, N, O. The halogen bond has directional and linear inclined geometric characteristics; as the atomic number of halogen increases, the number of electron donors that can be bonded increases, and the strength of the halogen bond formed increases. Based on the halogen bond effect, ordered and self-repairing dynamic polymers can be designed.
In embodiments of the present invention, when halogen bonding is present, the corresponding blocks of the flexible block polymer molecule may contain only halogen bond donor groups or only halogen bond acceptor groups, and may also contain both donor and acceptor groups. When one of the block polymer molecules contains only donor groups or only acceptor groups, the dynamic polymer also contains the corresponding block polymer molecules containing the acceptor groups or the donor groups, and the dynamic polymer and the acceptor groups and the donor groups cooperate to form dynamic halogen bond effect. When one of the block polymer molecules contains both a halogen bond acceptor group and a donor group, the positions of the acceptor group and the donor group in the blocks of the block polymer molecule are not limited at all, and may be in the same block or in different blocks. The dynamic polymer may optionally further comprise any one or combination of small molecules, polymers or minerals compatible with the phase in which it is located and containing the corresponding donor and/or acceptor groups, which interact with the block polymer molecules to form dynamic halogen bonding.
In embodiments of the invention, only one halogen bond donor group and/or one halogen bond acceptor group may be present in a polymer chain or in a dynamic polymer system, or any suitable combination of a plurality of halogen bond donor groups and/or halogen bond guest groups may be present simultaneously. The halogen bond donor group and/or the halogen bond acceptor group refer to a core structure. The halo donor groups and/or halo acceptor groups at different positions may have the same core structure, differing in the point of attachment and/or position of the core structure to a component such as a polymer chain or small molecule.
In the embodiment of the present invention, the combination of the atoms forming the halogen bond function is not limited as long as a stable halogen bond function can be formed in the dynamic polymer. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
—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 an embodiment of the invention, the cation-pi interaction is a non-covalent interaction between a cation and a pi-electron system of an aromatic system. There are three main classes of cation-pi action, the first being simple inorganic cations or ionic groups (e.g. Na)+、K+、Mg2+、NH4 +、Ca2+) And aromatic systems; the second is the interaction between organic cations (e.g., quaternary ammonium cations) and fragrance systems; the third type is the interaction between positively charged atoms in the dipole bond (e.g., H atoms in an N-H bond) and the aromatic system. The cation-pi effect has rich varieties and moderate intensity, can stably exist in various environments, and can prepare dynamic polymers with rich performance based on the cation-pi effect.
In the embodiment of the present invention, the kind of the cation-. pi.function is not particularly limited as long as it can form a stable cation-. pi.function in the dynamic polymer. Some suitable cationic groups may be exemplified by, but are not limited to:
Na+、K+、Li+、Mg2+、Ca2+、Be2+、H-O、H-S、H-N。
in an embodiment of the invention, the anionic-pi interaction is a non-covalent interaction between an anion and an electron deficient aromatic pi system. The anion may be a simple inorganic non-metallic ion or group of ions (e.g., Cl)-、Br-、I-、OH-) (ii) a Or an organic anionic group (e.g., a benzenesulfonic acid group); it may also be a negatively charged atom in a dipole bond (e.g. a chlorine atom in a C-Cl bond). The electron-deficient aromatic pi system refers to the ring formationDue to the difference of electronegativity of atoms, the distribution of pi electron clouds of rings is not uniform, and pi electrons are mainly deviated to the direction of electronegativity high atoms, so that the distribution density of pi electron clouds of aromatic rings is reduced, such as pyridine, fluorobenzene and the like. The anion-pi action has reversibility and controllable identification, and can be used for constructing dynamic polymers with special properties.
In the embodiment of the present invention, the kind of the anion- π action is not particularly limited as long as it can form a stable anion- π action in the dynamic polymer. Some suitable anions may be exemplified below, but the invention is not limited thereto:
Cl-、Br-、I-、OH-、SCN-；
some suitable electron deficient aromatic pi systems may be exemplified, but the invention is not limited thereto: pyridine, pyridazine, fluorobenzene, nitrobenzene, tetraoxacalix [2] arene [2] triazine and benzene tri-imide.
In an embodiment of the present invention, the benzene-fluorobenzene reaction is a non-covalent interaction between an aromatic hydrocarbon and a polyfluorinated aromatic hydrocarbon through the combination of dispersion force and quadrupole moment. Because the ionization potential of fluorine atoms is very high and the atomic polarizability and atomic radius are both small, the fluorine atoms around the polyfluorinated aromatic hydrocarbon are negatively charged due to large electronegativity, and the skeleton of the central carbon ring is positively charged due to small electronegativity. Because the electronegativity of the carbon atom is greater than that of the hydrogen atom, the direction of the electric quadrupole moment of the aromatic hydrocarbon is opposite to that of the polyfluorinated aromatic hydrocarbon, and because the volume of the fluorine atom is very small, the volume of the polyfluorinated aromatic hydrocarbon is similar to that of the aromatic hydrocarbon, the aromatic hydrocarbon and the polyfluorinated aromatic hydrocarbon are stacked in an alternate face-to-face mode to form a columnar stacking structure, and the stacking mode is basically not influenced by the introduced functional group. The reversibility and stacking effect of the benzene-fluorobenzene action are utilized to prepare the dynamic polymer with special functions.
In the embodiment of the present invention, the kind of the benzene-fluorobenzene action is not limited as long as a stable benzene-fluorobenzene action can be formed in the dynamic polymer. Some suitable benzene-fluorobenzene reactions may be exemplified by, but the invention is not limited to:
in the embodiment of the invention, the dynamic polymer contains a structure capable of providing pi-bond electron clouds, and the pi-pi stacking effect is formed by the mutual overlapping of the pi-bond electron clouds. Pi-pi stacking functions in three ways, including face-to-face stacking, offset stacking, and edge-to-face stacking. The surface accumulation means that the interactive ring surfaces are parallel to each other, the distance between the centers of the parallel ring surfaces is almost equal to the distance between the ring surfaces, the pi-pi action of the accumulation mode is electrostatic mutual exclusion and is relatively unstable, but when the electron-withdrawing property of a substituent group connected to the ring surfaces is relatively strong, the pi-pi action of the surface accumulation becomes relatively obvious; the offset accumulation means that the action ring surfaces are parallel to each other, but the center of the ring has certain offset, namely the distance of the center of the ring is larger than the distance between the ring surfaces, the accumulation mode relieves the mutual exclusion action between the two ring surfaces, correspondingly increases the attraction of sigma-pi, and is a common accumulation mode; stacking other than planar stacking and offset stacking is called edge-planar stacking, which has the smallest energy and the smallest intermolecular repulsion, and is often found between ring-conjugated molecules having smaller van der waals surfaces or between ring-conjugated molecules having flexible linkers.
Structures of compounds capable of providing a pi-bonded electron cloud, including but not limited to most condensed cyclic compounds and some heterocyclic compounds with pi-pi conjugation, suitable groups may be exemplified by, but not limited to, the following:
preference is given toThe pi-pi stacking effect has simple forming mode, can stably exist in the polymer, is less influenced by the external environment, and can be conveniently regulated and controlled by changing the conjugated compound and the content.
In the embodiment of the present invention, the combination of the compounds providing the pi-bonded electron cloud is not particularly limited as long as a suitable pi-pi stacking effect is formed between the compounds. Among them, a combination of an electron-rich compound and an electron-deficient compound is preferable. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
in one embodiment of the present invention, the ionic interaction comprises at least one pair of oppositely charged ionic groups in the dynamic polymer structure, and the ionic interaction is formed between the positive ionic group and the negative ionic group through coulomb force. The cationic group is an organic group that is relatively receptive to protons, and includes, by way of example and not limitation: preference is given toThe anionic group is an organic group that is relatively susceptible to losing a proton, and includes, by way of example and not limitation, those that are relatively susceptible to losing a protonPreference is given toIn particular, the positive and negative ionic groups may be in the same compound structure, such as choline glycerophosphate, 2-methacryloyloxyethyl phosphorylcholine, l-carnitine, methacryloylethyl sulfobetaine, and the like. The ionic action can be stably existed in the polymer, and the strength of the ionic action can be well controlled by changing the concentration and the type of the ionic group.
In the embodiment of the present invention, when the ionic action exists, the corresponding block of the flexible block polymer molecule may contain only a positive ion group or only a negative ion group or only a zwitterion group, and may contain both a positive ion group and a negative ion group. When one of the block polymer molecules only contains positive ion groups or only contains negative ion groups, the dynamic polymer also contains any one or more combinations of the block polymer molecules, small molecules, other polymers or inorganic matters which are compatible with the phase in which the dynamic polymer is located and contain corresponding negative ion groups or positive ion groups, and the combination of the block polymer molecules and the small molecules, the other polymers or the inorganic matters and the block polymer molecules are interacted to form dynamic ionic action. When one block polymer molecule contains both positive ion groups and negative ion groups, the positions of the positive ion groups and the negative ion groups in the blocks of the block polymer molecule are not limited at all, and the positive ion groups and the negative ion groups can be positioned in the same block or different blocks respectively, and the dynamic polymer can also selectively contain any one or combination of a plurality of small molecules, polymers or inorganic substances which are compatible with the located phase and contain the corresponding positive ion groups and/or negative ion groups, and can jointly act with the block polymer molecule to form dynamic ionic action.
In the embodiment of the present invention, the combination of the positive ionic group and the negative ionic group is not particularly limited as long as the positive ionic group can form a suitable ionic action with the negative ionic group. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
in an embodiment of the present invention, when two atoms with different electronegativities are bonded, the induced action of the atom with the larger electronegativity makes the charge distribution uneven, resulting in asymmetric distribution of electrons, and an electric dipole is generated, and the electric dipole interacts with the charged ion group to form the ion-dipole action. The ionic group may be any suitable charged organic group, such as the following, but the invention is not limited thereto: preference is given to The electric dipole may be generated by bonding any suitable two atoms with different electronegativities, such as the following, but the invention is not limited thereto: 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. The ion-dipole effect can stably exist in an electrochemical environment, the acting force is easy to regulate and control, and the conditions of generating and dissociating the acting force are mild.
In the embodiment of the present invention, when the ion-dipole effect exists, the corresponding block of the flexible block polymer molecule may contain only an ionic group or only an electric dipole, and may also contain both an ionic group and an electric dipole. When one of the block polymer molecules contains only ionic groups or only electric dipoles, the dynamic polymer also contains any one or more combinations of the block polymer molecules, small molecules, other polymers or inorganic substances which are compatible with the phase in which the dynamic polymer is located and contain corresponding electric dipoles or ionic groups, and the combination of the block polymer molecules and the small molecules form dynamic ion-dipole action. When one of the block polymer molecules contains both an ionic group and an electric dipole, the positions of the ionic group and the electric dipole in the blocks of the block polymer molecule are not limited at all, and may be located in the same block or in different blocks. The dynamic polymer may optionally contain any one or combination of small molecules, polymers or minerals compatible with the phase in which it is located and containing corresponding ionic groups and/or electric dipoles, which interact with the block polymer molecules to form dynamic ionic interactions.
In the embodiment of the present invention, the combination of the ionic group and the electric dipole is not particularly limited as long as the ionic group can form a suitable ion-dipole action with the electric dipole. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
it should be noted that, in the present invention, the ion-dipole effect only refers to the effect between the ionic group and the electric dipole other than the metal-ligand effect, and does not include the metal-ligand effect.
In an embodiment of the invention, the metalphilic effect is achieved when the two outermost electronic structures are d10Or d8When the metal ions are close to less than the sum of their van der waals radii, an interaction force is generated, and the two metal ions having a metallophilic interaction may be the same or different. The outermost electronic structure is d10Metal ions of (2) include, but are not limited to, Cu+、Ag+、Au+、Zn2+、Hg2+、Cd2+Preferably of Au+、Cd2+(ii) a The outermost electronic structureIs d8Metal ions of (2) include, but are not limited to, Co+、Ir+、Rh+、Ni2+、Pt2+、Pb2+Preferably Pt2+、Pb2+. The metallophilic action can exist stably in the polymer, has moderate action strength, certain directionality and no obvious saturation, can be aggregated to form a polynuclear complex, is less influenced by the external environment, and can ensure that the dynamic property of the prepared polymer is more sufficient.
In the embodiment of the present invention, the combination of forming the metallophilic action is not particularly limited as long as a suitable metallophilic action is formed between metal ions. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
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 an embodiment of the present invention, the ionic hydrogen bonding in the supramolecular interaction is composed of a positive ionic group and a negative ionic group capable of forming hydrogen bonding, and simultaneously forms hydrogen bonding and coulomb interaction between positive and negative ions, or is composed of a positive/negative ionic group and a neutral hydrogen bonding group capable of forming hydrogen bonding, and simultaneously forms hydrogen bonding and ion-dipole interaction between positive/negative ions and the neutral group.
In the embodiments of the present invention, some suitable combinations of ionic hydrogen bonding can be exemplified as follows, but the present invention is not limited thereto:
in the present invention, the building units of the free radical cationic dimerization in the supramolecular interaction are groups containing both a free radical and a cation. By way of example, the free radical cationic dimerization may be formed, including but not limited to the following:
in an embodiment of the present invention, some suitable combinations of free radical cationic dimerization may be exemplified as follows, but the present invention is not limited thereto:
in embodiments of the invention, the host (represented by H) is a compound (macromolecular or infinite organic ionic framework) with a cavity capable of molecular recognition, the guest (represented by G) is a compound (small molecule or ionic group) capable of being recognized by the host and inserted into the cavity of the host, one host molecule can recognize the binding of multiple guest molecules, and in embodiments of the invention, it is preferred that one host molecule recognizes at most two guest molecules, the host molecule includes, but is not limited to, crown ethers, benzocrown ethers, cyclophanes, α -cyclodextrins, β -cyclodextrins, gamma-cyclodextrins, cucurbit [6] ureas, cucurbit [7] ureas, cucurbit [8] ureas, calix [4] arenes, calix [5] arenes, column [6] arenes, column [7] arenes, and some suitable inorganic ionic frameworks, preferably crown ethers, β -cyclodextrins, cucurbit [8] ureas, calix [4] arenes, calix [5] arenes, column [6] arenes, and some suitable inorganic ionic frameworks, preferably, a compound capable of dissociating into a compound, a compound capable of forming a long chain cycloarene, a polymer, a compound capable of forming a polymer, a long chain, a polymer, and a polymer capable of a long chain, and a polymer, a.
In embodiments of the present invention, when a host-guest interaction is present, the corresponding blocks of the flexible block polymer molecule may contain only host groups or only guest groups, and may also contain both host and guest groups. When one of the block polymer molecules only contains a host group or only contains a guest group, the dynamic polymer also contains any one or more of the block polymer molecules, small molecules, other polymers or inorganic matters which are compatible with the phase in which the dynamic polymer is located and contain the corresponding guest group or host group, and the dynamic polymer and the block polymer molecules are interacted to form dynamic host-guest interaction. When one of the block polymer molecules contains both a host group and a guest group, the positions of the host group and the guest group in the block of the block polymer molecule are not limited at all, and the host group and the guest group can be located in the same block or in different blocks, and the dynamic polymer can also selectively contain any one or combination of a small molecule, a polymer or an inorganic substance which is compatible with the phase in which the dynamic polymer is located and contains the corresponding host group and/or guest group, and the dynamic polymer and the block polymer molecule can jointly act to form dynamic host-guest action.
In embodiments of the invention, only one host group and/or one guest group may be present in a polymer chain or in a dynamic polymer system, or any suitable combination of multiple host and/or guest groups may be present simultaneously. A host group and/or guest group refers to a core structure. Host groups and/or guest groups at different positions may have the same core structure, which differs in the point of attachment and/or position of the core structure to a component, such as a polymer chain or small molecule.
Suitable host groups may be exemplified by, but are not limited to:
suitable guest groups may be exemplified by, but are not limited to:
in the embodiment of the present invention, the combination of the host group and the guest group is not particularly limited as long as the host can form a suitable host-guest interaction with the guest. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
in the present invention, in addition to the eleven series of supramolecular interaction combinations described above, a supramolecular interaction group/unit selected from the group consisting of supramolecular interaction combinations of metal-ligand interaction, hydrogen bonding interaction, dipole-dipole interaction may be included.
In an embodiment of the invention, the ligand group (represented by L) in the metal-ligand interaction is selected from cyclopentadiene and a structural unit containing at least one coordinating atom (represented by X). A coordinating atom may form one or more coordination bonds to one or more metal centers (selected from, but not limited to, metal ions, metal centers of metal chelates, metal centers of metal organic compounds, metal centers of metal inorganic compounds, and represented by M), and a metal center may also form one or more coordination bonds to one or more coordinating atoms. The number of coordination bonds formed by a ligand group and a metal center is called the number of teeth of the ligand group, in the embodiment of the present invention, in the same system, a metal center can form a metal-ligand action with one or more of a bidentate ligand, a bidentate ligand and a tridentate ligand, and different ligands can also form a ring by connecting through the metal center, so that the present invention can effectively provide dynamic metal-ligand actions with sufficient variety, quantity and performance, and the structures shown in the following general formulas are some examples, but the present invention is not limited thereto:
wherein X is a coordinating atom, M is a metal center,is cyclopentadiene ligand, and each ligand group and metal center form an X-M bond as a tooth, wherein the X is connected by a single bond to indicate that the coordination atoms belong to the same ligand group, when one ligand group contains two or more coordination atoms, the X can be the same atom or different atoms, and is selected from the group consisting of but not limited to boron, nitrogen, oxygen, sulfur, phosphorus, silicon, arsenic, selenium and tellurium; preferably boron, nitrogen, oxygen, sulfur, phosphorus; more preferably nitrogen, oxygen; most preferably nitrogen. In some cases, X is present in the form of negative ions. In the present invention, it is preferred that one coordinating atom form only one coordination bond with one metal center, and therefore the number of coordinating atoms in a ligand group that can form coordination bonds with the same metal center is the number of teeth in the ligand group. The ligand group interacts with the metal-ligand formed by the metal center (as M-L)mRepresenting the number of ligand groups that interact with the same metal center) is related to the type and number of coordinating atoms on the ligand groups, the type and valence of the metal center, and the counter ion, etc.
In the embodiment of the present invention, toTo form crosslinks/polymerizations based on metal-ligand interactions, a metal center is capable of forming metal-ligand interactions with at least two moieties of the ligand group (i.e., M-L)2Structure) unless the metal center is already attached to the polymer; there may also be multiple ligands forming a metal-ligand interaction with the same metal center, where two or more ligand groups may be the same or different. The coordination number of one metal center is limited, the more the coordinating atoms of the ligand groups are, the fewer the number of ligands that can be coordinated by one metal center is, and the lower the supramolecular cross-linking degree based on the metal-ligand effect is; however, since the more denticity each ligand forms with the metal center, the stronger the coordination, the lower the dynamic properties, it is preferred in the present invention that no more than tridentate ligand groups form dynamic metal-ligand interactions, preferably more than tridentate ligand groups form structural metal-ligand interactions.
In embodiments of the invention, there may be only one ligand in a polymer chain or in a dynamic polymer system, or any suitable combination of ligands may be present simultaneously. The ligand refers to a core ligand structure. One backbone ligand, pendant ligand, and terminal ligand may have the same core ligand structure, which may differ in the point of attachment and/or location of the core ligand structure to a component, such as a polymer chain or small molecule. In the present invention, suitable ligand groups (core ligand structure) can be exemplified as follows, but the present invention is not limited thereto:
examples of monodentate ligand groups are as follows:
-C≡N；
bidentate ligand groups are exemplified as follows:
tridentate ligand groups are exemplified below:
tetradentate ligand groups are exemplified below:
the polydentate ligands are exemplified by:
in embodiments of the invention, polymer chains and/or groups may be grafted at any suitable position of the ligand group (core ligand structure) without affecting the coordination properties.
In embodiments of the present invention, the metal center M may be the metal center of any suitable metal ion or compound/chelate or the like, which may be selected from any suitable ionic form, compound/chelate form and combinations thereof of any one of the metals of the periodic table of the elements.
The metal is preferably a metal of the first to seventh subgroups and group eight. The metals of the first to seventh subgroups and group VIII also include the lanthanides (i.e., La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and the actinides (i.e., Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr).
More preferably, the metal is selected from the group consisting of the first subgroup (Cu, Ag, Au), the second subgroup (Zn, Cd), the eighth group (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), the lanthanoid group (La, Eu, Tb, Ho, Tm, Lu), and the actinide group (Th). Further preferably, Cu, Zn, Fe, Co, Ni, Pd, Ag, Pt, Au, La, Ce, Eu, Tb, Th are selected to obtain stronger dynamic property.
In the embodiment of the present invention, the metal organic compound is not limited, and suitable examples include the following:
other suitable metal organic compounds capable of providing a metal center include, but are not limited to, metal-organic cages, metal-organic frameworks. Such metal organic compounds may be used alone or introduced into the polymer chain at suitable locations by means of suitable covalent chemical linkages. Those skilled in the art may implement the present invention reasonably and effectively in light of the logic and spirit of the present invention.
In the embodiment of the present invention, the metal inorganic compound is not limited, but oxide or sulfide particles of the above metal, particularly nanoparticles, are preferable.
In embodiments of the present invention, there is also no limitation on the metal chelate that can provide a suitable metal center. Preferably chelates which still have a vacancy in coordination sites, or chelates in which part of the ligands may be replaced by said skeletal ligands of the invention.
In embodiments of the invention, the combination of ligand groups and metal centers is not particularly limited, as long as the ligands are capable of generating a suitable metal-ligand interaction with the metal centers, but the strengths and dynamics of different metal-ligand interactions formed by different metal centers with the same ligand may vary greatly. Some suitable dynamic metal-ligand interaction combinations may be exemplified, but the invention is not limited thereto:
wherein,refers to a linkage to a polymer chain, cross-link, or any other suitable group/atom, including a hydrogen atom. As will appear again hereinafterThe above definitions and ranges are used, and repeated explanation is omitted unless otherwise specified.
In embodiments of the invention, the hydrogen bonding in the supramolecular interaction may be of any number of teeth. Wherein the number of teeth refers to the number of hydrogen bonds formed by a donor (H, i.e., a hydrogen atom) and an acceptor (Y, i.e., an electronegative atom that accepts a hydrogen atom) of hydrogen bonding groups, each H … Y combining into one tooth. In the following formula, the bonding of the monodentate, bidentate and tridentate hydrogen bonds is schematically illustrated, respectively.
The bonding of the monodentate, bidentate and tridentate hydrogen bonds can be specifically exemplified as follows:
in the embodiment of the present invention, the number of teeth of the hydrogen bond is not limited. The more the number of teeth of the hydrogen bond, the greater the synergistic effect and the greater the strength of the hydrogen bond. If the number of teeth of the formed hydrogen bonds is large, the strength is high, the dynamic property of the hydrogen bond action is weak, and the hydrogen bonds can be used as structural hydrogen bonds to play a role in promoting the dynamic polymer to keep an equilibrium structure and improve the mechanical properties (modulus and strength). If the number of teeth of the formed hydrogen bond is small, the strength is low, the dynamic property of the hydrogen bond action is strong, and the dynamic property can be provided as the dynamic hydrogen bond together with the dynamic metal-ligand action. In embodiments of the invention, it is preferred that no more than four-tooth hydrogen bonds provide dynamic hydrogen bonding, and preferably more than four-tooth hydrogen bonds provide structural hydrogen bonding.
In embodiments of the present invention, the hydrogen bonding may be caused by the presence of non-covalent interactions between any suitable hydrogen bonding groups, which may contain only hydrogen bonding donors, only hydrogen bonding acceptors, or both hydrogen bonding donors and acceptors. Wherein the soft segment of the block polymer molecule with the hard segment and soft segment structure contains at least one dynamic hydrogen bond group containing a hydrogen bond donor and an acceptor simultaneously so that the block polymer can independently form hydrogen bond action, and the block polymer can effectively form dynamic hydrogen bonds between the soft segments in the absence of other components containing the hydrogen bond group of the hydrogen bond donor, and is used as a synergistic or orthogonal complement of the dynamic metal-ligand action. It preferably contains at least one of the following structural components:
in embodiments of the present invention, the dynamic hydrogen bonding group is preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, derivatives of the above, and the like.
Examples of the hydrogen bonding group include the following side groups and/or terminal groups, but the present invention is not limited thereto.
Wherein m, n and x are the number of repeating groups, and can be fixed values or average values. m and n are integers with the value range of 0 and more than or equal to 1; the value range of x is an integer greater than or equal to 1.
As an example, hydrogen bonding groups on the soft segment main chain/side chain (including branched and forked chains) skeleton as described below can be cited, but the present invention is not limited thereto.
As an example, hydrogen bonding groups on the backbone of a hard segment main chain/side chain (including branched and forked chains) as described below can be cited, but the present invention is not limited thereto.
In the embodiment of the present invention, the hydrogen bonding groups forming hydrogen bonding may be complementary combinations of different hydrogen bonding groups or self-complementary combinations of the same hydrogen bonding groups, as long as the groups can form proper hydrogen bonding. Some combinations of hydrogen bonding groups may be exemplified as follows, but the invention is not limited thereto:
in the embodiment of the present invention, when two atoms with different electronegativities are bonded, the charge distribution is not uniform due to the induction effect of the atom with the larger electronegativity, so that an electric dipole is generated, and the two electric dipoles interact with each other to form a dipole-dipole effect. The electric dipole may be generated by bonding any suitable two atoms with different electronegativities, such as the following, but the invention is not limited thereto: 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, and more preferably C ≡ N. The dipole-dipole effect can stably exist in the polymer and is easy to regulate, and the pairing of the acting groups can generate a micro-domain, so that the interaction is more stable; at higher temperatures, the dipole-dipole effect is reduced or even eliminated, and thus polymers containing dipole-dipole effects may exhibit differences in dynamics depending on the temperature differences.
In the embodiment of the present invention, the combination between dipoles is not particularly limited as long as a suitable dipole-dipole action can be formed between the dipoles. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
in an embodiment of the present invention, in addition to the supramolecular interaction between the groups/units present in the flexible block polymer molecules, other components which may contain groups/units capable of forming supramolecular interactions may be present as additives to form supramolecular interactions with the groups/units present in the block polymer molecules. Such other components that may participate in the formation of supramolecules include, but are not limited to, small molecules, polymers, inorganic materials. Supramolecular interactions may also be formed between such other components. Such other components may be selected from linear, cyclic, branched, clustered polymers and covalently cross-linked polymer particles, surface modified organic or inorganic particles, fibers. The other polymer components can form a compatible physical cross-linked network with the block polymer molecules, and can also form a cross-linked network with a structure of mutual blending/interpenetrating/semi-interpenetrating which is compatible or incompatible. Wherein the flexible block polymer molecule of the present invention is 5-100% of the total weight of the dynamic polymer composition, preferably 50-100% of the total weight of the dynamic polymer composition.
In an embodiment of the invention, when two different supramolecular interactions are present simultaneously in the dynamic polymer, different types of supramolecular interactions are preferred, more preferably different series of supramolecular interactions. When selected from two different series of supramolecular interactions, preferred combinations of supramolecular interactions include, but are not limited to, the following combinations: the method comprises the following steps of pi-pi stacking action and metallophilic action, wherein a group/unit combined with a metal element in the metallophilic action can also form the pi-pi stacking action generally, the two actions usually exist simultaneously, and the prepared dynamic polymer has stable mechanical property; the host-guest action and the ionic action/the ion-dipole action/the ionic hydrogen bond action are utilized to regulate and control the identifiability between the host and the guest, and the functional specificity of the dynamic polymer can be greatly improved under the combined action; the ionic action and the ionic hydrogen bond action/ionic dipole action utilize two or more ionic groups shared by the supermolecule action to make the dynamic polymer easy to prepare, and the content ratio of different supermolecule actions can be regulated by changing the content of one group so as to achieve the purpose of regulating and controlling performance; any two or more of ion action, ion-dipole action and ion hydrogen bond action, and the conductivity of the dynamic polymer can be greatly improved by utilizing the ions in the ion-dipole action and the ion hydrogen bond action; the pi-pi stacking effect and the metal-ligand effect are realized, the ligand group in the metal-ligand effect can also form the pi-pi stacking effect, the dynamic polymer with the two effects existing simultaneously is easy to prepare, and the prepared dynamic polymer has stable mechanical property; the host-guest interaction and the hydrogen bonding interaction/the metal-ligand interaction/the dipole-dipole interaction are utilized to regulate and control the identification between the host and the guest, and the dynamic polymer can have functional specificity under the combined action; the ionic action/ionic-dipole action/ionic hydrogen bond action and metal-ligand action, and the electric conductivity of the dynamic polymer can be greatly improved by utilizing ions in the two actions; the ion action/ion-dipole action/pi-pi stacking action/halogen bond action and hydrogen bond action, the two supermolecule actions have simple forming modes and can stably exist, and the prepared dynamic polymer has good self-repairing performance; the halogen bond effect and the metal-ligand effect, the two supermolecule effects have simple forming modes and can exist stably, and the prepared dynamic polymer has good controllability and self-repairing performance; the ion-dipole effect and the dipole-dipole effect are simple in forming mode and can stably exist, and the prepared dynamic polymer has good controllability and self-repairing performance; the ionic action, the ionic-dipole action and the dipole-dipole action are simple in action groups of the three supramolecular actions, and the combination of the three supramolecular actions can be formed only by containing ions with opposite electric properties and a proper amount of dipole groups in the dynamic polymer, so that the dynamic polymer not only has good conductivity, but also has good mechanical properties.
In the embodiment of the present invention, in addition to the supramolecular interaction between the groups/units present in the block polymer molecule, other components containing groups/units capable of forming supramolecular interaction may be used as additives to form supramolecular interaction with the groups/units present in the block polymer molecule. Such other components that may participate in the formation of supramolecules include, but are not limited to, small molecules, polymers, inorganic materials. Supramolecular interactions may also be formed between such other components. Such other components may be selected from linear, cyclic, branched, clustered polymers, and covalently cross-linked polymer particles, surface-modified organic or inorganic particles, fibers.
In an embodiment of the invention, in addition to the block polymer molecular components having a hard segment-soft segment structure comprising at least one of said dynamic supramolecular interactions, the dynamic polymer may comprise at least one of other supramolecular interaction combinations comprising only dynamic metal-ligand interactions, dynamic hydrogen bonding interactions, dynamic dipole-dipole interactions or any other suitable hard segment-soft segment polymer components compatible or incompatible with said block polymer molecular components, not comprising any supramolecular interactions, any suitable polymer component which is compatible or incompatible with the polymer component and can form any one or any number of supramolecular interactions, and other polymer components, and small molecules and fillers which can form any one or any number of supramolecular interactions, and the like. The other hard segment-soft segment polymer components can form a compatible physical cross-linked network with the block polymer molecules, and can also form a cross-linked network with structures such as compatible or incompatible mutual blending/interpenetrating/semi-interpenetrating, and the like. Wherein the block polymer molecule having a hard segment-soft segment structure comprising at least one dynamic supramolecular interaction described herein is present in an amount of from 5 to 100% by weight, preferably from 50 to 100% by weight, based on the total weight of the dynamic polymer composition.
In the embodiment of the present invention, the process for preparing the block polymer molecule having the hard segment-soft segment structure contained in the dynamic polymer may be any suitable means in principle. There are generally two ways to carry out the polymerization of the soft segment or the hard soft segment from the monomer in sequence from inside to outside or from outside to inside; or respectively synthesizing hard segment, soft segment or multi-segment copolymer with functionalized end group and/or side group, and then directly carrying out the reaction between chain segments or realizing the coupling or copolymerization through other small molecules. The block polymer molecule can also be prepared by combining the two modes, for example, firstly preparing a hard segment or a soft segment into a macroinitiator, initiating the polymerization of the adjacent soft segment and the hard segment, and then carrying out the end group reaction between the chain segments according to the requirement; for another example, a soft block-hard block diblock copolymer is formed, and two or more diblock molecules are coupled to obtain a polymer molecule having a hard block-soft block multistage structure according to the present invention. Wherein, the generation or introduction of the ligand group and the hydrogen bond group can be carried out before, after or in the process of connecting the soft segment and the hard segment. When a polymer containing hard and soft segments is first produced and then the ligand groups and hydrogen bonding groups are introduced or produced, the polymer segments must contain corresponding active sites, examples of which include, but are not limited to, amino groups, secondary amino groups, hydroxyl groups, carboxyl groups, mercapto groups, isocyanate groups, epoxy groups, ester groups, halogen atoms, acid halide groups, acid anhydrides, carbon-carbon double bonds, maleimide groups, carbon-carbon triple bonds, azide groups, nitrile groups, hydrazine, tetrazine, and succinimide esters.
The polymerization process includes, but is not limited to, polycondensation, polyaddition, coordination polymerization and ring-opening polymerization, depending on the type of prepolymer selected, polyaddition including, but not limited to, free radical polymerization, living radical polymerization, anionic polymerization, cationic polymerization, and the like. The polymerization process may be carried out in a solvent or may be carried out by bulk polymerization without a solvent.
Initiation of the above partial polymerization process requires the use of an initiator capable of causing activation of the monomer molecules during the polymerization reaction. Different types of initiators may be selected as desired in embodiments of the present invention. For example, the use of a monofunctional initiator facilitates the preparation of a single-end functionalized segment or a double-end heterofunctionalized segment; as another example, the use of a di/multi-functional initiator facilitates the preparation of di/multi-terminal homofunctionalized or di/multi-terminal heterofunctionalized segments; for another example, a macroinitiator prepared using a single-end functionalized segment or a telechelic polymer segment can continue to initiate polymerization of other monomers to obtain a block copolymer. The preparation of the single, double and multi-terminal functionalized polymer chain segment is realized by reasonably selecting an initiator with an active group, reasonably selecting a chain transfer agent and reasonably using a functional reagent capable of reacting with the residue of the initiator.
In the embodiment of the invention, partial polymerization reaction also needs to use a catalyst, so that the reaction path is changed during the polymerization reaction, and the reaction activation energy is reduced to accelerate the reaction rate of reactants during the reaction process. In part of the polymerization process, auxiliary agents such as a dispersant, an emulsifier and the like are required. For example, dispersants are required during suspension polymerization and emulsifiers are required during emulsion polymerization. The dispersant can disperse solid floccules in the polymer mixed solution into fine particles to be suspended in the liquid, uniformly disperse solid and liquid particles which are difficult to dissolve in the liquid, and simultaneously prevent the particles from settling and coagulating to form stable suspension. The emulsifier can improve the surface tension between various constituent phases in the polymer mixed solution containing the auxiliary agent to form a uniform and stable dispersion system or emulsion, and is preferably used for carrying out emulsion polymerization.
Specifically, by way of example, alternative aggregation methods of the present invention include, but are not limited to: thermal initiation common free radical polymerization of styrene monomers and (meth) acrylate monomers, photo initiation free radical polymerization of styrene monomers and (meth) acrylate monomers, initiation transfer terminator method free radical polymerization of vinyl chloride monomers, atom transfer free radical polymerization (ATRP) of styrene monomers and (meth) acrylate monomers, reversible addition-fragmentation transfer free radical polymerization (RAFT) of styrene monomers, reversible addition-fragmentation transfer free radical polymerization (ATRP) of (meth) acrylate monomers, nitrogen-oxygen stable free radical polymerization (NMP), coordination polymerization of ethylene and propylene, anionic polymerization of styrene monomers, lactone ring-opening polymerization, lactam ring-opening polymerization, epoxy ring-opening polymerization, cyclic olefin ring-opening metathesis polymerization, polycondensation between dibasic acid and dibasic alcohol, polycondensation between dibasic acid and dibasic amine, click reaction polymerization between dibasic thiol and dibasic alkene/alkyne, click reaction polymerization between binary azide and binary alkyne, ring-opening polymerization of 2-ethyl-2-oxazoline, polyurethane/polyurea reaction, and the like.
The initiator, catalyst, other auxiliary agents, reaction conditions, etc. required for the above-mentioned polymerization method and polymerization process are publicly known conventional techniques (e.g. main eds of panzu, high molecular chemistry (enhanced edition)), and those skilled in the art can make reasonable selection and combination according to the needs.
In embodiments of the present invention, reactions that may be employed for the generation or introduction of the backbone ligand group include, but are not limited to, the following types: reaction of isocyanate with amino/hydroxyl/mercapto/carboxyl, electrophilic substitution reaction of heterocycle, nucleophilic substitution reaction of heterocycle, double bond (including acrylate, acrylamide, etc.) free radical reaction, azide-alkyne click reaction, mercapto-double bond/alkyne click reaction, urea-amine reaction, amidation reaction, tetrazine-norbornene reaction, reaction of active ester with amino; preferably isocyanate and amino/hydroxyl/sulfhydryl reaction, double bond free radical reaction, azide-alkyne click reaction, sulfhydryl-double bond/alkyne click reaction, urea-amine reaction, amidation reaction, reaction of active ester and amino; more preferred are the reaction of isocyanate with amino/hydroxyl/thiol, double bond radical reaction, azide-alkyne click reaction, thiol-double bond/alkyne click reaction.
In embodiments of the present invention, the generation or introduction of pendant or terminal ligand groups may employ any suitable reaction, including but not limited to the following types: esterification reaction, reaction of isocyanate and amino/hydroxyl/sulfydryl/carboxyl, electrophilic substitution reaction of heterocycle, nucleophilic substitution reaction of heterocycle, double bond free radical reaction, side chain reaction of heterocycle, azide-alkyne click reaction, sulfydryl-double bond/alkyne click reaction, urea-amine reaction, amidation reaction, tetrazine-norbornene reaction and reaction of active ester and amino; preferably, esterification reaction, reaction of isocyanate with amino/hydroxyl/sulfhydryl, azide-alkyne click reaction, urea-amine reaction, amidation reaction, reaction of active ester with amino, and sulfhydryl-double bond/alkyne click reaction; more preferred are esterification, reaction of isocyanate with amino/hydroxy/mercapto, mercapto-double bond/alkyne click, azide-alkyne click.
In embodiments of the invention, the introduction of the metal centre may be carried out at any suitable time. There are at least three methods, which can be introduced before the introduction/formation of the ligand, after the composition which has previously formed a metal-ligand interaction with the ligand, or after the preparation of the polymer molecule has been completed. Preferably after the ligand groups are generated.
In embodiments of the present invention, the generation or introduction of hydrogen bonding groups may employ any suitable reaction, including but not limited to the following types: reaction of isocyanate with amino/hydroxyl/mercapto/carboxyl, double bond (including acrylate, acrylamide and the like) free radical reaction, double bond cyclization reaction, reaction of epoxy with amino/hydroxyl/mercapto, azide-alkyne click reaction, mercapto-double bond/alkyne click reaction, urea-amine reaction, esterification reaction, amidation reaction, tetrazine-norbornene reaction, reaction of active ester with amino/hydroxyl/mercapto, and silicon hydroxyl condensation reaction; preferably the reaction of isocyanates with amino/hydroxy/mercapto groups, urea-amines, reactive esters with amino/hydroxy/mercapto groups; more preferably the reaction of isocyanates with amino/hydroxy/mercapto groups. The generation or introduction of hydrogen bonding groups can have one or more reaction types and reaction means, and the hydrogen bonding between the hydrogen bonding groups can have one or more types and structures.
In embodiments of the present invention, reactions between the reactive groups at the ends of the segments, such as the following, may be used to link the soft and hard segments of the block polymer molecule or to obtain covalent bonds within the segments: the reaction of isocyanate with amino/hydroxyl/mercapto, carboxyl, epoxy with amino/hydroxyl/mercapto, phenolic, azide-alkyne click reaction, mercapto-double bond/alkyne click reaction, urea-amine reaction, amidation, esterification, tetrazine-norbornene reaction, reaction of active ester with amino/hydroxyl/mercapto, silicon hydroxyl condensation reaction.
Those skilled in the art can also select appropriate preparation means to achieve the desired purpose according to the understanding of the present invention.
In the present invention, the form of the dynamic polymer and the composition containing the same may be a general solid, an elastomer, a gel, a foam, or the like. Wherein the content of soluble low molecular weight components contained in common solid and foam materials is generally not higher than 10 wt%, and the content of low molecular weight components contained in gel is generally not lower than 50 wt%. Ordinary solids and elastomers are preferred because they have better mechanical properties and the preparation process is the simplest and most convenient. The foam is more preferable because of its light weight and the like.
In an embodiment of the present invention, the dynamic polymer gel may be obtained by crosslinking in a swelling agent (including one or a combination of water, an organic solvent, an oligomer, a plasticizer, and an ionic liquid), or may be obtained by swelling with a swelling agent after the preparation of the dynamic polymer is completed. Of course, the present invention is not limited to this, and those skilled in the art can implement the present invention reasonably and effectively according to the logic and context of the present invention.
In embodiments of the invention, a swelling agent that is compatible with the soft phase but incompatible with the hard phase may be incorporated into the dynamic polymer to prepare a dynamic polymer gel. The swelling agent may include, but is not limited to, water, organic solvents, ionic liquids, oligomers, plasticizers. The oligomers can also be regarded as plasticizers. Adopting a water swelling system to form hydrogel, wherein the organic solvent swelling system is called organic gel, the ionic liquid swelling system is called ionic liquid gel, the oligomer swelling system is called oligomer swelling gel, and the plasticizer swelling system is called plasticizer swelling gel; the gel swollen by the ionic liquid, the oligomer and the plasticizer can also be called organogel.
The dynamic polymer gel provided by the invention is preferably an ionic liquid gel, an oligomer swelling gel and a plasticizer swelling gel, and more preferably a plasticizer swelling gel. Gels have the advantage of softness, while plasticizers have the advantage of high boiling point and good stability.
The preferred preparation method of the dynamic polymer ionic liquid gel comprises the following steps: and (2) blending the raw materials for preparing the dynamic polymer and the ionic liquid to ensure that the mass fraction of the raw materials for preparing the dynamic polymer is 0.5-70%, carrying out polymerization, coupling or other types of chemical reactions by the proper means, and preparing the dynamic polymer ionic liquid gel after the reaction is finished. Another preferred method for preparing a dynamic polymer ionic liquid gel of the present invention includes, but is not limited to, the following steps: and swelling the block polymer and the raw material of the metal center in a solvent containing ionic liquid to ensure that the mass fraction of the block polymer is 0.5-70%, and removing the solvent after full swelling to prepare the dynamic polymer ionic liquid gel. The block polymer molecule for preparing the ionic liquid gel is preferably a polymer soft segment skeleton which is a segment based on a polymer containing acrylate monomers, fluorine substituted poly saturated olefin and a polymer containing acrylonitrile.
The preferred preparation method of the swelling gel of the dynamic polymer oligomer comprises the following steps: and (2) blending the raw materials for preparing the dynamic polymer and the oligomer to ensure that the mass fraction of the raw materials for preparing the dynamic polymer is 0.5-70%, carrying out polymerization, coupling or other types of chemical reactions by the proper means, and preparing the gel swollen by the dynamic polymer oligomer after the reaction is finished. Another preferred method for preparing the swollen gel of the dynamic polymer oligomer of the invention includes, but is not limited to, the following steps: and swelling the raw materials in the block polymer and the metal in a solvent containing an oligomer to ensure that the mass fraction of the block polymer is 0.5-70%, and removing the solvent after full swelling to prepare the gel swollen by the dynamic polymer oligomer.
A preferred method for preparing a dynamic polymer plasticizer swollen gel of the present invention includes, but is not limited to, the following steps: the raw materials for preparing the dynamic polymer and the plasticizer are blended to enable the mass fraction of the raw materials for preparing the dynamic polymer to be 0.5-70%, polymerization, coupling or other types of chemical reactions are carried out through the appropriate means, and after the reactions are finished, the gel swelled by the dynamic polymer plasticizer is prepared. Another preferred method for preparing the dynamic polymer plasticizer swollen gel of the present invention includes, but is not limited to, the following steps: and swelling the block polymer and the raw material of the metal center in a solvent containing a plasticizer to ensure that the mass fraction of the block polymer is 0.5-70%, and removing the solvent after full swelling to prepare the gel swelled by the dynamic polymer plasticizer. The block polymer for preparing the plasticizer-swollen gel is preferably a polymer segment in which the soft segment is a polymer based on a vinyl chloride-containing monomer, a norbornene-containing monomer, or a saturated olefin-containing monomer.
In an embodiment of the invention, another preferred form of the dynamic polymer and its composition is a foam.
In the embodiments of the present invention, the structure of the dynamic polymer foam material relates to three structures, i.e., an open-cell structure, a closed-cell structure, a semi-open and semi-closed structure, and the like. In the open pore structure, the cells are communicated with each other or completely communicated with each other, gas or liquid can pass through the single dimension or the three dimensions, and the cell diameter is different from 0.01 to 3 mm. The closed cell structure has an independent cell structure, the inner cells are separated from the cells by wall membranes, most of the inner cells are not communicated with each other, and the cell diameter is 0.01-3 mm. The contained cells have a structure which is not communicated with each other, and the structure is a semi-open cell structure.
In the embodiment of the present invention, the foaming method may be classified into a physical foaming method and a chemical foaming method according to the difference of the foaming agent used.
Physical foaming is a method of foaming a dynamic polymer by a physical method, and generally includes three methods: (1) firstly, dissolving inert gas in a dynamic polymer under pressure, and releasing the gas through decompression so as to form air holes in the material for foaming; (2) foaming by heating a low boiling point liquid dissolved in a polymer or a raw material component thereof to vaporize the liquid; (3) hollow spheres and/or expandable polymer microspheres are added to the raw material components, and a foam is formed and expanded during or after the formation of the dynamic polymer. The physical foaming agent used in the physical foaming method has relatively low cost, particularly low cost of carbon dioxide and nitrogen, flame retardance and no pollution, so the application value is high; and the physical foaming agent has no residue after foaming, and has little influence on the material performance. The method of adding the hollow spheres is simplest in process.
Chemical foaming is a process of foaming a dynamic polymer by generating gas by a chemical method, and generally includes two methods: (1) heating the chemical foaming agent added into the dynamic polymer (raw material) to decompose and release gas for foaming; (2) the foaming may also be effected by gases released by chemical reactions between the components of the raw materials, for example the reaction of carbonates with acids to release carbon dioxide.
In the invention, part of the polymer generates gas in the process of polymerization or other chemical reaction, and in this case, an additional foaming agent is not needed. Physical foaming is preferred in embodiments of the present invention because the physical foaming agent used in the physical foaming process is relatively low in cost, flame retardant, non-polluting, and does not leave a residue after foaming, and does not significantly affect the properties of the foamed polymer. The gel-type material is particularly suitable for foaming by hollow spheres and/or expandable polymer microspheres.
In addition to the usual methods of preparing foams described above, freeze-drying may also be used to prepare the foams. A method of preparing a foam material using a freeze-drying process comprising the steps of: the dynamic polymer, which swells in a solvent compatible with the soft phase, incompatible with the hard phase and volatile, is frozen and then escapes in a sublimating manner under near vacuum conditions. During and after solvent evolution, the dynamic polymer can maintain its pre-frozen shape, thereby resulting in a porous sponge-like foam.
One embodiment for preparing the dynamic polymer foam is to mix the dynamic polymer, the foaming agent and other auxiliary agents thoroughly and inject them into a mold to complete the foaming. Among them, the block polymer for preparing the foam is preferably a polymer based on polyurethane, polyurea, i.e., a polymer having urethane bond and urea bond as a linking group, and is preferably a polymer in which the soft segment is based on saturated olefin, unsaturated olefin, halogenated olefin, polyether, polyester, silicone rubber, polyacrylate-based polymer, polyvinyl acetate-based polymer, polyacrylonitrile-based polymer.
The dynamic polymer foam material provided by the invention also relates to: converting the dynamic polymeric foam material into any desired shape, such as tubes, rods, sheaths, containers, spheres, sheets, rolls, and tapes, by welding, gluing, cutting, routing, perforating, embossing, laminating, and thermoforming; use of the dynamic polymer foam in a floating device; use of the dynamic polymer foam material in any desired shape for thermal insulation; combining the dynamic polymeric foam material with sheets, films, foams, fabrics, reinforcements, and other materials known to those skilled in the art into a complex sandwich structure by lamination, bonding, fusing, and other joining techniques; use of the dynamic polymer foam in a gasket or seal; use of the dynamic polymer foam in a packaging material or in a container. With respect to the dynamic polymers of the present invention, the foamable dynamic polymers are of a type such that they can be deformed by extrusion, injection molding, compression molding or other forming techniques known to those skilled in the art.
In the embodiment of the present invention, other polymers, swelling agents, auxiliaries, fillers may be optionally added or used as formulation components of the dynamic polymer, or may play a role in improving processability in the preparation process of the dynamic polymer, within a range not interfering with the object of the present invention.
The other polymers can be used as additives to improve material performance, endow materials with new performance, improve material use and economic benefits and achieve the effect of comprehensive utilization of the materials in a system. Other polymers can be added, which can be selected from natural high molecular compounds and synthetic high molecular compounds. The invention does not limit the character and molecular weight of the added polymer, and can be oligomer or high polymer according to the difference of molecular weight, and can be homopolymer or copolymer according to the difference of polymerization form, and the polymer is selected according to the performance of the target material and the requirement of the actual preparation process in the specific using process.
When the other polymer is selected from natural high molecular compounds, it can be selected from any one or several of the following natural high molecular compounds: natural rubber, chitosan, chitin, natural protein, polysaccharide, etc.
When the other polymer is selected from synthetic macromolecular compounds, it can be selected from any one or several of the following: polychlorotrifluoroethylene, chlorinated polyethylene, chlorinated polyvinyl chloride, polyvinylidene chloride, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultrahigh-molecular-weight polyethylene, melamine-formaldehyde resin, polyamide, polyacrylic acid, polyacrylate, polyacrylamide, polyacrylonitrile, polybenzimidazole, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyethylene glycol, polyester, polyethersulfone, polyarylsulfone, polyetheretherketone, tetrafluoroethylene-perfluoropropane copolymer, polyimide, polyacrylate, polyacrylonitrile, polyphenylene ether, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high-impact polystyrene, polysulfone, polytetrafluoroethylene, polyurethane, polyurea, polyvinyl acetate, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyethylene terephthalate, Acrylonitrile-acrylate-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-vinyl acetate copolymer, polyvinylpyrrolidone, epoxy resin, phenol resin, urea resin, unsaturated polyester, polyisoprene, polybutadiene, styrene-butadiene copolymer, butadiene-acrylonitrile copolymer, poly (2-chloro-1, 3-butadiene), isobutylene-isoprene copolymer, ethylene-propylene-1, 4-hexadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-ethylidene norbornene copolymer, polydimethylsiloxane, polymethylvinylsiloxane, polymethylphenylsiloxane, polymethylvinylphenylsiloxane, poly (vinyl-co-styrene), poly (vinyl chloride-co-butadiene), poly (vinyl chloride-co-vinyl acetate), poly (vinyl pyrrolidone), poly (vinyl, Polymethyl vinyl trifluoropropyl siloxane, vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-propylene copolymer, polyepichlorohydrin, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-ethylene oxide-propylene oxide copolymer, etc.
Wherein, the auxiliary agent can include but is not limited to one or a combination of several of the following, such as synthesis auxiliary agents, including catalysts and initiators; stabilizing aids including antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants; the auxiliary agent for improving the mechanical property comprises a toughening agent and a coupling agent; the auxiliary agents for improving the processing performance comprise a solvent, a lubricant, a release agent, a thickening agent, a thixotropic agent and a flatting agent; the color light changing auxiliary agent comprises a coloring agent, a fluorescent whitening agent and a delustering agent; other auxiliary agents include antistatic agents, sterilization and mildew proofing agents, foaming agents, foam stabilizers, nucleating agents, rheological agents and the like.
The catalyst in the auxiliary may be selected from ① catalysts for polyurethane synthesis such as amine catalysts like triethylamine, triethylenediamine, bis (dimethylaminoethyl) ether, 2- (2-dimethylamino-ethoxy) ethanol, trimethylhydroxyethylpropylenediamine, N, N-bis (dimethylaminopropyl) isopropanolamine, N- (dimethylaminopropyl) diisopropanolamine, N, N, N ' -trimethyl-N ' -hydroxyethyldiaminoethyl ether, tetramethyldipropylenetriamine, N, N-dimethylcyclohexylamine, N, N, N ', N ' -tetramethylalkylenediamine, N, N, N ', N ', N ' -pentamethyldiethylenetriamine, N, N-dimethylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylaminomethyl) phenol, trimethyl-N-2-hexanoic acid, N, N-dimethylbenzylamine, N, N-dimethylhexadecylamine, N-ethylmorpholine, 2,4,6- (dimethylaminomethyl) phenol, trimethyl-N-2-ethylhexanoic acid, hydroxypropyl-2-dimethylbenzylamine, N-dimethyloctylammonium chloride, potassium octylate, potassium chloride, potassium octylate, potassium chloride, potassium octylaluminum chloride, potassium chloride, sodium chloride, potassium chloride, sodium chloride, potassium chloride, sodium chloride, potassium chloride, sodium chloride, potassium chloride, sodium chloride, potassium chloride, sodium chloride, potassium chloride, sodium chloride, potassium chloride, sodium chloride, potassium3CN)4]PF6、[Cu(CH3CN)4]OTf、CuBr(PPh3)3Etc.; the amine ligand may be selected from the group consisting of tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TBTA), tris [ (1-tert-butyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TTTA), tris (2-benzimidazolemethyl) amine (TBIA), sodium bathophenanthroline disulfonate hydrate and the like, ④ thiol-ene reaction catalyst, photocatalyst such as benzoin dimethyl ether, 2-hydroxy-2-methylphenyl acetone, 2-dimethoxy-2-phenyl acetophenone and the like, nucleophile catalyst such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazole, diisopropylethylamine and the like, the amount of the catalyst used is not particularly limited, and is generally 0.01 to 0.5% by weight.
The initiator in the assistant is capable of causing monomer molecules to activate to generate free radicals during the polymerization reaction, thereby increasing the reaction rate and promoting the reaction, and includes, but is not limited to, ① radical polymerization initiators such as organic peroxides, e.g., lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxypivalate, di-t-butylperoxide, diisopropylbenzene hydroperoxide, azo compounds, e.g., Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, inorganic peroxides, e.g., ammonium persulfate, potassium persulfate, etc., ② polymerization initiators such as 2,2,6, 6-tetramethyl-1-oxypiperidine, 1-chloro-1-phenylethane/cuprous chloride/bipyridine ternary system, etc., ③ ionic polymerization initiators such as butyllithium, sodium/naphthalene system, boron trifluoride/water system, stannic chloride/haloalkane system, ④ coordination initiator system such as aluminum chloride/cuprous chloride/bipyridine ternary system, preferably, 2, 5-methyl-acetyl-zirconium chloride/stannous chloride system, 2, 539 polymerization initiators such as ethylene-2, 2-butyl lithium, 2, 6-ethyl-1-stannous chloride/bis-pyridine, and the like.
The antioxidant in the aid can retard the oxidation process of polymer samples and ensure that the materials can be processed smoothly and have a prolonged service life, and includes, but is not limited to, any one or more of hindered phenols such as 2, 6-di-tert-butyl-4-methylphenol, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2 '-methylenebis (4-methyl-6-tert-butylphenol), sulfur-containing hindered phenols such as 4,4' -thiobis- [ 3-methyl-6-tert-butylphenol ], 2 '-thiobis- [ 4-methyl-6-tert-butylphenol ], triazine-based hindered phenols such as 1,3, 5-bis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] -hexahydro-triazine, tri-isocyanate hindered phenols such as tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -triisocyanate, N' -bis [3, 5-tert-butyl-4-hydroxyphenyl) propionyl ] -hexahydro-triazine, tri-phenylene phosphite, N '-bis [3, 5-butyl-4-hydroxyphenyl ] bis (BHT, N' -hydroxy-phenyl) propionate, N-butyl-4-hydroxy-phenyl) propionate, BHT, N '-bis (3, N' -tert-butyl-4-hydroxy-phenyl) phosphite, N '-bis (3, N' -tert-butyl-4-butyl-phenyl) phosphite, N '-hydroxy-phenyl) phosphite, N' -tert-butyl-6-butyl-4-butyl-tert-butyl-phenyl phosphite, N '-hexahydro-4-tert-phenyl phosphite, BHT, N' -hexahydro-4-butyl-.
The light stabilizer in the assistant can prevent the polymer sample from photo-aging and prolong the service life of the polymer sample, and the assistant comprises any one or more than one of the following light stabilizers: light-shielding agents such as carbon black, titanium dioxide, zinc oxide, calcium sulfite; ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2,4, 6-tris (2-hydroxy-4-n-butoxyphenyl) -1,3, 5-s-triazine, 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate; precursor type ultraviolet absorbers such as p-tert-butyl benzoate salicylate, bisphenol A disalicylate; ultraviolet ray quenchers, such as bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester), 2' -thiobis (4-tert-octylphenoloxy) nickel; hindered amine light stabilizers such as bis (2,2,6, 6-tetramethylpiperidine) sebacate, 2,2,6, 6-tetramethylpiperidine benzoate, tris (1,2,2,6, 6-pentamethylpiperidyl) phosphite; other light stabilizers, such as 2, 4-di-tert-butyl-4-hydroxybenzoic acid (2, 4-di-tert-butylphenyl) ester, alkylphosphoric acid amide, zinc N, N '-di-N-butyl dithiocarbamate, nickel N, N' -di-N-butyl-N-butyldithiocarbamate, etc.; among them, carbon black and bis (2,2,6, 6-tetramethylpiperidine) sebacate (light stabilizer 770) are preferable as the light stabilizer. The amount of the light stabilizer to be used is not particularly limited, but is usually 0.01 to 0.5% by weight.
The heat stabilizer in the additive can prevent the polymer sample from generating chemical changes due to heating in the processing or using process, or delay the changes to achieve the purpose of prolonging the service life, and the heat stabilizer comprises any one or more of the following heat stabilizers: lead salts, such as tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead benzoate, tribasic lead maleate, basic lead silicate, lead stearate, lead salicylate, dibasic lead phthalate, basic lead carbonate, silica gel coprecipitated lead silicate; metal soaps: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate; organotin compounds, such as di-n-butyltin dilaurate, di-n-octyltin dilaurate, di (n) -butyltin maleate, mono-octyl di-n-octyltin dimaleate, di-n-octyltin isooctyl dimercaptoacetate, tin C-102, dimethyl tin isooctyl dimercaptoacetate, dimethyl tin dimercaptolate, and combinations thereof; antimony stabilizers such as antimony mercaptide, antimony thioglycolate, antimony mercaptocarboxylate, antimony carboxylate; epoxy compounds, such as epoxidized oils, epoxidized fatty acid esters, epoxy resins; phosphites, such as triaryl phosphites, trialkyl phosphites, triarylalkyl phosphites, alkyl-aryl mixed esters, polymeric phosphites; polyols, such as pentaerythritol, xylitol, mannitol, sorbitol, trimethylolpropane; composite heat stabilizers such as coprecipitated metal soaps, liquid metal soap composite stabilizers, organic tin composite stabilizers and the like; among them, barium stearate, calcium stearate, di-n-butyltin dilaurate, and di (n) -butyltin maleate are preferable as the heat stabilizer. The amount of the heat stabilizer to be used is not particularly limited, but is usually 0.1 to 0.5% by weight.
The dispersing agent in the auxiliary agent can disperse solid floccules in the polymer mixed solution into fine particles to be suspended in the liquid, uniformly disperse solid and liquid particles which are difficult to dissolve in the liquid, and simultaneously can prevent the particles from settling and coagulating to form a stable suspension, and the dispersing agent comprises any one or more of the following dispersing agents: anionic type, such as sodium alkyl sulfate, sodium alkyl benzene sulfonate, sodium petroleum sulfonate; a cationic type; nonionic types, such as fatty alcohol polyoxyethylene ether, sorbitan fatty acid polyoxyethylene ether; inorganic types such as silicates, condensed phosphates; polymer type, such as starch, gelatin, water soluble gum, lecithin, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, lignosulfonate, polyvinyl alcohol, etc. Among them, the dispersant is preferably sodium dodecylbenzene sulfonate, naphthalene methylene sulfonate (dispersant N) and fatty alcohol-polyoxyethylene ether, and the amount of the dispersant used is not particularly limited, and is generally 0.3 to 0.8 wt%.
The emulsifier in the auxiliary can improve the surface tension between various constituent phases in the polymer mixed solution containing the auxiliary to form a uniform and stable dispersion system or emulsion, and the emulsifier comprises any one or more of the following emulsifiers: anionic type, such as higher fatty acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, sodium alkylnaphthalenesulfonate, succinic acid ester sulfonate, petroleum sulfonic acid salts, fatty alcohol sulfate salts, castor oil sulfate ester salts, sulfated butyl ricinoleate salts, phosphate ester salts, fatty acyl-peptide condensates; cationic, such as alkyl ammonium salts, alkyl quaternary ammonium salts, alkyl pyridinium salts; zwitterionic, such as carboxylate, sulfonate, sulfate, phosphate; nonionic, such as fatty alcohol polyoxyethylene ether, alkylphenol ethoxylates, fatty acid polyoxyethylene ester, polypropylene oxide-ethylene oxide adduct, glycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester, sucrose fatty acid ester, alcohol amine fatty acid amide, etc. Among them, sodium dodecylbenzenesulfonate, sorbitan fatty acid ester, triethanolamine stearate (emulsifier FM) are preferable, and the amount of the emulsifier used is not particularly limited, but is generally 1 to 5 wt%.
The flame retardant in the auxiliary agent can increase the flame resistance of the material, and includes but is not limited to any one or any several of the following flame retardants: phosphorus series such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate; halogen-containing phosphates such as tris (2, 3-dibromopropyl) phosphate, tris (2, 3-dichloropropyl) phosphate; organic halides such as high chlorine content chlorinated paraffins, 1,2, 2-tetrabromoethane, decabromodiphenyl ether, perchlorocyclopentadecane; inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate; reactive flame retardants such as chlorendic anhydride, bis (2, 3-dibromopropyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride, and the like; among them, decabromodiphenyl ether, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, and antimony trioxide are preferable as the flame retardant. The amount of the flame retardant to be used is not particularly limited, but is generally 1 to 20% by weight.
The toughening agent in the auxiliary agent can reduce the brittleness of a polymer sample, increase the toughness and improve the bearing strength of the material, and the toughening agent comprises any one or more of the following toughening agents: methyl methacrylate-butadiene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modified product, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene rubber, ethylene-propylene-diene monomer rubber, butadiene rubber, styrene-butadiene-styrene block copolymer, etc.; among them, the toughening agent is preferably ethylene-propylene rubber, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), methyl methacrylate-butadiene-styrene copolymer resin (MBS) or chlorinated polyethylene resin (CPE). The amount of the toughening agent to be used is not particularly limited, but is generally 5 to 10% by weight.
The coupling agent in the additive can improve the interface performance of a polymer sample and an inorganic filler or a reinforcing material, reduce the viscosity of a material melt in the plastic processing process, improve the dispersion degree of the filler to improve the processing performance, and further enable a product to obtain good surface quality and mechanical, thermal and electrical properties, wherein the coupling agent comprises any one or more of the following coupling agents: organic acid chromium complex, silane coupling agent, titanate coupling agent, sulfonyl azide coupling agent, aluminate coupling agent and the like; among them, gamma-aminopropyltriethoxysilane (silane coupling agent KH550) and gamma- (2, 3-glycidoxy) propyltrimethoxysilane (silane coupling agent KH560) are preferable as the coupling agent. The amount of the coupling agent to be used is not particularly limited, but is generally 0.5 to 2% by weight.
The solvent in the auxiliary agent can adjust the viscosity, is convenient for process operation, and is used in the preparation process or preparation of products. It includes but is not limited to any one or any several of the following: hydrocarbons (e.g., cyclohexane, heptane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, tetrachloromethane), aromatic hydrocarbons (e.g., toluene, xylene), ketones (e.g., acetone, methyl ethyl ketone), ethers (e.g., diethyl ether, tetrahydrofuran, dioxane), esters (e.g., ethyl acetate, butyl acetate), glycol ether esters (e.g., ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate), Dimethylformamide (DMF), N-methylpyrrolidone (NMP), and the like. The amount of the solvent used is not particularly limited, but is generally 1 to 200% by weight.
The lubricant in the additive can improve the lubricity, reduce the friction and reduce the interfacial adhesion performance of a polymer sample, and comprises but is not limited to any one or any several of the following lubricants: saturated and halogenated hydrocarbons, such as paraffin wax, microcrystalline wax, liquid paraffin wax, low molecular weight polyethylene, oxidized polyethylene wax; fatty acids such as stearic acid, hydroxystearic acid; fatty acid esters such as fatty acid lower alcohol esters, fatty acid polyol esters, natural waxes, ester waxes and saponified waxes; aliphatic amides, such as stearamide or stearamide, oleamide or oleamide, erucamide, N' -ethylene bis stearamide; fatty alcohols and polyols, such as stearyl alcohol, cetyl alcohol, pentaerythritol; metal soaps such as lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate, etc.; among them, the lubricant is preferably paraffin wax, liquid paraffin wax, stearic acid, low molecular weight polyethylene. The amount of the lubricant used is not particularly limited, but is generally 0.5 to 1% by weight.
The release agent in the auxiliary agent can make the polymer sample easy to release, and has smooth and clean surface, and the auxiliary agent comprises any one or more of the following release agents: paraffin, soaps, dimethyl silicone oil, ethyl silicone oil, methylphenyl silicone oil, castor oil, waste engine oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicone rubber, polyvinyl alcohol and the like; among them, the release agent is preferably dimethyl silicone oil or polyethylene glycol. The amount of the release agent to be used is not particularly limited, but is generally 0.5 to 2% by weight.
The plasticizer in the auxiliary agent can increase the plasticity of a polymer sample, so that the hardness, modulus, softening temperature and brittle temperature of the polymer are reduced, and the elongation, flexibility and flexibility of the polymer are improved, and the auxiliary agent comprises any one or more of the following plasticizers: phthalic acid esters: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, diheptyl phthalate, diisodecyl phthalate, diisononyl phthalate, butylbenzyl phthalate, butyl glycolate phthalate, dicyclohexyl phthalate, bis (tridecyl) phthalate, bis (2-ethyl) hexyl terephthalate; phosphoric acid esters such as tricresyl phosphate, diphenyl-2-ethyl hexyl phosphate; fatty acid esters such as di (2-ethyl) hexyl adipate, di (2-ethyl) hexyl sebacate; epoxy compounds, such as epoxy glycerides, epoxy fatty acid monoesters, epoxy tetrahydrophthalic acid esters, epoxy soybean oil, epoxy stearic acid (2-ethyl) hexyl ester, epoxy soybean oleic acid 2-ethylhexyl ester, 4, 5-epoxy tetrahydrophthalic acid di (2-ethyl) hexyl ester, methyl chrysene acetyl ricinoleate, and dihydric alcohol esters, such as C5-9 acid ethylene glycol ester, C5-9 acid triethylene glycol ester; chlorine-containing compounds such as greening paraffin, chlorinated fatty acid ester; polyesters such as 1, 2-propanediol ethanedioic acid polyesters, 1, 2-propanediol sebacic acid polyesters; phenyl petroleum sulfonate, trimellitate, citrate, pentaerythritol, dipentaerythritol, and the like; among them, the plasticizer is preferably dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), or tricresyl phosphate (TCP). The amount of the plasticizer to be used is not particularly limited, but is generally 5 to 20% by weight.
The thickening agent in the additive can endow the polymer mixed solution with good thixotropy and proper consistency, and is generally used in the production and semi-finished product storage processes of the invention, and the thickening agent comprises any one or more of the following thickening agents: low molecular substances such as fatty acid salts, fatty alcohol-polyoxyethylene ether sulfates, alkyldimethylamine oxides, fatty acid monoethanolamides, fatty acid diethanolamides, fatty acid isopropylamides, sorbitan tricarboxylates, glycerol trioleate, cocamidopropyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazoline, titanate coupling agents; high molecular substances such as bentonite, artificial hectorite, fine silica, colloidal aluminum, plant polysaccharides, microbial polysaccharides, animal proteins, celluloses, starches, alginic acids, polymethacrylates, methacrylic acid copolymers, maleic anhydride copolymers, crotonic acid copolymers, polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, polyether, polyvinylmethylether urethane polymers, etc.; among them, the thickener is preferably hydroxyethyl cellulose, coconut oil diethanolamide, or acrylic acid-methacrylic acid copolymer. The amount of the thickener to be used is not particularly limited, and is generally 0.1 to 1.5% by weight.
The thixotropic agent in the auxiliary agent is added into a hybrid dynamic polymer system to increase the thixotropy of the polymer system. Including but not limited to any one or any of the following: fumed silica, hydrogenated castor oil, bentonite, silicic anhydride, silicic acid derivatives, urea derivatives, and the like. The amount of the thixotropic agent used is not particularly limited, and is generally 0.5 to 2% by weight.
The leveling agent in the auxiliary agent can ensure the smoothness and the evenness of a polymer coating, improve the surface quality of the coating and improve the decoration, and the auxiliary agent comprises any one or more of the following leveling agents: polydimethylsiloxane, polymethylphenylsiloxane, cellulose acetate butyrate, polyacrylates, silicone resins, and the like; among them, polydimethylsiloxane and polyacrylate are preferable as the leveling agent. The amount of the leveling agent to be used is not particularly limited, but is usually 0.5 to 1.5% by weight.
The colorant in the additive can make the polymer product present the required color and increase the surface color, and the colorant comprises any one or more of the following colorants: inorganic pigments such as titanium white, chrome yellow, cadmium red, iron red, molybdenum chrome red, ultramarine, chrome green, carbon black; organic pigments, such as lithol rubine BK, lake red C, perylene red, galyl R red, phthalocyanine red, permanent carmine HF3C, plastic scarlet R and cromo red BR, permanent orange HL, fast yellow G, sparkle plastic yellow R, permanent yellow 3G, permanent yellow H2G, phthalocyanine blue B, phthalocyanine green, plastic violet RL, aniline black; organic dyes such as thioindigo red, vat yellow 4GF, Vaseline blue RSN, basic rose essence, oil-soluble yellow, etc.; the colorant is selected according to the color requirement of the sample, and is not particularly limited. The amount of the colorant to be used is not particularly limited, but is generally 0.3 to 0.8% by weight.
The fluorescent whitening agent in the auxiliary agent can enable the dyed materials to obtain the fluorite-like flash luminescence effect, and the fluorescent whitening agent comprises any one or more of the following fluorescent whitening agents: stilbene type, coumarin type, pyrazoline type, benzoxazine type, phthalimide type, and the like; among the fluorescent whitening agents, sodium diphenylethylene disulfonate (fluorescent whitening agent CBS), 4-bis (5-methyl-2-benzoxazolyl) stilbene (fluorescent whitening agent KSN), 2- (4, 4' -distyryl) bisbenzoxazole (fluorescent whitening agent OB-1) are preferable. The amount of the fluorescent whitening agent to be used is not particularly limited, but is generally 0.002 to 0.03% by weight.
The matting agent in the auxiliary agent can diffuse and reflect incident light to generate low-gloss matte and matte appearance when the incident light reaches the surface of the polymer, and the matting agent comprises any one or more of the following matting agents: settling barium sulfate, silicon dioxide, hydrous gypsum powder, talcum powder, titanium dioxide, polymethyl urea resin and the like; among them, the matting agent is preferably silica. The amount of the matting agent to be used is not particularly limited, but is generally 2 to 5% by weight.
The antistatic agent in the additive can guide or eliminate harmful charges accumulated in polymer samples, so that the harmful charges do not cause inconvenience or harm to production and life, and the antistatic agent comprises any one or more of anionic antistatic agents such as alkyl sulfonate, sodium P-nonylphenoxypropane sulfonate, alkyl phosphate diethanol amine salt, alkylphenol polyoxyethylene ether sulfonate triethanolamine, potassium P-nonylphenyl ether sulfonate, alkyl polyoxyethylene ether sulfonate triethanolamine, phosphate derivatives, phosphate, polyethylene oxide alkyl ether phosphate, alkyl bis [ di (2-hydroxyethyl amine) ] phosphate, phosphate derivatives, fatty amine sulfonate, sodium butyrate sulfonate, cationic antistatic agents such as fatty ammonium hydrochloride, lauryl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, N, N-cetyl-ethylmorpholine ethyl sulfate, stearamidopropyl (2-hydroxyethyl) dimethyl ammonium nitrate, alkyl hydroxyethyl dimethyl ammonium perchlorate, 2-alkyl-3, 3-diethoxyethyl imidazoline perchlorate, 2-heptadecyl-3-hydroxyethyl-4-carboxyethyl imidazoline, N, N-bis (3-hydroxyethyl) dimethyl ammonium nitrate, N-ethylene glycol alkyl-polyoxyethylene-3-polyoxyethylene-ether sulfate, polyoxyethylene-2-polyoxyethylene.
The dehydrating agent in the auxiliary agent can remove moisture in a system, and the dehydrating agent comprises any one or more of the following components: oxazolidine compounds (e.g., 3-ethyl-2-methyl-2- (3-methylbutyl) -1, 3-oxazolidine), p-toluenesulfonyl isocyanate, triethyl orthoformate, vinylsilane, calcium oxide, and the like. The amount of the dehydrating solvent to be used is not particularly limited, but is usually 0.1 to 2% by weight.
The sterilization mildew preventive in the auxiliary agent can inhibit the growth of bacteria, keep the neat appearance of the product and prolong the service life; or protect the user and improve the health of the user, such as reducing beriberi and the like. It includes organic and inorganic substances, including but not limited to any one or more of the following: isothiazolinone derivatives such as 5-chloro-2-methyl-4-isothiazolin-3-one, N-butyl-1, 2-benzisothiazolin-3-one, octylisothiazolinone, 2,4, 4-trichloro-2-hydroxy-diphenyl ether, 2- (4-thiazolyl) benzimidazole, 8-hydroxyquinolinecarboxylic acid copper or bis (8-hydroxyquinolinyl) copper; organotin compounds such as tributyltin fumarate, tributyltin acetate, bis (tributyltin) sulfide, bis (tributyltin) oxide; n, N-dimethyl-N' -phenyl (fluorodichloromethylthio) sulfonamide; inorganic compound or compound, such as nano silver, nano titanium dioxide, nano silicon dioxide, nano zinc oxide, superfine copper powder, inorganic antibacterial agent YY-Z50, XT inorganic antibacterial agent, and composite antibacterial agent KHFS-ZN. The amount of the fungicidal agent to be used is not particularly limited, but is generally 0.5 to 2% by weight.
The foaming agent in the auxiliary agent can enable a polymer sample to be foamed into pores, so that a light and heat-insulating polymer material is obtained, and the foaming agent comprises any one or more of the following foaming agents: physical blowing agents such as carbon dioxide, nitrogen, argon, methane, ethane, propane, butane, isobutane, pentane, neopentane, hexane, isopentane, heptane, isoheptane, acetone, benzene, toluene, methyl ether, diethyl ether, petroleum ether, methyl chloride, dichloromethane, dichloroethylene, dichlorodifluoromethane, chlorotrifluoromethane, hydrochlorofluorocarbon-22, hydrochlorofluorocarbon-142 b, hydrofluorocarbon-134 a, hydrofluorocarbon-152 a, chlorofluorocarbon-11, chlorofluorocarbon-12, chlorofluorocarbon-114; inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium ammonium carbonate, azide compounds, borohydride compounds, and the like; organic blowing agents, such as N, N '-dinitrosopentamethylenetetramine, N' -dimethyl-N, N '-dinitrosoterephthalamide, azodicarbonamide, barium azodicarbonate, diisopropyl azodicarbonate, potassium azoformamide formate, azodiisobutyronitrile, 4' -oxybis-benzenesulfonyl hydrazide, 3 '-disulfonyl hydrazide diphenylsulfone, 1, 3-benzenedihuanyl hydrazide, benzenesulfonyl hydrazide, trihydrazinyltriazine, p-toluenesulfonyl semicarbazide, biphenyl-4, 4' -disulfonyl azide, diazoaminobenzene; physical microsphere/particle blowing agents such as expandable microspheres from Acksonobel, et al. Among them, the foaming agent is preferably environmentally friendly and harmless carbon dioxide, nitrogen, argon, sodium bicarbonate, ammonium carbonate, azodicarbonamide (foaming agent AC), N ' -dinitropentamethylenetetramine (foaming agent H), N ' -dimethyl-N, N ' -dinitrosoterephthalamide (foaming agent NTA), or physical microsphere foaming agent. The amount of the blowing agent to be used is not particularly limited, but is usually 0.1 to 30% by weight.
The auxiliary foaming agent in the auxiliary agent includes, but is not limited to, a foaming promoter, a foaming inhibitor, a foam stabilizer, and the like. The foaming promoter includes, but is not limited to, any one or any several of the following: urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, lead stearate, cadmium stearate, zinc oxide, ZB-530, KZ-110 and MS-1; the foaming inhibitor comprises any one or more of the following components: maleic acid, fumaric acid, stearoyl chloride, phthaloyl chloride, maleic anhydride, phthalic anhydride, hydroquinone, naphthalenediol, aliphatic amines, amides, oximes, isocyanates, thiols, thiophenols, thioureas, sulfides, sulfones, cyclohexanone, acetylacetone, hexachlorocyclopentadiene, dibutyltin maleate, etc.; the foam stabilizer comprises any one or more of the following components in percentage by weight: : silicone oils, sulfonated fatty alcohols, sulfonated fatty acids, sodium lauryl sulfate, dodecyl dimethyl amine oxide, alkylolamides, polyethylene oxides, alkylaryl polyvinyl alcohol oxides, tridecyl ethers, polyethylene oxide sorbitan glyceryl laurate, block copolymers of silicone-ethylene oxides, and the like. The amount of the co-blowing agent to be used is not particularly limited, but is usually 0.05 to 10% by weight.
The nucleating agent in the additive can accelerate the crystallization rate, increase the crystallization density and promote the grain size to be micronized by changing the crystallization behavior of the polymer, so as to achieve the purposes of shortening the molding period of the material and improving the physical and mechanical properties of the product, such as transparency, surface gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance and the like, and the nucleating agent comprises any one or more of the following nucleating agents: benzoic acid, adipic acid, sodium benzoate, talcum powder, sodium p-phenolsulfonate, silicon dioxide, dibenzylidene sorbitol and derivatives thereof, ethylene propylene rubber, ethylene propylene diene monomer and the like; among them, the nucleating agent is preferably silica, dibenzylidene sorbitol (DBS), ethylene propylene diene monomer. The amount of the nucleating agent used is not particularly limited, but is generally 0.1 to 1% by weight.
The rheological agent in the auxiliary agent can ensure that the polymer has good brushing property and proper coating thickness in the coating process, prevents the solid particles from settling during storage, and can improve the redispersibility, and the rheological agent comprises any one or more of the following rheological agents: inorganic species such as barium sulfate, zinc oxide, alkaline earth metal oxides, calcium carbonate, lithium chloride, sodium sulfate, magnesium silicate, fumed silica, water glass, colloidal silica; organometallic compounds such as aluminum stearate, aluminum alkoxides, titanium chelates, aluminum chelates; organic compounds such as organobentonite, hydrogenated castor oil/amide wax, isocyanate derivatives, acrylic emulsion, acrylic copolymer, polyethylene wax, cellulose ester, etc.; among them, the rheological agent is preferably organic bentonite, polyethylene wax, hydrophobically modified alkaline expandable emulsion (HASE), and alkaline expandable emulsion (ASE). The amount of the rheology agent used is not particularly limited, but is generally 0.1 to 1% by weight.
The filler mainly plays a role in reducing the shrinkage rate of a molded part, improving the dimensional stability, surface smoothness, flatness or dullness of the product and the like in a polymer sample ①, adjusting the viscosity of a material ②, meeting different performance requirements such as improving the impact strength, compression strength, hardness, rigidity and modulus of the material, improving the wear resistance, heat deformation temperature, electrical conductivity and thermal conductivity and the like in ③, improving the coloring effect of a pigment ④, endowing the material with light stability and chemical corrosion resistance in ⑤, playing a role in increasing the volume and reducing the cost and improving the market competitiveness of the product ⑥.
The filler is selected from any one or any several of the following fillers: inorganic non-metal filler, metal filler and organic filler.
The inorganic non-metal filler includes, but is not limited to, any one or more of the following: calcium carbonate, china clay, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos fiber, orthoclase, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene oxide, fullerene, carbon nano tube, molybdenum disulfide, slag, flue dust, wood powder and shell powder, diatomite, red mud, wollastonite, silicon aluminum black, aluminum hydroxide, magnesium hydroxide, fly ash, oil shale powder, expanded perlite powder, conductive carbon black, vermiculite, iron mud, white mud, alkali mud, boron mud, glass bead, resin bead, glass powder, cement, glass fiber, carbon fiber, quartz fiber, carbon core boron fiber, titanium diboride fiber, calcium titanate fiber, carbon silicon fiber, ceramic fiber, whisker and the like.
The metal filler includes, but is not limited to, any one or any several of the following: metal powders, fibers including but not limited to powders, fibers of copper, silver, nickel, iron, gold, and the like, and alloys thereof; nano metal particles including, but not limited to, nano gold particles, nano silver particles, nano palladium particles, nano iron particles, nano cobalt particles, nano nickel particles, nano Fe3O4Particulate, nano gamma-Fe2O3Particulate, nano MgFe2O4Particulate, nano-MnFe2O4Granular, nano CoFe2O4Granular, nano-CoPt3Particles, nano FePt particles, nano FePd particles, nickel-iron bimetal magnetic nanoparticles, other nano metal particles capable of heating under the infrared or ultraviolet or electromagnetic action and the like; liquid metals including, but not limited to, mercury, gallium indium liquid alloys, gallium indium tin liquid alloys, other gallium based liquid metal alloys; metal organic compound molecules or crystals and other substances which can generate heat under the action of infrared or ultraviolet or electromagnetism, and the like.
The organic filler includes, but is not limited to, ① natural organic fillers such as natural rubber, cotton linters, hemp, jute, flax, asbestos, cellulose acetate, lignin, starch, wood flour, etc., ② synthetic resin fillers such as acrylonitrile-acrylate-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, cellulose acetate, polychlorotrifluoroethylene, chlorinated polyethylene, chlorinated polyvinyl chloride, epoxy resin, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, high density polyethylene, high impact polystyrene, low density polyethylene, medium density polyethylene, melamine-formaldehyde resin, polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polyarylsulfone, polybenzimidazole, polybutylene terephthalate, polycarbonate, polydimethylsiloxane, polyethylene glycol, polyester, polysulfone, polyethersulfone, polyethylene terephthalate, phenolic resin, tetrafluoroethylene-perfluoropropane copolymer, polyimide, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride, polypropylene, styrene-butadiene, sulfone, polystyrene, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl chloride-polyvinyl butyral, polyvinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinyl chloride-polyvinyl acetal, polyvinyl chloride-polyvinyl butyral, polyvinyl chloride-ethylene-vinyl acetate copolymer, polyvinyl butyral, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride-ethylene-vinyl acetate copolymer, polyvinyl butyral, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate fiber, polyvinyl alcohol, polyvinyl butyral, polyvinyl alcohol, polyvinyl acetate fiber, polyvinyl butyral, polyvinyl alcohol, polyvinyl acetate fiber, polyvinyl butyral, polyvinyl alcohol, polyvinyl butyral, polyvinyl alcohol, polyvinyl acetate fiber, polyvinyl alcohol, polyvinyl butyral, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate fiber, polyvinyl butyral, polyvinyl alcohol.
Among them, the type of the filler is not limited, and is mainly determined according to the required material properties, and calcium carbonate, barium sulfate, talc, carbon black, graphene, (hollow) glass beads, foamed microspheres, foamable particles, glass fibers, carbon fibers, metal powder, natural rubber, protein, resin beads are preferable, and the amount of the filler used is not particularly limited, and is generally 1 to 30 wt%.
In the preparation process of the dynamic polymer material, the auxiliary agent is preferably selected from an antioxidant, a light stabilizer, a heat stabilizer, a toughening agent, a plasticizer, a foaming agent and a flame retardant. The filler is preferably calcium carbonate, barium sulfate, talcum powder, carbon black, glass beads, graphene, glass fiber and carbon fiber.
Wherein, the swelling agent can include but is not limited to water, organic solvent, ionic liquid, oligomer and plasticizer. The oligomers can also be regarded as plasticizers.
The organic solvent in the swelling agent is selected from any one or any several of the following by way of example and not limitation: hydrocarbons (e.g., cyclohexane, heptane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, tetrachloromethane), aromatic hydrocarbons (e.g., toluene, xylene), ketones (e.g., acetone, methyl ethyl ketone), ethers (e.g., diethyl ether, tetrahydrofuran, dioxane), esters (e.g., ethyl acetate, butyl acetate), glycol ether esters (e.g., ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate), Dimethylformamide (DMF), N-methylpyrrolidone (NMP), and the like.
The ionic liquid in the swelling agent is generally composed of an organic cation and an inorganic anion, and the cation is selected from, by way of example, but not limited to, alkyl quaternary ammonium ions, alkyl quaternary phosphine ions, 1, 3-dialkyl-substituted imidazolium ions, N-alkyl-substituted pyridinium ions, and the like; the anion is selected from the group including but not limited to halogen, tetrafluoroborate, hexafluorophosphate, and also CF3SO3 -、(CF3SO2)2N-、C3F7COO-、C4F9SO3 -、CF3COO-、(CF3SO2)3C-、(C2F5SO2)3C-、(C2F5SO2)2N-、SbF6 -、AsF6 -And the like. In the ionic liquid used in the present invention, the cation is preferably an imidazolium cation, and the anion is preferably a hexafluorophosphate ion or a tetrafluoroborate ion.
The oligomer in the swelling agent is selected from any one or more of the following substances by way of example and not limitation: polyethylene glycol oligomer, polyvinyl alcohol oligomer, polyvinyl acetate oligomer, poly (n-butyl acrylate) oligomer, liquid paraffin and the like.
The plasticizer in the swelling agent is selected from any one or any several of the following by way of example and not limitation: phthalic acid esters: dibutyl phthalate (DBP), o-phthalic acidDioctyl phthalate (DOP), diisooctyl phthalate (DIOP), diheptyl phthalate, diisodecyl phthalate (DIDP), diisononyl phthalate (DINP), butyl benzyl phthalate, butyl glycolate, dicyclohexyl phthalate, bis (tridecyl) phthalate, bis (2-ethyl) hexyl terephthalate; phosphoric acid esters such as tricresyl phosphate (TCP), diphenyl-2-ethyl hexyl phosphate; fatty acid esters such as di (2-ethyl) hexyl adipate, di (2-ethyl) hexyl sebacate; epoxy compounds, e.g. epoxyglycerides, epoxyfatty acid monoesters, epoxytetrahydrophthalates, epoxidized soybean oil, epoxyhexyl (2-ethyl) stearate, epoxy2-ethylhexyl soyate, di (2-ethyl) hexyl 4, 5-epoxytetrahydrophthalate, methyl chrysene acetylricinoleate, glycols, e.g. C5～9Acid ethylene glycol ester, C5～9Triethylene glycol diacetate; chlorine-containing compounds such as greening paraffin, chlorinated fatty acid ester; polyesters such as 1, 2-propanediol ethanedioic acid polyesters, 1, 2-propanediol sebacic acid polyesters; phenyl petroleum sulfonate, trimellitate, citrate, pentaerythritol, dipentaerythritol, and the like. Among them, DBP, DOP, DIOP, DIDP, DINP, TCP, epoxidized soybean oil are preferable as the plasticizer. The epoxidized soybean oil is an environment-friendly plastic plasticizer with excellent performance, is prepared by performing epoxidation reaction on refined soybean oil and peroxide, is resistant to volatilization, difficult to migrate and difficult to dissipate in a polymer product, and is very beneficial to keeping the light and heat stability of the product and prolonging the service life. Epoxidized soybean oil is extremely toxic and has been approved by many countries for use in food and pharmaceutical packaging materials, and is the only epoxy plasticizer approved by the U.S. food and drug administration for use in food packaging materials, and is therefore more preferred.
In the preparation process of the dynamic polymer, the amount of each component raw material of the dynamic polymer is not particularly limited, and can be adjusted by those skilled in the art according to the actual preparation situation and the target polymer property.
The method for producing the composition of the present invention is not particularly limited, and for example, the additive may be blended with the dynamic polymer as necessary by a roll, a kneader, an extruder, a universal mixer, or the like, and the mixture may be subjected to a subsequent operation such as foaming.
The dynamic polymer of the invention contains block polymer molecules with hard blocks and soft blocks, the hard blocks and the soft blocks can form physical phase separation, and the phase formed by the hard blocks can be used as physical crosslinking/polymerization, thereby being beneficial to processing, molding and recycling of materials. The block polymer molecule also has dynamic supermolecule effect, and when the dynamic supermolecule effect forms interchain cross-linking, the obtained dynamic polymer has good self-repairing performance. Meanwhile, due to the existence of dynamic supermolecule effect, the toughness of the material can be increased. Through proper component selection and formula design, materials with shape memory and self-repairing functions and polymer materials with excellent toughness can be prepared, such as shape memory splints, force sensors, self-repairing coatings, self-repairing plugging glue and conductive glue, self-repairing sealing elements and the like, and the composite material has wide application in the fields of biomedical materials, military, aerospace, energy, buildings and the like. In addition, when the dynamic polymer of the present invention contains at least two kinds of supramolecules, the obtained polymer material can have a multi-property with rich layers. Due to the self-repairability and the recyclability of the material, the use cost of the material can be greatly reduced, and the utilization rate of resources and energy conservation and emission reduction are facilitated to be improved.
The dynamic polymer materials of the present invention are further described below in conjunction with certain embodiments. The specific examples are intended to illustrate the present invention in further detail, and are not intended to limit the scope of the present invention.
Example 1
The modified SBS containing the host group and the hydrogen bond group simultaneously is obtained by reacting commercially available styrene-butadiene-styrene triblock copolymer (SBS), sulfydryl β -cyclodextrin, 2- (tert-butoxycarbonyl-amino) ethanethiol and photoinitiator Benzil Dimethyl Ketal (BDK) in tetrahydrofuran, the molar ratio of alkenyl to sulfydryl β -cyclodextrin, 2- (tert-butoxycarbonyl-amino) ethanethiol and BDK in a polybutadiene chain segment is kept to be about 50:5:5:1, the modified SBS containing the host group and the hydrogen bond group simultaneously is obtained by reacting commercially available SBS, 1-mercaptoadamantane, 2- (tert-butoxycarbonyl-amino) ethanethiol and the photoinitiator BDK in tetrahydrofuran, the molar ratio of alkenyl to 1-mercaptoadamantane, 2- (tert-butoxycarbonyl-amino) ethanethiol and BDK is kept to be about 50:5:5:1, the modified SBS containing the object group and the hydrogen bond group simultaneously is obtained by mixing the modified SBS containing the object group, 2- (tert-butoxycarbonyl-amino) ethanethiol and the photoinitiator in a foaming machine, the modified SBS containing the object group and the polystyrene-butadiene-styrene triblock copolymer is obtained by extruding, the modified SBS, the foamed product is obtained by mixing the foamed product with the foaming agent, the polystyrene-butadiene-styrene triblock copolymer, the foaming agent, the foamed product is obtained by mixing the foamed product by mixing the foaming agent by stirring, the stirring.
Example 2
2 molar equivalents of 1,4,5, 8-naphthalenetetracarboxylic anhydride were dissolved in aqueous KOH (both concentrations 5g/L) and the pH was adjusted to 6.3 using phosphoric acid. Adding 1 molar equivalent of 2,2' - (ethylene dioxy) bis (ethylamine) and stirring for 20 minutes, adding phosphoric acid to adjust the pH value to 6.3, and reacting at 110 ℃ for 24 hours to obtain the tetranaphthalimide compound 2 a. Under the protection of inert gas, 5 molar equivalents of the compound 2a and 6 molar equivalents of polyisobutylene (with the average molecular weight of about 1000Da) with both end amino terminated are refluxed in a mixed solution of DMSO and toluene for 20 hours to obtain modified polyisobutylene with the terminal amino terminated frameworks containing naphthalene tetracarbodiimide groups. And (2) initiating the polymerization of styrene at 90-100 ℃ by using Benzoyl Peroxide (BPO) as an initiator and mercaptoacetic acid as a chain transfer agent, and keeping the molar ratio of the initiator to the monomer to the chain transfer agent to be 1:30:1 to obtain the polystyrene with the end capped by the single-end carboxyl. Carrying out acylation reaction on the modified polyisobutylene obtained by 1 molar equivalent and the polystyrene terminated by 2 molar equivalents of single-end carboxyl to obtain the polystyrene-modified polyisobutylene-polystyrene three-stage copolymer. Carrying out acylation reaction on 2 molar equivalents of 1-pyrenebutyric acid and 1 molar equivalent of polyisobutene (average molecular weight is about 2000Da) with two end amino end terminations in the presence of a condensing agent 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline to obtain polyisobutene with two end terminations by pyrenyl. And (2) blending the obtained three-stage copolymer with polyisobutylene with two ends capped by pyrenyl, taking the blending as 100 parts by mass, keeping the molar ratio of naphthalene tetracarbodiimide group to pyrenyl as 2:1, and performing compression molding to obtain the dynamic polymer. The material has good toughness and strength, and can be used for preparing extruded profiles, plates, blown or cast films, sheets, wires and cable sheaths.
Example 3
Reacting pentafluoroiodobenzene with excessive 1, 4-butanediol at 80 ℃ in the presence of cesium carbonate to obtain the compound 4- (4-iodo-2, 3,5, 6-tetrafluorophenoxy) butyl-1-ol. And reacting the obtained compound with acryloyl chloride under the catalysis of triethylamine to obtain the acrylate monomer 3a with the halogenated phenyl. The acrylic acid and 6-hydroxymethyl quinoline with equal molar equivalent react under the catalysis of DCC and DMAP to obtain the acrylate monomer 3b containing ligand groups.
Firstly, dissolving 1 molar equivalent of AIBN, 1 molar equivalent of cumyl dithiobenzoate (2-phenylpropan-2-yl dithiobenzoate) and 30 molar equivalents of sodium p-styrenesulfonate in tetrahydrofuran, sealing, keeping anhydrous oxygen-free low pressure, carrying out photoinitiated polymerization at room temperature under the irradiation of an ultraviolet lamp, adding a mixed solution containing 50 molar equivalents of n-butyl acrylate, 10 molar equivalents of 3a and 40 molar equivalents of 3b after the added monomers are completely reacted, continuing the reaction, obtaining a modified polyacrylate-sodium polystyrene sulfonate two-stage polymer with a polyacrylate end as dithiobenzoate and containing a side hydrogen bond group and a side ligand group, adding 20 molar equivalents of tributylphosphine and 50 molar equivalents of acrylic acid in tetrahydrofuran, adding 20 molar equivalents of sodium borohydride, reacting for 20 hours at room temperature, precipitating the product in methanol, obtaining a polyacrylate-carboxyl-terminated polystyrene-polyacrylate copolymer, adding 70 molar equivalents of tributylphosphine and 70 molar equivalents of acrylic acid in tetrahydrofuran, adding a proper amount of polystyrene-sodium borohydride, obtaining a polystyrene-polyacrylate-polyoxyethylene-.
Example 4
Dropping 1 molar equivalent of delta-valerolactone into a tetrahydrofuran solution containing 1 molar equivalent of lithium diisopropylamide at-78 ℃, fully and uniformly stirring, adding a toluene solution containing 1.1 molar equivalent of 3-bromopropyne, reacting at-40 ℃, after the reaction, carrying out short-range distillation on a crude product at 140 ℃ to obtain a lactone monomer 4a, sequentially adding bipyridyl, cuprous bromide, α -bromopropionic acid ethyl ester and styrene into a reaction container under the anhydrous and oxygen-free conditions, keeping the molar ratio of the four components at 1:1:1:20, reacting at 110 ℃, adding tetrahydrofuran into the obtained polystyrene for dissolution, reacting for 6 hours at room temperature by taking lithium aluminum hydride as a reducing agent to obtain hydroxyl-terminated polystyrene 4b, and reacting the obtained polystyrene 4b with 50 molar equivalents of lactone monomer 4a and 50 molar equivalent of epsilon-caprolactone under the catalysis of stannous octoate to obtain a two-stage type polystyrene-modified polycaprolactone 4 c.
Under the protection of inert gas, 1 mol equivalent of styrene-maleic anhydride copolymer and 6 mol equivalents of the obtained two-stage copolymer 4c are dissolved in xylene, catalyst sodium p-toluenesulfonate is added under stirring, and stirring reaction is carried out at 105 ℃ to obtain the styrene-maleic anhydride copolymer grafted (modified polyester-polystyrene) multi-stage copolymer. Acylation of the compound 4d with 2-azidoethylamine affords the compound 4e bearing an azido group at one terminus. Dissolving methyl bromide in tetrahydrofuran, adding excessive sodium azide, and reacting to obtain a compound, namely methyl azide. Dissolving the obtained multistage copolymer, methyl azide and a compound 4e in tetrahydrofuran, keeping the molar ratio of alkynyl to the methyl azide and the compound 4e to be 5:3:2, and reacting at 35 ℃ under the catalysis of cuprous iodide and pyridine to obtain the polyester stage multistage copolymer containing side triazolyl and side amino acid groups. And deprotecting the obtained copolymer in trifluoroacetic acid, dissolving the product in a solution containing a proper amount of copper chloride, fully stirring, and removing the solvent to obtain the dynamic polymer. The dynamic polymer has good toughness and self-repairing property, has multiple transition temperatures, and can be used as a material with self-repairing and shape memory functions.
Example 5
Under the protection of nitrogen, 10 molar equivalents of ethylene glycol monoallyl ether (average molecular weight is about 500Da) and 1 molar equivalent of potassium methoxide are blended, 70 molar equivalents of epoxy propanol is slowly dripped at 95 ℃ to obtain an olefin monomer 5a with a branched structure and a hydroxyl end group, under the protection of nitrogen, the olefin monomer 5a with the branched structure and the hydroxyl end group is reacted with ethyl isocyanate with the same molar equivalent of the hydroxyl end group in dichloromethane under the catalysis of DBTDL to obtain an olefin monomer 5b, the olefin monomer 5b is equimolar blended with 1-mercaptoglycerol, 1 wt% of photoinitiator 2, 2-dimethoxy-2-phenylacetophenone is added, under the catalysis of DCC and DMAP, a diol compound 5c is obtained, under the action of a 300W ultraviolet lamp for 30 minutes, an excessive 1 molar equivalent of the obtained diol 5c and 2 molar equivalents of polycaprolactone terminated with two carboxyl ends (average molecular weight is about 300Da), 1, 4-butanediol is added to obtain polycaprolactone containing hydroxyl end groups, 1 molar equivalent of 3, 9-perylene two end equivalents of polycaprolactone terminated with 2, polycaprolactone terminated with two carboxyl end groups of two equivalents (average molecular weight is catalyzed by about 300Da), the molecular weight of the polycaprolactone is filtered, the polycaprolactone-terminated polycaprolactone terminated by the two ends, the hydrolysis of triethylamine is catalyzed by the hydrolysis of triethylamine, the hydrolysis of the hydrolysis catalyst, the hydrolysis of.
100 parts by mass of polycaprolactone containing hydrogen bond groups and terminated by hydroxyl groups at two ends, 100 parts by mass of modified polyester containing a condensed ring framework and hydroxyl groups at two ends, 2 parts by mass of 1, 4-butanediol, 2 parts by mass of DBTDL, 1 part by mass of organic silicone oil, 50 parts by mass of montmorillonite, 60 parts by mass of dichloromethane and 35 parts by mass of water are fully blended at 35 ℃, and the blend is marked as component A. 200 parts by mass of toluene diisocyanate and 50 parts by mass of the compound 5d are fully blended and stirred at 90 ℃ for 40 hours, and then the temperature is reduced to 35 ℃, and the component B is marked. Mixing the component A and the component B according to the mass ratio of 1.2:1, quickly stirring until bubbles are generated, then quickly injecting into a mould, reacting for 30 minutes at room temperature, and then preserving the temperature for 2 hours at 120 ℃ to obtain the rigid polyurethane-based foam material. The product has excellent toughness and good self-repairing property, and can be used for manufacturing heat-insulating materials and insulating materials.
Example 6
Under anhydrous conditions, a 2L reactor was charged with ethylene and maintained at 1 atmosphere, with 14% by volume of toluene and 0.95% by volume of butadiene in toluene (9 wt%) added to the reactor. Adding catalyst 6a, Al at 40 deg.CiBu3And [ Ph3C][B(C6F5)4]20 ml of the catalyst solution, and at the same time, 6 ml of a 6% by volume butadiene toluene solution (9 wt%) was dropped into the reactor at a rate of 6 ml per minute. After the butadiene solution was completely added dropwise, 20 ml of acidified methanol was rapidly added, and the product was precipitated in ethanol to obtain an ethylene-butadiene random copolymer. The resulting random copolymer was reacted with 2-mercaptoethanol and photoinitiator BDK in tetrahydrofuran, maintaining the molar ratio of alkenyl groups to 2-mercaptoethanol and BDK at about 50:5:1, yielding an ethylene-butadiene random copolymer with pendant hydroxyl groups.
Dissolving 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one and 4-nitrochlorobenzene in DMF, and catalyzing by potassium carbonate to obtain 1, 2-dihydro-2- (4-nitrophenyl) -4- [4- (4-nitrophenoxy) -phenyl ] -naphthyridin-1-one. The obtained compound reacts with hydrazine monohydrate under the catalysis of platinum-carbon to obtain 1, 2-dihydro-2- (4-aminophenyl) -4- [4- (4-aminophenoxy) -phenyl ] -naphthyridine-1-ketone which is one of monomers for synthesizing the polyarylamine. Fully mixing 5 molar equivalents of the obtained polyarylamine monomer with 6 molar equivalents of terephthalic acid under anhydrous and anaerobic conditions, taking triphenyl phosphite and pyridine as dehydrating agents, taking N-methyl pyrrolidone and calcium chloride as media, and reacting for 3 hours at 100 ℃. And settling, washing and refining the reaction solution to obtain the carboxyl-terminated polyarylamine. Reacting the ethylene-butadiene random copolymer with lateral hydroxyl with a certain amount of polyarylamine and 4-carboxyl oxazolidinone under the catalysis of DCC and DMAP, and keeping the molar ratio of the hydroxyl, the polyarylamine and the 4-carboxyl oxazolidinone to be 10:1:4 to obtain the ethylene-butadiene random copolymer grafted polyarylamine. Reacting 1 molar equivalent of heptafluoro-2-naphthol with 10 molar equivalents of oxalyl chloride under the catalysis of triethylamine to obtain fluoronaphthalene with one end being acyl chloride group. Reacting the obtained graft copolymer with the obtained fluoronaphthalene with one end of acyl chloride group and 4-phenylbutyryl chloride under the catalysis of triethylamine, and keeping the molar ratio of hydroxyl, the fluoronaphthalene with one end of acyl chloride group and the 4-phenylbutyryl chloride to be 2:1:1 to obtain the dynamic polymer. The product has wide working temperature range, and is particularly suitable for products with large working temperature range, such as components in aerospace vehicles.
Example 7
20 molar equivalents of 2, 2-bis (allyloxymethyl) -1-butanol and 10 molar equivalents of polyethylene glycol terminated with both terminal alkenyl groups (average molecular weight of about 500) were subjected to diene metathesis polymerization at 80 ℃ in the presence of 0.3 molar equivalent of Hoveyda-Grubbs' generation catalyst to obtain a modified polyether containing a hydroxyl skeleton as a pendant group and double bonds. And reacting the obtained polyether with a certain amount of isoxazole-5-carboxylic acid, and keeping the molar ratio of hydroxyl to isoxazole-5-carboxylic acid in the polyether to be 3:2 to obtain the modified polyether with the pendant group containing hydroxyl and the isoxazolyl skeleton containing double bonds. Reacting 16-amino anthrone violet with 1, 6-hexamethylene diisocyanate with equivalent molar equivalent to obtain anthrone violet with isocyanate group. Blending the obtained anthrone violet with the isocyanate group and the obtained modified polyether with the side group containing hydroxyl skeleton and double bonds, keeping the molar ratio of the isocyanate group to the side hydroxyl group at 1:2, and reacting under the catalysis of DBTDL to obtain the modified polyether with the anthrone violet side group and the side hydroxyl group. Dissolving a certain amount of the obtained modified polyether in pyridine under anhydrous and anaerobic conditions, slowly dropwise adding 2-bromine isobutyryl bromide at 0 ℃ under stirring, keeping the molar ratio of lateral hydroxyl groups in the polyether to the 2-bromine isobutyryl bromide at 2:1, and then heating to room temperature for reaction for 24 hours to obtain polyether with lateral groups containing bromine. And (3) under anhydrous and anaerobic conditions, keeping the molar ratio of bromine to butyl acrylate to acrylonitrile in the obtained polyether side group to be 1:25:15, and polymerizing under the catalysis of cuprous bromide and PMDETA by using anisole as a solvent to obtain the polyether graft (ethyl acrylate-acrylonitrile random copolymer). And (2) taking stannous octoate as a catalyst, taking the obtained modified polyether as an initiator, initiating ring-opening polymerization of the levorotatory lactide in toluene at 100 ℃, keeping the molar ratio of hydroxyl in the modified polyether to lactide monomer at 1:30, and reacting to obtain the modified polyether grafted poly (levorotatory lactic acid) copolymer. Dissolving the obtained copolymer and a certain amount of 4-methyl-triazolidine-3, 5-diketone in tetrahydrofuran, keeping the molar ratio of double bonds in polyether to 4-methyl-triazolidine-3, 5-diketone to be 2:1, stirring and fully reacting to obtain modified polyether graft (ethyl acrylate-acrylonitrile random copolymer) or poly-L-lactic acid copolymer with a polyether chain segment side group containing hydrogen bond groups. Dissolving the obtained copolymer in a solution containing a proper amount of copper trifluoromethanesulfonate, fully stirring, and removing the solvent to obtain the dynamic polymer. The product has excellent toughness, good self-repairing property and good biodegradability, and has potential application value in the aspect of biological materials.
Example 8
Under the protection of nitrogen, 5 mol equivalent of bisphenol A and 6 mol equivalent of dichlorodiphenyl sulfone are dissolved in N-methylpyrrolidone, toluene is used as a dehydrating agent, anhydrous calcium carbonate is used as a salt forming agent, the temperature is increased to 140 ℃, the reaction is carried out for 1 hour, water generated in the reaction is taken out and separated by methylbenzene, then the temperature is increased to 160 ℃, the reaction is carried out for 4 hours, and the reaction is carried out for 4 hours at 180 ℃. After the reaction was completed, it was cooled to room temperature, 2 molar equivalents of p-aminophenol, toluene and potassium carbonate were added, and the above process was repeated. And precipitating the crude product by using ethanol to obtain the polysulfone with amino groups at two ends. Under the protection of nitrogen, 11 molar equivalents of 2-bromoisobutyryl bromide and 5 molar equivalents of ethylene glycol are dissolved in dichloromethane, and the mixture reacts at 0 ℃ under the catalysis of 12 molar equivalents of triethylamine to obtain the dual initiator 1, 2-bis (bromoisobutyryl oxide). Under the anhydrous and anaerobic condition, 100 mol equivalent of n-butyl methacrylate and 50 mol equivalent of 2-methacryloyloxyethyl phosphorylcholine are dissolved in toluene, cuprous bromide and PMDETA are used as catalysts, 1 mol equivalent of 1, 2-bis (bromoisobutyryloxy) is used as an initiator, and the reaction is carried out for 6 hours at 90 ℃ to obtain the polymethacrylate chain segment with two bromine atom end caps. Dissolving 1 molar equivalent of the obtained polymethacrylate chain segment and 4 molar equivalents of 2-mercaptoethanol in dimethyl sulfoxide (DMSO), and reacting at 40 ℃ under the catalysis of triethylenediamine to obtain the polymethacrylate with two end hydroxyl groups blocked. Under the anhydrous and oxygen-free conditions, 3 molar equivalents of the obtained polymethacrylate and 6 molar equivalents of isophorone diisocyanate are reacted at 60 ℃ under the catalysis of DBTDL. And after the reaction is completed, adding the polysulfone obtained by 4 molar equivalents, and continuing the reaction to obtain the modified polymethacrylate-polysulfone multi-section copolymer. Fully stirring and swelling the obtained copolymer in a 1, 4-dioxane solvent, placing the mixture in a mold, completely freezing the mixture at the temperature of minus 80 ℃, starting an air pump at the temperature of minus 50 ℃, maintaining the dry air pressure to be less than 50 mu atm for 24 hours, placing the obtained foam material in a vacuum drying oven at the temperature of 20 ℃ for drying, and extracting all solvents to obtain the corresponding foam material. The product has excellent toughness at the temperature higher than room temperature, can be used for preparing products with the working temperature higher than room temperature, and can also be used as a filter material or a carrier.
Example 9
1 mol equivalent of ethylamine, 2.5 mol equivalents of Dithiothreitol (DTT) and 6 mol equivalents of gamma-thiobutyrolactone were added to a mixed solution of ethanol and 0.5M sodium bicarbonate (the volume ratio of the two was 1: 1). The reaction was carried out at 50 ℃ under nitrogen to give compound 9 a.
Fully blending 8 molar equivalents of 4,4' -difluorobenzophenone and diphenyl sulfone (the mass ratio of the two is about 1:4) at 180 ℃ under the protection of nitrogen, adding 12 molar equivalents of hydroquinone, 1 molar equivalent of anhydrous potassium carbonate and 10 molar equivalents of anhydrous sodium carbonate, slowly heating to 250 ℃, reacting at constant temperature for 30 minutes, and then heating to 290 ℃ for 1 hour to obtain the hydroxyl-terminated polyether-ether-ketone chain segment. Under the anhydrous and oxygen-free conditions, cyclooctene is used as a monomer, Grubbs second-generation catalyst is used as a catalyst, maleic acid is used as a chain transfer agent, and the molar ratio of the catalyst to the chain transfer agent to the monomer is kept at 1:4000: 20000. Tetrahydrofuran is used as a solvent, and the reaction is carried out for 2 hours at 40 ℃. The polymerization reaction was quenched with vinyl ethyl ether and the product was precipitated in methanol to give polycyclooctene with carboxyl groups at both end groups. Dissolving polyether ether ketone obtained by 3 molar equivalents and polycyclooctene obtained by 4 molar equivalents in dichloromethane, and obtaining the polyether ether ketone-polycyclooctene multistage copolymer by taking DCC and DMAP as catalysts. The multistage copolymer obtained by 1 molar equivalent, a compound 9a with 10 molar equivalents and 2-amino-4-mercaptobutyric acid with 15 molar equivalents are dissolved in toluene, and Azodiisobutyronitrile (AIBN) with 0.1 molar equivalent is added to react at 60 ℃ to obtain the dynamic polymer of the invention. Adding 100 parts by mass of the obtained dynamic polymer into age resister D1 parts by mass, promoter CZ1 parts by mass, paraffin oil 6 parts by mass and foaming agent H8 parts by mass, fully mixing, placing in a mold, foaming at 125 ℃ for 20 minutes, cooling, demolding, and continuing to keep the temperature at 150 ℃ for 15 minutes to obtain a corresponding foam product. The product has excellent toughness, and can be used for preparing various daily necessities and product components.
Example 10
Dissolving 1 molar equivalent (4-vinylphenyl) methanol and 1.1 molar equivalent pyridine in anhydrous dichloromethane, dripping 1 molar equivalent 2-bromo-2-methylpropanoyl bromide at 0 ℃, reacting for 3 hours, concentrating the solution, filtering, and removing impurities by using a silica gel column to obtain the styrene monomer 10 a. And reacting the triphenylformamide compound 10b with acryloyl chloride under the catalysis of triethylamine to obtain the acrylate monomer containing triphenylformamide. The acrylic acid and the pyridazine-3-methyl alcohol with equal molar equivalent react under the catalysis of DCC and DMAP to obtain the acrylate monomer 10c containing the ligand group.
Using 1 molar equivalent of AIBN as an initiator, copolymerizing 90 molar equivalents of styrene and 10 molar equivalents of the obtained styrene macromonomer 10a to obtain the polystyrene macroinitiator. Under the anhydrous and anaerobic conditions, keeping the molar ratio of the side group bromine atoms in the obtained polystyrene macroinitiator to the n-butyl acrylate, the acrylic ester monomer containing the tribenzoyl formamide to the 10c at 1:30:5:20, reacting in toluene at 80 ℃ under the catalysis of cuprous bromide and pentamethyldiethylenetriamine, and adding a solution containing a proper amount of gold nitrate after the reaction is completed to obtain the dynamic polymer. The product has good toughness and self-repairability, and can be used for preparing durable adhesives and the like.
Example 11
Cationic ring-opening polymerization of 20 molar equivalents of 2-n-butyl-2-oxazoline and 10 molar equivalents of 2-butenyl-2-oxazoline was initiated using 1 molar equivalent of methyl p-toluenesulfonate as an initiator, and water was used as a chain terminator to obtain poly (2-oxazoline) having an alkenyl group as a partial side group. The obtained poly (2-oxazoline), 3-mercapto-1-propanol and photoinitiator BDK were reacted in tetrahydrofuran, maintaining the molar ratio of the pendant alkenyl group to the 3-mercapto-1-propanol and BDK in the poly (2-oxazoline) segment at 5:5:1, to obtain poly (2-oxazoline) having a hydroxyl group in the pendant group. Dissolving a certain amount of the obtained modified poly (2-oxazoline) in pyridine under anhydrous and anaerobic conditions, slowly dropwise adding 2-bromine isobutyryl bromide at the temperature of 0 ℃ under stirring, keeping the molar ratio of lateral hydroxyl groups in the poly (2-oxazoline) to the 2-bromine isobutyryl bromide at 1:1, and then heating to room temperature for reaction for 24 hours to obtain the poly (2-oxazoline) with a lateral group containing bromine. Keeping the molar ratio of bromine to styrene monomer in the obtained poly (2-oxazoline) to be 1:20 under anhydrous and anaerobic conditions, carrying out bulk polymerization at 100 ℃ under the catalysis of cuprous bromide and Pentamethyldiethylenetriamine (PMDETA), dissolving a crude product in tetrahydrofuran after reaction, filtering by alumina, and precipitating in methanol to obtain the poly (2-oxazoline) grafted polystyrene. Dissolving 4-hydroxybutyl acrylate and ethyl acrylate with the same molar equivalent weight in dichloromethane, and reacting under the catalysis of DBTDL to obtain the carbamate-group-containing acrylate monomer 11 a. Under the anhydrous and oxygen-free conditions, reacting ethanol and isocyanate ethyl acrylate with equal molar equivalent in dichloromethane under the catalysis of triethylamine to obtain the acrylate monomer 11b containing thiocarbamate groups.
Under the anhydrous and anaerobic conditions, keeping the molar ratio of bromine to n-butyl acrylate, the acrylate monomer 11a, the acrylate monomer 11b, acryloyloxyethyl trimethyl ammonium chloride and sodium allylsulfonate in the obtained poly (2-oxazoline) grafted polystyrene to be 1:30:15:15:10:10, carrying out polymerization at 60 ℃ under the catalysis of cuprous bromide and PMDETA by using anisole as a solvent, adding acetone after reaction, filtering by alumina, and precipitating in methanol to obtain the poly (2-oxazoline) grafted (polystyrene-modified polyacrylate). Keeping the molar ratio of terminal bromine to methyl methacrylate in the obtained graft copolymer at 1:20 under anhydrous and anaerobic conditions, carrying out bulk polymerization at 70 ℃ under the catalysis of cuprous bromide and PMDETA, dissolving the crude product in diethyl ether after reaction, and precipitating the crude product in methanol to obtain the poly (2-oxazoline) graft (polystyrene-modified polyacrylate-polymethyl methacrylate). And (3) taking 100 parts by mass of the copolymer, fully blending with 100 parts by mass of alkyl-terminated polyethylene glycol oligomer, and removing the solvent to obtain the multi-section polymer polyethylene glycol oligomer swelling gel. The product has good toughness, and can be used as a coating and an adhesive.
Example 12
Under the protection of nitrogen, high molecular weight nylon 6 (average molecular weight is about 50000), n-decylamine with equal molar equivalent and diphenyl sulfone with equal mass of nylon 6 are put into a closed container and react at 235 ℃ to obtain the single-end amino-terminated low molecular weight nylon 6 (average molecular weight is about 3000). Dissolving low-density polyethylene (with average molecular weight of about 50000) in xylene, adding 100 mol equivalents of maleic anhydride, adding dicumyl peroxide as an initiator dissolved in the xylene when the temperature of the solution rises to 130 ℃, and reacting at constant temperature for 1-3 hours to obtain the low-density polyethylene grafted maleic anhydride. And (3) melting and blending 1 molar equivalent of the obtained low-density polyethylene grafted maleic anhydride and 10 molar equivalents of the single-end amino-terminated low-molecular-weight nylon 6 at 200 ℃ to obtain the low-density polyethylene with maleic anhydride side groups and nylon 6 side chains. Heating and dissolving 1 molar equivalent of the obtained low-density polyethylene in xylene, adding 50 molar equivalents of 4- (2-aminoethyl) pyridine and a proper amount of sodium p-toluenesulfonate, and stirring at 130 ℃ for reaction to obtain the low-density polyethylene with a side ligand group, a side carboxyl group and a nylon 6 side chain. Reacting the obtained polyethylene 1 molar equivalent with 25 molar equivalents of 2-pentafluorophenoxyethanol and 2-naphthyl ethanol respectively under the catalysis of DCC and DMAP to obtain the low-density polyethylene with lateral supermolecular groups and nylon 6 side chains. And mixing the obtained low-density polyethylene with a proper amount of silver nitrate solution, and removing the solvent to obtain the dynamic polymer. 100 parts by mass of the obtained dynamic polymer, 20 parts by mass of sodium stearate, 5 parts by mass of sodium bicarbonate and 0.1 part by mass of vaseline oil are fully blended, and then a corresponding foam product is obtained through extrusion molding. The product has light weight and good toughness, and can be used as toy filling material.
Example 13
And (2) initiating copolymerization of lithium acrylate and ethyl acrylate by using di-tert-butyl peroxide as an initiator and trithiocarbonate as a chain transfer agent, and keeping the molar ratio of the initiator to the chain transfer agent to the lithium acrylate to the ethyl acrylate to be 1:1:10:40 to obtain the lithium acrylate-ethyl acrylate random copolymer with one end capped by carboxyl. Reacting branched polyethyleneimine with a certain amount of carboxyl-terminated polyisoprene, and keeping the molar ratio of terminal amino groups to carboxyl groups to be 2:1 to obtain polyethyleneimine graft (lithium acrylate-ethyl acrylate random copolymer). Under the protection of nitrogen, the obtained branched polyethyleneimine and a certain amount of L-alanine-N-carboxyl-cyclic internal anhydride are dissolved in dimethylformamide, the molar ratio of the terminal amino group to the L-alanine-N-carboxyl-cyclic internal anhydride is kept at 1:8, and the reaction is carried out at room temperature. After the reaction is completed, the product is precipitated by methanol to obtain polyethyleneimine grafted polypeptide or (lithium acrylate-ethyl acrylate random copolymer). And (3) blending 100 parts by mass of the obtained polymer and 3 parts by mass of graphene, and placing the blend in a mold for compression molding to obtain the dynamic polymer product. The product has good toughness, can be used as a functional coating and an adhesive, and can also be used for preparing a film with heat, electricity and stress sensing functions.
Example 14
Ethyl isocyanate is reacted with 1, 4-pentadiene-3-amine in an equivalent molar amount under anhydrous and oxygen-free conditions to obtain the diolefin compound 14a with carbamido on its side group. 3, 4-diiodobenzoic acid and 1, 4-pentadiene-3-ol with equal molar equivalent are reacted under the catalysis of DCC and DMAP to obtain the diene compound 14b with iodo-phenyl in the side group. 1 molar equivalent of 1-methyl-1H-imidazole-4, 5-dicarboxylic acid and 2 molar equivalents of allyl alcohol react under the catalysis of DCC and DMAP to obtain the diene compound 14c containing imidazole in the framework.
Under the anhydrous and oxygen-free conditions, 1 mol equivalent of 1, 3-diaminourea and 2 mol equivalent of 2,4-TDI are dissolved in ethanol and react for 16 hours at room temperature to obtain a triurea intermediate with two ends of isocyanate groups. Dissolving 1 molar equivalent of the obtained intermediate in DMSO2 molar equivalents of hydroxyethyl acrylate, and reacting at 60 ℃ to obtain a segment 14d which is provided with allyl groups at two ends and is rich in hydrogen bond groups.
10 molar equivalents of diallyl-terminated polyethylene glycol, 5 molar equivalents of compound 14a, 3 molar equivalents of compound 14b, 3 molar equivalents of compound 14c, 4 molar equivalents of segment 14d and 24 molar equivalents of 1, 2-ethanedithiol are mixed in DMF, benzoin dimethyl ether is used as a photoinitiator, and the mixture is subjected to a light reaction under an ultraviolet lamp. After the reaction was complete, 2 molar equivalents of methyl acrylate cap were added to give a polythioether-based multistage copolymer. Before removing the solvent, adding 1-ethyl-3-methylimidazole tetrafluoroborate with the same mass as the total weight of the raw materials, carbon nano tubes with the total mass of 4 percent and a proper amount of ferrous tetrafluoroborate, uniformly mixing, and removing the solvent to obtain the polyether-based dynamic polymer/1-ethyl-3-methylimidazole tetrafluoroborate ionic gel. The modulus of the ionic liquid gel prepared in the example is 59kPa, the strain can reach 8 times, and the breaking stress is 97 kPa. The ionic liquid gel has good stability and strong mechanical property, can be applied to the fields of dye solar cells, brakes, supercapacitors, artificial muscles, electrochromic devices and the like, and can also be used as sensing materials of electricity, stress and the like.
Example 15
5 molar equivalent of 6, 6' -dichloro (2, 2' -bipyridyl) -4, 4' dimethyl diformate and 6 molar equivalent of polyethylene glycol with two hydroxyl end groups blocked are subjected to ester exchange reaction to obtain polyether with a framework containing bipyridyl. And (2) reacting the obtained polyether with diphenylphosphine lithium at 0 ℃ for 6 hours under anhydrous and oxygen-free conditions, and keeping the molar ratio of chlorine atoms on the bipyridyl to the diphenylphosphine lithium to be 1:1 to obtain the polyether with a skeleton containing bipyridyl and phenylphosphine side groups. The polyether obtained in 4 molar equivalents (calculated as 100 parts by mass), an appropriate amount of silver tetrafluoroborate (wherein the molar ratio of silver ions to bipyridyl is 1:2), 2 parts by mass of DBTDL, 1 part by mass of silicone oil, 50 parts by mass of methylene chloride, and 30 parts by mass of water were thoroughly blended at 35 ℃, and this was designated as component a. 6 molar equivalent of urea is dropped into 9 molar equivalent of 4, 4-diisocyanate dicyclohexylmethane, and after fully blending and stirring for 24 hours at 70 ℃, the temperature is reduced to 35 ℃, and the component B is marked. And mixing the component A and the component B, rapidly stirring until bubbles are generated, then freely foaming, and then carrying out heat preservation and dehydration on the obtained foam at 120 ℃ to obtain the dynamic polymer open-cell soft foam with the hard section being the triurea soft section and based on polyether. The product is light and soft, and can be used as filler for toys, etc.
Example 16
At 0 ℃,1 molar equivalent of pentaerythritol and 4 molar equivalents of pyridine are dissolved in anhydrous tetrahydrofuran, and 4 molar equivalents of 2-bromopropionyl bromide are slowly dropped into the solution under the protection of nitrogen. The solution was warmed to room temperature and reacted for 16 hours, and then the precipitate was removed by filtration. The filtrate was concentrated to remove the solvent and recrystallized from ethanol to give intermediate 16 a. Respectively dissolving 1 molar equivalent of 16a and 6 molar equivalents of sodium iodide in acetone, rapidly mixing the two solutions, stirring, filtering out precipitates after complete reaction, removing the solvent, removing impurities from the crude product by using dichloromethane as a washing liquid through a short silica gel column, and recrystallizing in methanol to obtain the tetrafunctional initiator 16 b.
X＝Br，16a；X＝I，16b
Under the oxygen-free condition, sodium sulfite is used as a catalyst, sodium bicarbonate is used as an auxiliary agent, the obtained 16b is used as an initiator, vinyl chloride monomer is polymerized in water, the molar ratio of the monomer, the catalyst, the auxiliary agent and the initiator is kept at 200:2:2.2:1, Celvol540(0.293g/mL) and Methocel K100(0.11g/mL) are used as stabilizers, and the reaction is carried out at the temperature of 25 ℃ to obtain the four-arm polyvinyl chloride terminated by iodine atoms. And repeating the steps, replacing 16a with 2-bromomethyl propionate, and reacting to obtain the polyvinyl chloride with the single end being the end capping of the iodine atom. Dissolving the obtained polyvinyl chloride with the end capped with iodine atom at one end and 4-mercaptobenzyl alcohol in cyclohexane, and reacting at 60 ℃ for 12 hours, and keeping the molar ratio of the chlorine atom on the side group to the 4-mercaptobenzyl alcohol to be about 20:1 to obtain the polyvinyl chlorideTo modified polyvinyl chloride containing pendant hydroxyl groups. And (3) reacting the obtained modified polyvinyl chloride with a certain amount of (6-phenyl-2, 2' -bipyridine) -4-carboxylic acid, keeping the molar ratio of side hydroxyl to carboxyl to be 1:1, and using DCC and DMAP as catalysts to obtain polyvinyl chloride 16c containing side supermolecular groups. Under the anhydrous and oxygen-free conditions, 1 molar equivalent of the obtained four-arm polyvinyl chloride terminated by iodine atoms, 4 molar equivalents of copper, 12 molar equivalents of tris (2-dimethylaminoethyl) amine and 60 molar equivalents of methyl methacrylate are dissolved in DMSO, the mixture is stirred and reacted at 25 ℃, after the reaction is completed, tetrahydrofuran is added, and the mixed solution of the tetrahydrofuran, the precipitate and water/methanol is precipitated, so that the polyvinyl chloride-polymethyl methacrylate four-arm copolymer is obtained. The resulting 1 molar equivalent of the four-arm copolymer, 4 molar equivalents of sodium disulfite, 4.4 molar equivalents of sodium bicarbonate and 20 molar equivalents of allyl hydroxyethyl ether were dissolved in DMSO under anhydrous and oxygen-free conditions, reacted at 70 ℃ for 4 hours, and the concentrated reaction solution was precipitated in methanol to obtain a hydroxyl-terminated four-arm copolymer. And repeating the step, and replacing the four-arm copolymer with the modified polyvinyl chloride with the end capped with iodine atoms at the single end to react to obtain the modified polyvinyl chloride with the end capped with hydroxyl at the single end. And dissolving the obtained single-end hydroxyl-terminated polyvinyl chloride and equimolar 2,4-TDI in dichloromethane, and reacting under the catalysis of TDBDL to obtain the polyvinyl chloride with one end terminated by isocyanate group. Dissolving 4 molar equivalents of the modified polyvinyl chloride with one end blocked by isocyanate groups and 1 molar equivalent of the four-arm polymer in dichloromethane, and reacting under the catalysis of TDBDL to obtain the four-arm polymer blocked by the modified polyvinyl chloride. 100 parts by mass of the dynamic polymer thus obtained, PtCl in an amount equivalent to the molar equivalents of the side supramolecular groups2(DMSO)2Uniformly mixing 70 parts by mass of epoxidized soybean oil, 50 parts by mass of tricresyl phosphate and 20 parts by mass of polyvinylpyrrolidone microspheres, placing the mixture in a mold, keeping the temperature for 30 minutes at 180 ℃, and cooling to obtain the corresponding dynamic polymer plasticizer swelling gel. The product has good strength and toughness and certain hygroscopicity, and can be used as orthopedic material.
Example 17
Dissolving allyl hydroxyethyl ether and 5-chloromethyl-2-oxazolidinone in toluene in a molar ratio of 1:1, using potassium carbonate AS a catalyst and tetrabutylammonium bromide AS a phase transfer agent to obtain a compound 17a with one end being allyl and one end being oxazolidinone, reacting 3A-amino-3A-deoxy- (2AS,3AS) - α -cyclodextrin with 3-isocyanopropylene in an equivalent molar amount to obtain α -cyclodextrin with one alkenyl group, alkynylating 1, 4-diiodobenzene, coupling with 4-iodoaniline to obtain a conjugated chain segment 17b with two end amino end caps, and acylating 1 molar equivalent of the conjugated chain segment 17b with 2 molar equivalents of 2,2':6', 2' -terpyridine-4-carboxylic acid to obtain a conjugated chain segment 17c with two end caps by terpyridyl groups.
The preparation method comprises the steps of mixing 1 molar equivalent of octamethylcyclotetrasiloxane and 1 molar equivalent of tetramethylcyclotetrasiloxane in acetic acid, reacting at 130 ℃ under the catalysis of 0.02 molar equivalent of concentrated sulfuric acid, fully reacting, standing and cooling the reaction solution, washing the reaction solution to be neutral by using sodium chloride aqueous solution and calcium carbonate aqueous solution, removing solvent and low-boiling-point substances to obtain hydrogenpolysiloxane with two ends blocked by hydroxyl groups, reacting 1 molar equivalent of hydrogenpolysiloxane with two ends blocked by hydroxyl groups with 2 molar equivalents of 2,2', 6', 2' -terpyridine-4-formic acid under the catalysis of DCC and DMAP to obtain hydrogenpolysiloxane blocked by terpyridyl groups, reacting the polysiloxane containing 5 molar equivalents of hydrosilation with 3 molar equivalents of compound 17a, 1 molar equivalent of α -cyclodextrin with one alkenyl group, 1 molar equivalent of hexapolyethylene glycol blocked by one end of alkenyl group in cyclohexanone at 90 ℃ for 3 hours by using chloroplatinic acid as a catalyst to obtain polysiloxane with one end blocked by terpyridyl groups, mixing 100 parts of the obtained polysiloxane containing side ligand groups and side hydrogen bond groups, 30 parts of conjugated zinc oxide, and injecting a certain amount of hygroscopic foam material which can be molded and has good heat preservation.
Example 18
Cyanuric acid and 6-chloro-1-hexene are dissolved in anhydrous dimethyl sulfoxide with a molar ratio of 4:1, and are stirred and reacted for 15 hours at 80 ℃ under the catalysis of potassium carbonate to obtain the olefin monomer containing the hydrogen bond group. Adding 10 molar equivalents of the obtained olefin monomer containing the hydrogen bond group into toluene, cooling the reaction vessel to 5 ℃, and dropwise adding 13 molar equivalents of cyclopentadiene while stirring at low temperature. After the dropwise addition, the temperature is raised to the reflux temperature, and the stirring reaction is continued to obtain a compound 18 a. The allyl hydroxyethyl ether with equal molar equivalent and 4-carbonic acid benzo-18-crown ether-6 react under the catalysis of DCC and DMAP to obtain the olefin monomer containing crown ether. Adding 10 molar equivalents of the obtained olefin monomer containing crown ether into toluene, cooling the reaction vessel to 5 ℃, and dropwise adding 13 molar equivalents of cyclopentadiene while stirring at low temperature. After the dropwise addition, the temperature is raised to the reflux temperature, and the stirring reaction is continued to obtain a compound 18 b. Dissolving 1 molar equivalent of 2, 6-diisopropylimine bis-tert-butoxy molybdenum serving as an initiator in toluene under anhydrous and oxygen-free conditions, adding 5 molar equivalents of trimethyl phosphorus serving as a regulator and 30 molar equivalents of norbornene serving as a crystalline polymer monomer, reacting for 1 hour, and adding 20 molar equivalents of methyltetracyclododecene serving as a glassy polymer monomer. After 1 hour of continued reaction, 600 molar equivalents of rubbery polymer monomer 5-n-hexyl-2-norbornene, 200 molar equivalents of monomer 18a and 50 molar equivalents of monomer 18b were added. Finally, 0.5 molar equivalent of coupling agent m-phthalaldehyde is added, and after the reaction is completed, the product is precipitated in methanol to obtain the pentablock copolymer.
Dissolving the obtained pentablock copolymer in cyclohexane, and carrying out catalytic hydrogenation at 100 ℃ by using platinum as a catalyst to obtain a multi-end-single middle-section multi-section polymer based on hydrogenated polynorbornene, wherein the middle section of the two-block copolymer with a crystalline-glassy state end section is a rubbery random copolymer. The resulting polymer was blended with an appropriate amount of N, N-diethyl-1, 6-hexanediamine hydrochloride, maintaining the molar ratio of pendant crown ether to N, N-diethyl-1, 6-hexanediamine hydrochloride at 2:1, and compression molded to give a dynamic polymer article of the invention. The product has excellent toughness, good rebound resilience and small permanent deformation, can be stretched in a large range, and can be used for preparing conveyor belt components and the like.
Example 19
And initiating polymerization of 30 molar equivalents of ethyl methacrylate at 90 ℃ by using 1 molar equivalent of Benzoyl Peroxide (BPO) as an initiator and 1 molar equivalent of thioglycolic acid as a chain transfer agent to obtain the single-end carboxyl-terminated polyethyl methacrylate. Under the protection of nitrogen, adding urea into aminated dimethyl siloxane 19a (average molecular weight is about 10000Da, x: y is about 3:2), keeping the molar ratio of urea to amino at 7:10, slowly heating to 160 ℃ under stirring, preserving the temperature for about 30 minutes, and then cooling to room temperature to obtain the modified polydimethylsiloxane with part of amino converted into imidazolinone. The obtained polydimethylsiloxane and 4-pyridazine carboxylic acid are subjected to acylation reaction in the presence of a condensing agent 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline, and the molar ratio of side amino groups to carboxyl groups is kept to be 5:2, so that the modified polydimethylsiloxane 19b is obtained.
And (3) carrying out acylation reaction on the obtained polydimethylsiloxane 19b and the single-end carboxyl-terminated polyethylmethacrylate in the presence of a condensing agent 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline, and keeping the molar ratio of side amino groups to carboxyl groups at 10:1 to obtain the modified polydimethylsiloxane grafted polyethylmethacrylate. The obtained polymer is mixed with a proper amount of copper bromide solution, and the dynamic polymer is obtained after the solvent is removed. The product has excellent toughness, and can be applied to sealing, protecting and waterproofing of components of electronic products, such as waterproof sealing plugs of mobile phone earphone holes and the like; the material can also be used as a base material of electric, thermal and stress sensors such as graphene and carbon nano tubes.
Example 20
The preparation method comprises the steps of initiating 20 molar equivalents of methyl methacrylate to polymerize by taking 1 molar equivalent of 4,4' -azobis (4-cyanopentanol) as an initiator and 4-pentene-1-ol as a chain transfer agent to obtain polymethyl methacrylate with end-capped hydroxyl groups at two ends, under anhydrous conditions, initiating 50 molar equivalents of α -chloro-epsilon-caprolactone and 50 molar equivalents of epsilon-caprolactone to perform ring-opening polymerization at 110 ℃ by taking 1 molar equivalent of the obtained polymethyl methacrylate as a macromolecular diinitiator and stannous octoate as a catalyst to obtain a three-stage copolymer with hydroxyl groups at two ends, blending the obtained three-stage copolymer and polystyrene with hydroxyl groups at one end according to a molar ratio of 1:1, reacting under the catalysis of DCC and DMAP to obtain a polystyrene-modified polyester-polymethyl methacrylate-modified polyester-polystyrene five-stage copolymer, adding 2 molar equivalents of sodium azide with chlorine atoms into the obtained copolymer containing chlorine atoms as a side group, reacting to obtain a copolymer containing azido groups on the side groups, blending one end of the copolymer containing alkynyl groups as an azido group, adding a proper amount of the copolymer into a mould to obtain a cuprous chloride-containing copolymer, and adding a cuprous iodide-containing cuprous chloride group-containing copolymer to obtain a good-containing cuprous chloride-containing copolymer, and adding a good-2 molar-iodine-containing copolymer to obtain a mould for a mould under the formation reaction, and keeping the good quality of a good-forming material for the formation of the invention.
Example 21
1 molar equivalent of 2-vinylterephthalic acid and 2.1 molar equivalents of triphenylphosphine were dissolved in anhydrous pyridine to obtain solution A. 2.1 molar equivalents of 4-methoxyphenol and 2.2 molar equivalents of hexachloroethane were dissolved in anhydrous pyridine to give solution B. And slowly dripping the solution B into the solution A, and reacting at 60 ℃ to obtain the liquid crystal monomer vinyl terephthalic acid di-p-methoxyphenyl ester (MPCS). Dissolving equal molar equivalents of ethyl isocyanate and N- (2-hydroxyethyl) acrylamide in chloroform, and reacting under the catalysis of TDBDL to obtain the acrylamide monomer 21a containing the carbamate group. Reacting equivalent molar weight of tetrazoleacetic acid and N- (2-hydroxyethyl) acrylamide under the catalysis of DCC and DMAP to prepare the acrylamide monomer 21b containing ligand groups. The 2-methoxy-5 a,9 a-dihydrodibenzo [ b, d ] pyran-3-amine with equal molar equivalent and acryloyl chloride react under the catalysis of triethylamine to obtain acrylamide monomer 21c containing dihydrodibenzopyran. Under the protection of nitrogen, 13 molar equivalents of 2-bromoisobutyryl bromide and 3 molar equivalents of pentaerythritol are dissolved in dichloromethane and react at 0 ℃ under the catalysis of 15 molar equivalents of triethylamine to obtain the tetrafunctional initiator. Under anhydrous and anaerobic conditions, 1 molar equivalent of the obtained tetrafunctional initiator, 2 molar equivalents of cuprous bromide, 2 molar equivalents of PMDETA, 400 molar equivalents of acrylamide, 200 molar equivalents of the monomer 21a, 40 molar equivalents of the monomer 21b and 16 molar equivalents of the monomer 21c are sequentially added into a reaction vessel, and the reaction is carried out at 80 ℃ to obtain the polyacrylamide-based four-arm polymer. Under the anhydrous and anaerobic conditions, 4 molar equivalents of cuprous chloride, 4 molar equivalents of PMDETA and 200 molar equivalents of monomer MPCS are placed in a reaction vessel, and a chlorobenzene solution containing 1 molar equivalent of the obtained modified polyacrylamide is added to react at 110 ℃ to obtain the polymer with the side chain type liquid crystal polymer as an end section and the four-arm star structure. And fully blending the obtained polymer with 1-butyl-3-methylimidazolium hexafluorophosphate with equal mass, a proper amount of ferric trifluoromethanesulfonate solution and cucurbit [8] urea, and removing the solvent to obtain the corresponding ionic gel. The ionic liquid gel prepared by the embodiment has good conductivity and mechanical strength, can be stable in a wide temperature range and an electrochemical window, and can be prepared into an ideal electrolyte material.
Example 22
Under the protection of nitrogen, 2 molar equivalents of methyl p-hydroxybenzoate are dissolved in tetrahydrofuran, and a catalyst triethylamine is added and mixed uniformly. A tetrahydrofuran solution containing 1 molar equivalent of terephthaloyl chloride was dropped at 0 to 5c, and after keeping and reacting for 10 hours, a liquid crystal hard segment 22a was obtained.
Under the condition of anhydrous and air-free temperature of 90 ℃, dissolving limonene oxide and a catalyst 22b in toluene, keeping the molar ratio of the limonene oxide to the catalyst at 50:1, introducing 10bar of carbon dioxide into a reaction container, and after the reaction is completed, precipitating a crude product with methanol to obtain a poly-limonene carbonate chain segment. The resulting poly (limonene carbonate) segment and 1, 3-propylene glycol were dissolved in toluene, added with the catalyst 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, and reacted at 80 ℃ for 3 hours to obtain a poly (limonene carbonate) segment 22c having an average molecular weight of about 2000 with both ends capped with hydroxyl groups. Under the protection of nitrogen, 1 molar equivalent of hydroxyl-terminated poly (limonene carbonate) 22c and 1.1 molar equivalent of liquid crystal hard segment 22a are blended to carry out transesterification reaction and distill methanol, and after the reaction is completed, the liquid crystal-poly (limonene carbonate) multi-stage polymer is obtained.
And (3) blending 4-mercaptobutyric acid and 4-hydroxymethyl-tetrathiafulvalene with equal molar equivalent, and reacting under the catalysis of DCC and DMAP to obtain the mercapto-functionalized tetrathiafulvalene. The segmented polymer of the invention is obtained by dissolving a liquid crystal-poly-limonene carbonate multi-segment polymer containing 100 molar equivalents of side alkenyl, 30 molar equivalents of obtained sulfydryl functionalized tetrathiafulvalene, 10 molar equivalents of sulfydryl mono-functionalized calixarene [8] hydrocarbon and 60 molar equivalents of 3-mercaptopropionic acid n-butyl ester in tetrahydrofuran, fully blending, and reacting under the irradiation of an ultraviolet lamp in the presence of a photoinitiator BDK. And (3) blending 70 parts by mass of the obtained liquid crystal-poly (limonene carbonate), 30 parts by mass of the obtained polyester-polystyrene copolymer in example 4 and 5 parts by mass of cellulose nanocrystal, removing a solvent, and forming to obtain the dynamic polymer alloy product with the interpenetrating network structure. The main raw materials of the product are renewable raw materials, and the product can be widely used as disposable packaging films, daily products and the like.
Example 23
Reacting acryloyl chloride and 3-iodine-1-propanol with equal molar equivalent under the catalysis of triethylamine, blending the obtained product and 1-butylimidazole with equal molar equivalent, reacting for 2 days at 40 ℃, and adding a small amount of sodium fluoborate to obtain the acrylate monomer containing the ionic liquid group. Dissolving 1 molar equivalent of 4- (chloromethyl) benzoyl chloride in a mixed solution of diethyl ether/normal hexane in the same volume ratio, slowly dripping an aqueous solution containing 1.3 molar equivalents of lithium peroxide at 0 ℃, and reacting for 6 hours at 0 ℃ to obtain the peroxide bifunctional initiator. Acetonitrile is used as a solvent, and the obtained bifunctional initiator initiates the free radical copolymerization of vinylidene fluoride and hexafluoropropylene at 90 ℃ to obtain the fluorine-containing copolymer with two ends of chlorine atoms. And initiating the free radical copolymerization of the obtained acrylate monomer containing the ionic liquid group by using the obtained bifunctional initiator to obtain the polyion liquid with chlorine atoms at two ends. Respectively carrying out an azide reaction on the obtained fluorine-containing copolymer with chlorine atoms at two ends and the obtained polyionic liquid by using sodium azide as an azide reagent to obtain the fluorine-containing copolymer with azide groups at two ends and the polyionic liquid. The polycyclooctene obtained in example 9 was subjected to hydrogenation to obtain polyethylene having carboxyl groups at both ends. And reacting the polyethylene with carboxyl at two ends obtained by 1 molar equivalent and 2-propyn-1-ol by 2 molar equivalents under the catalysis of DCC and DMAP to obtain the polyethylene with alkynyl end-capped at two ends. 3 molar equivalent of fluorine-containing copolymer with two ends of azido group, 3 molar equivalent of polyion liquid with two ends of azido group and 7 molar equivalent of polyethylene with two ends of alkynyl group blocked are subjected to azide-alkyne click reaction to obtain the dynamic polymer. The obtained dynamic polymer is blended with 2-8% of graphene by mass fraction, so that the polymer has conductivity and pressure responsiveness, and has different conductivities under the action of different stresses; and the faster the stress stimulation speed, the better the mechanical property, and the stress stimulation speed can be used for preparing a force sensor.
Example 24
Equimolar amounts of furan and maleimide were reacted in dichloromethane to give the furan-maleimide adduct. Mixing a certain amount of monomer furan-maleimide adduct and cyclooctene under anhydrous and oxygen-free conditions, controlling the ratio of the two molar numbers to be about 1:10, using Grubbs second generation catalyst as a catalyst, using maleic acid as a chain transfer agent, and keeping the molar ratio of the catalyst, the chain transfer agent and the monomer to be 1:4000: 100000. Tetrahydrofuran is used as a solvent, and the reaction is carried out for 2 hours at 40 ℃. Quenching the polymerization reaction by vinyl ethyl ether, and precipitating the product in methanol to obtain the modified polycyclooctene with two end groups of carboxyl skeleton and maleimide. 1 molar equivalent of 4,4' -azobis (4-cyanopentanol) is taken as an initiator, 4-penten-1-ol is taken as a chain transfer agent, and 20 molar equivalents of styrene are initiated to polymerize to obtain the polystyrene with two end hydroxyl groups terminated. And dissolving the modified polycyclooctene in 2 molar equivalents and the polystyrene in 3 molar equivalents in dichloromethane, and using DCC and DMAP as catalysts to obtain the multi-stage copolymer. And carrying out mercapto-alkene click reaction on the obtained multi-section copolymer, 2-mercaptoethylguanidine and 3-mercaptopropionic acid under the initiation of BDK, and keeping the molar ratio of alkenyl to the 2-mercaptoethylguanidine to the 3-mercaptopropionic acid to be 10:1:1 to obtain the dynamic polymer. 100 parts by mass of the polymer and 30 parts by mass of a polystyrene-polybutadiene-polystyrene thermoplastic elastomer are blended to obtain the dynamic polymer alloy. Adding 5.5 parts by mass of azodicarbonamide and 1 part by mass of tribasic lead sulfate into 100 parts by mass of the obtained alloy, fully mixing, placing the mixture in a mould, plasticizing and foaming at the temperature of 170 ℃ and under the pressure of 3.5MPa, then carrying out heat treatment at the temperature of 100 ℃ for 8 minutes, cooling and demoulding to obtain a corresponding foam product. The product has good toughness and repairability, and can be used for preparing self-repairability device shells, electrical elements, automobile parts and sealing elements.
Example 25
Taking toluene as solvent, zirconium complex Et [ H ]4-Ind]2ZrCl2As catalyst, and methyl aluminoxane as cocatalyst, to obtain isotactic polypropylene with one end of alkenyl end-capped. 1 molar equivalent of the resulting polypropylene was added to chlorobenzene under anhydrous and oxygen-free conditions and dissolved well at 105 ℃. Adding 20 molar equivalents of 3-mercaptopropionic acid and 0.5 molar equivalent of AIBN, reacting for 5 hours, and precipitating a product in ethanol to obtain crystalline isotactic polypropylene with one end blocked by carboxyl. 1 molar equivalent of azodimethyl N-2-hydroxybutylpropamide is dissolved in toluene under anhydrous and oxygen-free conditions, and 105 molar equivalents of vinyl acetate are added. And reacting for 16 hours at the reflux temperature to obtain polyvinyl acetate with two ends of hydroxyl. Dissolving 2 molar equivalents of isotactic polypropylene and 1 molar equivalent of polyvinyl acetate in toluene, and reacting at 110 ℃ for 5 hours under the catalysis of tetrabutyl titanate to obtain the isotactic polypropylene-polyvinyl acetate-isotactic polypropylene three-stage copolymer. And dissolving the obtained three-stage polymer in tetrahydrofuran, adding a methanol solution containing potassium hydroxide, and reacting at room temperature to obtain the copolymer with the polyvinyl acetate chain segment partially subjected to alcoholysis. And reacting the obtained copolymer with 5-carboxypyrrolidone and 9-anthracenecarboxylic acid under the catalysis of DCC and DMAP, and keeping the molar ratio of side hydroxyl to the 5-carboxypyrrolidone and the 9-anthracenecarboxylic acid to be 3:2:1 to obtain the three-stage polymer with side supermolecular groups. 1 molar equivalent of azodimethyl N-2-hydroxybutylpropamide is dissolved in toluene under anhydrous and oxygen-free conditions, and 105 molar equivalents of vinyl acetate are added. And reacting for 16 hours at the reflux temperature to obtain polyvinyl acetate with two ends of hydroxyl. And reacting the obtained polyvinyl acetate with hydroxyl at two ends with 2 molar equivalents of 5-carboxyl pyrrolidone under the catalysis of DCC and DMAP to obtain the polyvinyl acetate with hydrogen bond groups at two ends.And fully blending 100 parts by mass of the obtained three-stage polymer and 30 parts by mass of polyvinyl acetate with hydrogen bond groups at two ends to obtain the dynamic polymer. The product has excellent toughness, and can be used as various daily necessities, self-repairing plugs, sealing elements and the like.
Example 26
4,4' -methylenebis (phenyl isocyanate) and 2-ethylbutyrylchloride in equal molar equivalents were dissolved in xylene, and a xylene solution containing 1.5 molar equivalents of triethylamine was slowly dropped. After 4 hours of reaction at reflux temperature, the temperature is reduced to-15 ℃, insoluble substances are filtered, and the solvent is removed to obtain a crude product containing the compound 26 a. Dissolving 1 molar equivalent of aniline and the crude product containing 1 molar equivalent of compound 26a in toluene under anhydrous and oxygen-free conditions, reacting at 4 ℃ for 2 hours, and filtering to obtain an intermediate insoluble in toluene. 1 molar equivalent of N-aminoethylpiperazine was dissolved in DMF, reacted at 20 ℃ for 1 hour, and precipitated with water to give water-insoluble product 26 b. Compound 26b was dissolved in acetone and reacted with the crude product containing an equimolar amount of intermediate 26a, after 20 minutes, and precipitated with cyclohexane to give an intermediate. Under the protection of nitrogen, the intermediate and N-aminoethyl piperazine with equal molar equivalent are dissolved in anhydrous DMF, reacted at 20 ℃ for 1 hour, and precipitated with water to obtain the water-insoluble product 26 c.
Under the catalysis of DBTDL, diphenylmethane diisocyanate and low molecular weight poly β -hydroxybutyrate with the same molar equivalent weight and one hydroxyl end blocked are dissolved in DMF to react to obtain polyester blocked by isocyanate groups, 1 molar equivalent weight of compound 26c is added into polyester solution blocked by isocyanate groups with the same molar equivalent weight of 1 molar equivalent weight, after the reaction is completed, two-section type polymer based on polyester is obtained, the obtained polymer and maleic anhydride are dissolved in chlorobenzene, the initial mass volume concentration of the maleic anhydride is 3%, benzoyl peroxide is added at 130 ℃, the initial concentration of the benzoyl peroxide is 0.2%, the temperature is kept for reaction for 6 hours, modified poly β -hydroxybutyrate grafted maleic anhydride is obtained, under the protection of inert gas, the obtained modified poly β -hydroxybutyrate grafted maleic anhydride, 2-amino-anthracene, amino α -cyclodextrin and 3-aminopyrazole are dissolved in xylene, the molar ratio of the obtained maleic anhydride, 2-amino-anthracene, amino α -cyclodextrin and 3-aminopyrazole is kept to be multistage type reaction, the multi-section modified poly α -cyclodextrin and the biodegradable polyester microsphere with good quality is obtained by mixing, the biodegradable polyester microsphere with the good quality, the biodegradable polyester can be prepared by injecting the biodegradable polyester, and the biodegradable polyester with good quality of the biodegradable polyester.
Example 27
Under anhydrous and oxygen-free conditions, polymerization of 30 molar equivalents of styrene was initiated at 140 ℃ with 1 molar equivalent of cumyl dithiobenzoate as a chain transfer agent. After 6 hours of reaction, the product is precipitated in frozen absolute methanol, washed by ethanol and filtered, and the polystyrene macromolecular chain transfer agent with the average polymerization degree of about 20 is obtained. Dissolving 1 molar equivalent of the obtained polystyrene macromolecular chain transfer agent, 5 molar equivalents of acrylonitrile, 45 molar equivalents of ethyl acrylate, 10 molar equivalents of tert-butyl methacrylate and 1 molar equivalent of AIBN in DMF, and reacting at 65 ℃ for 48 hours to obtain the polystyrene-polyacrylonitrile/acrylate two-stage copolymer with dithiobenzoate at the end of polyacrylonitrile/acrylate. Under the anhydrous and oxygen-free conditions, 1 molar equivalent of the obtained dithiobenzoate-terminated two-section copolymer, 20 molar equivalents of tributylphosphine and 50 molar equivalents of acrylic acid are dissolved in tetrahydrofuran, 20 molar equivalents of sodium borohydride is added, the reaction is carried out for 20 hours at room temperature, and the product is precipitated in methanol to obtain the polystyrene-polyacrylonitrile-two-section copolymer with the carboxyl group at the polyacrylonitrile end. Dissolving the two-stage copolymer obtained by 2 molar equivalents and polystyrene with hydroxyl at two ends by 1 molar equivalent in dichloromethane, and obtaining the five-stage copolymer of polystyrene-polyacrylonitrile/acrylate-polystyrene by using DCC and DMAP as catalysts. And completely hydrolyzing the obtained five-stage polymer in trifluoroacetic acid to obtain the polystyrene-acrylonitrile/acrylate/methacrylic acid ternary random copolymer-polystyrene five-stage copolymer. 1, 10-decamethylenediamine and triethyl orthoacetate which is equivalent to a catalyst in mole are reacted in the presence of phenol to obtain the polyamidine with two end amino end caps. And (3) carrying out acylation reaction on 1 molar equivalent of the obtained polyamidine and 2 molar equivalents of polystyrene with one end blocked by carboxyl to obtain the polystyrene-polyamidine-polystyrene three-stage polymer. The dynamic polymer of the present invention was obtained by thoroughly blending 100 parts by mass of the obtained five-stage copolymer and 60 parts by mass of the obtained three-stage copolymer. The elastomer material has excellent toughness and self-repairing property, and can be used for preparing sectional materials, plates, films, sheets and the like with self-repairing function.
Example 28
The ring-opening polymerization of 20 molar equivalents of 2-phenyloxazoline was initiated with 1 molar equivalent of methyl p-toluenesulfonate as an initiator, and poly (2-phenyloxazoline) having a hydroxyl group at one end was obtained with water as a chain terminator. 1, 4-butanediol, 70-epoxypropane and 30-epoxy-5-hexene are mixed and reacted to prepare the polypropylene glycol with two ends containing the alkenyl on the hydroxyl side group. Under the anhydrous condition, polypropylene glycol with two hydroxyl end terminations obtained by 1 molar equivalent reacts with 60 molar equivalent of caprolactone and 30 molar equivalent of caprolactone monomer 4a under the catalysis of stannous octoate at 110 ℃ to obtain the polyester hydroxyl end termination modified polyester-modified polyether-modified polyester three-stage copolymer. Reacting 2 molar equivalents of poly (2-phenyloxazoline) with 2 molar equivalents of TDI under the catalysis of DBTDL, and adding 1 molar equivalent of the obtained polyester end hydroxyl terminated three-segment copolymer after the reaction is completed to obtain the poly (2-phenyloxazoline) -modified polyester-modified polyether-modified polyester-poly (2-phenyloxazoline) five-segment copolymer. Dissolving the obtained five-segment copolymer and 2-azido ethylamine in tetrahydrofuran, keeping the molar ratio of alkynyl to azido at 1:1, and reacting at 35 ℃ under the catalysis of cuprous iodide and pyridine to obtain the five-segment copolymer with the polyester segment side group containing amino. Mixing the obtained five-segment copolymer with a certain amount of 2-mercaptoethanesulfonic acid, keeping the molar ratio of the side alkenyl of the polyether segment to the 2-mercaptoethanesulfonic acid to be 1:1, taking benzoin dimethyl ether as a photoinitiator, and carrying out illumination reaction under an ultraviolet lamp to obtain the block polymer. And (3) blending 100 parts by mass of the obtained copolymer and 100 parts by mass of the alkyl-terminated polyethylene glycol oligomer to obtain the dynamic polymer polyethylene glycol oligomer swelling gel. The gel can be used as coating and adhesive.
Example 29
The method comprises the steps of using 1 molar equivalent of hydroxyethyl methacrylate as an initiator, using boron fluoride as a catalyst, initiating 100 molar equivalents of ethylene oxide and 50 molar equivalents of 3- (ethylene oxide-2-yl) pyridine cation to perform ring-opening polymerization, preparing modified polyether containing pyridyl in a side group with an alkenyl end and a hydroxyl end, dissolving the modified polyether obtained in 1 molar equivalent and polystyrene with a single-terminal carboxyl end capping in dichloromethane, using DCC and DMAP as catalysts, obtaining a polystyrene-modified polyether two-stage copolymer with an alkenyl end, adding PMDETA, cuprous bromide, α -bromoethyl propionate and methyl methacrylate into a reaction vessel in sequence under anhydrous and oxygen-free conditions, keeping the molar ratio of four to be 1:1:20, performing reaction at 70 ℃, adding tetrahydrofuran to the obtained polymethyl methacrylate to dissolve, using lithium aluminum hydride as a reducing agent, precipitating in methanol to obtain polymethyl methacrylate with a hydroxyl end capping at 6 hours under room temperature, obtaining a copolymer with a modified terminal hydroxyl end, adding the copolymer containing a modified polymethyl methacrylate with a corresponding substituent group and a corresponding substituent of ethylene imine, heating under a temperature of 1:1:20, adding a corresponding to a corresponding tetrahydrofuran, heating to a modified polyether to a copolymer containing a corresponding terminal carboxyl end, heating to a modified polyether to obtain a copolymer containing a copolymer, and a copolymer containing a copolymer with a corresponding terminal carboxyl end, heating to a modified polyether to a copolymer, and a corresponding terminal imine-modified polyether to obtain a copolymer, heating to a copolymer, and a modified polyether to a copolymer, and a copolymer containing a copolymer, and a copolymer, heating to obtain a copolymer, and a copolymer, which contains a copolymer, and a copolymer, which contains a copolymer, wherein the copolymer, and a terminal carboxyl end, wherein the copolymer, the copolymer contains a copolymer, the copolymer is a copolymer is.
Example 30
Respectively reacting isocyanate ethyl acrylate with n-propylamine in a solvent dichloromethane, and keeping the molar ratio of isocyanate to amino at 1:1 to obtain the acrylate monomer containing the urea bond. Under the anhydrous and anaerobic conditions, the initiator methyl 2-bromopropionate, n-butyl acrylate and tert-butyl methacrylate are kept in the molar ratio of 1:150:20:80, and the obtained acrylate monomer containing urea bonds is polymerized at 70 ℃ under the catalysis of cuprous bromide and PMDETA to react to obtain the modified polyacrylate. Under the anhydrous and anaerobic conditions, the molar ratio of bromine to styrene monomer in the obtained modified polyacrylate is kept at 1:20, and the modified polyacrylate-polystyrene is obtained by polymerization at 100 ℃ under the catalysis of cuprous bromide and PMDETA. 1 molar equivalent of the resulting copolymer and 25 molar equivalents of 5-amino-1-pentanol were dissolved in DMSO and reacted at 40 ℃ for 30 minutes. The reaction solution was dropped into methylene chloride, washed with hydrochloric acid, sodium bicarbonate solution and water, and dried over anhydrous magnesium sulfate to obtain a copolymer having a hydroxyl group at the polystyrene end. And reacting the obtained copolymer with acryloyl chloride under the catalysis of triethylamine to obtain the acrylate macromonomer. Under the anhydrous and anaerobic conditions, the molar ratio of the initiator 2-bromomethyl propionate to the n-butyl acrylate to the obtained acrylate macromonomer to the dimethylaminoethyl acrylate is kept at 1:200:10:200, and the polymerization is carried out at 70 ℃ under the catalysis of cuprous bromide and PMDETA to obtain the modified polyacrylate graft (polystyrene-modified polyacrylate). The obtained three-stage copolymer is hydrolyzed in trifluoroacetic acid to obtain the dynamic polymer of the invention. The product has excellent toughness, and can be used for manufacturing adhesives and plugging adhesives.
Example 31
Under the anhydrous and anaerobic conditions, 1 molar equivalent of polyacrylonitrile/acrylate end is dithiobenzoate polystyrene-polyacrylonitrile/acrylate two-section copolymer (see example 27), 20 molar equivalents of tributylphosphine and 50 molar equivalents of hydroxyethyl acrylate are dissolved in tetrahydrofuran, 20 molar equivalents of sodium borohydride is added, reaction is carried out for 20 hours at room temperature, a product is precipitated in methanol, polystyrene-polyacrylonitrile/acrylate copolymer with polyacrylonitrile/acrylate end as hydroxyl is obtained, di-tert-butyl peroxide is used as an initiator, trithiocarbonate is used as a chain transfer agent, isoprene is polymerized at 125 ℃ to obtain polyisoprene macromolecules, AIBN is used as an initiator, the obtained polyisoprene is used as a chain transfer agent, 1, 4-dioxane is used as a solvent, styrene polymerization is carried out at 60 ℃ to obtain polyisoprene-polystyrene two-section copolymer with carboxyl end capped at the polyisoprene end, the polystyrene-polyacrylonitrile two-section copolymer with carboxyl end as the acrylonitrile end as hydroxyl and polyisoprene-polystyrene-polyacrylonitrile two-section copolymer with carboxyl end as the equivalent end as the polyisoprene end as a copolymer are dissolved in dichloromethane, a polystyrene-polyacrylonitrile-acrylate two-section copolymer with carboxyl end as a carboxyl group, a polystyrene-terminated polystyrene-polyacrylonitrile copolymer with a carboxyl end as a carboxyl group, a polystyrene-terminated copolymer with a molar equivalent ratio of acrylonitrile-terminated polystyrene-.
Example 32
The polystyrene-modified polyether two-segment copolymer (see example 29) with the polyether end being the alkenyl side group and the carbamate group being the side group reacts with mercaptoacetic acid with equal molar equivalent under the combined action of BDK and ultraviolet light to convert the alkenyl into carboxyl. The obtained carboxyl-terminated polystyrene-modified polyether two-stage copolymer and an equimolar amount of polyester-polymethyl methacrylate two-stage copolymer (see example 29) of which the polyester end is terminated with hydroxyl and the side group contains triazolyl react under the catalysis of DCC and DMAP to obtain the polystyrene-modified polyether-polyester-polymethacrylate copolymer. The obtained copolymer is mixed with a proper amount of cerium trifluoromethanesulfonate solution, and the dynamic polymer is obtained after the solvent is removed. The material has good toughness and self-repairing property, also has a shape memory function, and can be used for preparing multifunctional parts.
Example 33
The cationic ring-opening polymerization of 10 molar equivalents of 2- (3-ethylheptyl) -2-oxazoline was carried out using 1 molar equivalent of propynyl p-toluenesulfonate as an initiator and 1 molar equivalent of hexynoic acid as a terminator to give poly (2-oxazoline) whose both ends were terminated with alkynyl groups. Under anhydrous condition, 1 mol equivalent of the compound 33a and 1 mol equivalent of 2, 6-diisopropylbenzene isocyanate are dissolved in tetrahydrofuran and reacted for 16 hours at room temperature to obtain the UPy derivative with one end being alkenyl. And respectively reacting the obtained UPy derivative with one end being alkenyl with mercaptoacetic acid with the same molar equivalent under the combined action of BDK and ultraviolet light to convert the alkenyl into carboxyl. 2 molar equivalents of 6-heptynoic acid and 1 molar equivalent of 4, 5-dibromocatechol are subjected to esterification reaction to obtain a compound 33b with alkynyl at two ends.
5 molar equivalents of the compound 33b, 5 molar equivalents of poly (2-oxazoline) terminated with propynyl at both ends and 9 molar equivalents of undecyl polyethylene glycol terminated with azido at both ends are subjected to azido-alkyne reaction to obtain a modified polyether/poly (2-oxazoline) copolymer terminated with alkynyl at both ends. Polystyrene terminated with a hydroxyl group at one end and a bromine atom at one end (see example 4) was reacted with excess sodium azide to give polystyrene terminated with a hydroxyl group at one end and an azide group at the other end. And (3) carrying out azide-alkyne click reaction on the polystyrene obtained by 2 molar equivalents and the modified polyether/poly (2-oxazoline) copolymer obtained by 1 molar equivalent to obtain the polystyrene-modified polyether/poly (2-oxazoline) copolymer-polystyrene three-stage copolymer with two ends capped by hydroxyl. And (3) reacting the obtained three-section copolymer with a UPy derivative with one end being carboxyl under the catalysis of DCC and DMAP to obtain the UPy-polystyrene-modified polyether/poly (2-oxazoline) copolymer-polystyrene-UPy copolymer. And mixing the obtained copolymer with a proper amount of europium chloride solution, and removing the solvent to obtain the dynamic polymer. The material has excellent toughness and can be used for preparing various daily necessities.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (14)

1. A physical phase separation supermolecular dynamic polymer is characterized in that the physical phase separation supermolecular dynamic polymer contains block polymer molecules with hard blocks and soft blocks; the hard segments of the block polymer molecules are mutually mixed or are respectively independent or are partially mixed with each other and partially respectively independent to form a crystalline phase or a phase incompatible with the soft segments or both the crystalline phase and the phase incompatible with the soft segments so as to form phase-separated physical crosslinking or crosslinking and polymerization based on the hard segments; each soft segment of the block polymer molecule is in an amorphous state; at least one soft segment of the block polymer molecule contains at least one group or unit capable of forming supramolecular interaction, and the group or unit forms dynamic supramolecular interaction; the supramolecular interaction is selected from at least the group consisting of halogen bond interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic interaction, ion-dipole interaction, ionic hydrogen bonding interaction, metallophilic interaction, free radical cation dimerization, host-guest interaction.
2. A physically phase-separated supramolecular dynamic polymer as claimed in claim 1, wherein said dynamic polymer comprises block polymer molecules having both hard a and soft B segments, having at least one or a combination of any of the structures as defined in the following formulae:
wherein, the formula (1A) is a straight chain structure, n is the number of hard segment-soft segment alternating units and is more than or equal to 0;
the formula (1B) is a straight chain structure, two end sections are hard sections, n is the number of hard section-soft section alternating units and is more than or equal to 0;
the formula (1C) is a straight chain structure, two end sections are soft sections, n is the number of hard section-soft section alternating units and is more than or equal to 0;
the formula (1D) is a branched structure, and x is the number of hard segment branched chain units connected to the soft segment B; n is the number of hard segment-soft segment alternating units and is more than or equal to 0; y is the number of hard segment-soft segment branch chain units connected to the soft segment B; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3;
the formula (1E) is a branched structure, and x is the number of hard segment branched chain units connected to the soft segment B; n is the number of hard segment-soft segment alternating units and is more than or equal to 0; y is the number of branch chain units which are connected to the soft segment B and have hard segment-soft segment alternation and take the hard segment as an end segment; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3;
the formula (1F) is a branched structure, and x is the number of soft segment branched chain units connected to the hard segment A; n is the number of soft segment-hard segment alternating units and is more than or equal to 0; y is the number of soft segment-hard segment branch chain units connected to the hard segment A; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3;
the formula (1G) is a branched structure, and x is the number of soft segment branched chain units connected to the hard segment A; n is the number of soft segment-hard segment alternating units and is more than or equal to 0; y is the number of branch chain units which are connected to the hard segment A and have soft segment-hard segment alternation and soft segment as an end segment; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3;
the formula (1H) is a ring structure, n is the number of hard segment-soft segment alternating units, and is more than or equal to 1.
3. A physically phase-separated supramolecular dynamic polymer as claimed in claim 1, wherein said dynamic polymer comprises block polymer molecules having both hard a and soft B segments, having at least one or a combination of any of the structures as defined in the following formulae:
wherein, the formula (1A) is a straight chain structure, n is the number of hard segment-soft segment alternating units and is more than or equal to 1;
the formula (1B) is a straight chain structure, two end sections are hard sections, n is the number of hard section-soft section alternating units and is more than or equal to 0;
the formula (1C) is a straight chain structure, two end sections are soft sections, n is the number of hard section-soft section alternating units and is more than or equal to 1;
the formula (1D) is a branched structure, and x is the number of hard segment branched chain units connected to the soft segment B; n is the number of hard segment-soft segment alternating units and is more than or equal to 0; y is the number of hard segment-soft segment branch chain units connected to the soft segment B; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3;
the formula (1E) is a branched structure, and x is the number of hard segment branched chain units connected to the soft segment B; n is the number of hard segment-soft segment alternating units and is more than or equal to 0; y is the number of branch chain units which are connected to the soft segment B and have hard segment-soft segment alternation and take the hard segment as an end segment; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3;
the formula (1F) is a branched structure, and x is the number of soft segment branched chain units connected to the hard segment A; n is the number of soft segment-hard segment alternating units and is more than or equal to 0; y is the number of soft segment-hard segment branch chain units connected to the hard segment A; x is greater than or equal to 0, y is greater than or equal to 1, and the sum of x and y is greater than or equal to 3;
the formula (1G) is a branched structure, and x is the number of soft segment branched chain units connected to the hard segment A; n is the number of soft segment-hard segment alternating units and is more than or equal to 0; y is the number of branch chain units which are connected to the hard segment A and have soft segment-hard segment alternation and soft segment as an end segment; x is greater than or equal to 0, y is greater than or equal to 1, and the sum of x and y is greater than or equal to 3;
the formula (1H) is a ring structure, and n is the number of hard segment-soft segment alternating units, which is more than or equal to 2.
4. A physically separated phase supramolecular dynamic polymer as claimed in claim 1, wherein the main chain of the soft segment of the block polymer molecule is selected from carbon chain structure, carbon hetero chain structure, carbon element chain structure, element hetero chain structure, carbon hetero element chain structure; the main chain of the hard segment of the block polymer molecule is selected from a carbon chain structure, a carbon-mixed chain structure, a carbon element chain structure, an element-mixed chain structure and a carbon-mixed element chain structure.
5. A physically phase-separated supramolecular dynamic polymer as claimed in claim 1, wherein the glass transition temperature of each soft segment in said block polymer molecule is not higher than 25 ℃.
6. A physically phase-separated supramolecular dynamic polymer as claimed in claim 1, characterized in that said hard segment of block polymer molecule is selected from amorphous polymer segment with high glass transition temperature, polymer segment or group rich in hydrogen bonding group, polymer segment or group rich in crystalline phase, polymer segment rich in conjugated structure.
7. The physically separated phase supramolecular dynamic polymer as claimed in claim 1, wherein said block polymer molecule optionally contains any one or more of hydrogen bonding, metal-ligand interaction, and dipole-dipole interaction.
8. A physically separated phase supramolecular dynamic polymer as claimed in claim 1, wherein said block polymer molecule further comprises structural supramolecular interactions.
9. A physically phase-separated supramolecular dynamic polymer as claimed in claim 1, wherein said block polymer molecule contains at least two dynamic supramolecular interactions selected from the group consisting of: pi-pi stacking interactions and metallophilic interactions, host-guest interactions and ionic interactions, host-guest interactions and ion-dipole interactions, host-guest interactions and ionic hydrogen bonding interactions, ionic interactions and ionic dipole interactions, ionic interactions, ion-dipole interactions and ionic hydrogen bonding interactions.
10. A physically phase-separated supramolecular dynamic polymer as claimed in claim 7, characterized in that said block polymer molecule contains at least two dynamic supramolecular interactions selected from the group consisting of: pi-pi stacking interactions and metal-ligand interactions, host-guest interactions and hydrogen bonding interactions, host-guest interactions and metal-ligand interactions, host-guest interactions and dipole-dipole interactions, ionic interactions and metal-ligand interactions, ion-dipole interactions and metal-ligand interactions, ion hydrogen bonding interactions and metal-ligand interactions, ionic interactions and hydrogen bonding interactions, ion-dipole interactions and hydrogen bonding interactions, pi-pi stacking interactions and hydrogen bonding interactions, halogen bonding interactions and metal-ligand interactions, ion-dipole interactions and dipole-dipole interactions, ionic interactions, ion-dipole interactions and dipole-dipole interactions.
11. A physically phase-separated supramolecular dynamic polymer as claimed in any one of claims 1 to 10, wherein said dynamic polymer has any one of the following properties: common solids, elastomers, gels, foams.
12. A physically phase-separated supramolecular dynamic polymer as claimed in any one of claims 1 to 10, wherein the formulation components comprising said dynamic polymer further comprise any one or any of the following additives or utilizable materials: other polymers, auxiliaries, fillers, swelling agents.
13. A physically phase-separated supramolecular dynamic polymer as claimed in claim 12, wherein said other polymer is selected from any one or more of the following: natural polymer compounds and synthetic polymer compounds; the auxiliary agent is selected from any one or more of the following components: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants, toughening agents, coupling agents, solvents, lubricants, mold release agents, plasticizers, thickeners, thixotropic agents, leveling agents, colorants, optical brighteners, delustering agents, antistatic agents, dehydrating agents, sterilization and mold inhibitors, foaming agents, co-foaming agents, nucleating agents, and rheological agents; the filler is selected from any one or more of the following materials: inorganic non-metallic fillers, organic fillers; the swelling agent is selected from any one or more of the following components: water, organic solvent, ionic liquid, oligomer and plasticizer.
14. A physically phase-separated supramolecular dynamic polymer as claimed in any one of claims 1-10, 13, wherein said dynamic polymer is applied to the following materials or articles: self-repairing coating, self-repairing plate, self-repairing sealing material, self-repairing plugging glue, self-repairing conductive glue, tough material, tough elastomer material, flexible material, heat insulation material, shape memory material, force sensor, toy and toy filler.
CN201710522388.5A 2017-06-30 2017-06-30 A kind of physics split-phase supermolecule dynamic aggregation object and its application Pending CN109206824A (en)

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