A dynamic polymer with a dynamic cross-linked structure

A dynamic cross-linking and polymer technology, applied in the field of intelligent polymers, can solve problems such as slowness, difficulty in stabilizing imine bonds, and poor stability of thiols

Active Publication Date: 2020-04-10
厦门天策材料科技有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] However, the chemical equilibrium process in traditional dynamic polymers is often slow because it involves the breaking and formation of covalent bonds, and it is often necessary to add catalysts or provide energy from the outside to accelerate the equilibrium process.
In addition, some reversible covalent bonds themselves have certain defects in the actual use process, which limit the use environment and application fields of dynamic polymers.
For example, the traditional transesterification reaction is the earliest reversible exchange reaction used by people, but the conditions of the transesterification reaction are relatively harsh, and generally need to be completed under the conditions of adding alkali and reflux. At the same time, the dynamic activity of the traditional ester bond is poor. The application of dynamic polymers constructed by transesterification has limitations; products based on furan-maleimide Diels-Alder cycloaddition generally require dissociation reactions at high temperatures, and this reaction in organic solvents The process is slow; the imine bond formed by the reaction of primary amine and aldehyde is strongly affected by the pH, which makes it difficult to stabilize such imine bond under normal conditions; the reversible exchange reaction of amino transfer needs to be carried out under the action of special protease; Based on the dynamic reversible bond of the alkoxynitrogen group, the dissociation reaction temperature often has to reach 100-130°C. At the same time, the carbon-centered free radical generated by the dissociation of the alkoxynitrogen group is sensitive to oxygen and high temperature, and the resulting irreversible The bonding will affect the performance of the material; the dynamic polymer containing trithioester group needs to be irradiated by ultraviolet light to undergo dynamic exchange reaction; the disulfide bond in the dynamic covalent bond has better dynamics, and its The exchange reaction can be carried out under low temperature conditions, but the mercaptan itself is less stable, and it will react with the surrounding air to produce continuous oxidation during use, so that the mercaptan content in the reversible system is continuously reduced, which affects the use of materials
The existence of such situations makes it difficult for the characteristics of the dynamic reversible covalent bond itself to be fully reflected under normal conditions. It is necessary to develop a new type of dynamic polymer so that the dynamic reversible covalent bond in the system can simultaneously satisfy the requirements of reversible reactions. Fast speed, mild reaction conditions, and controllable reversible reaction conditions to solve the above-mentioned problems in the prior art

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  • A dynamic polymer with a dynamic cross-linked structure
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preparation example Construction

[0261] In the above-mentioned preparation embodiment, it is also possible to selectively introduce a suitable amount of monofunctional organoboron compound (I) and / or monofunctional silicon-containing compound (II) components, which can be adjusted through component formulation , to obtain the dynamic cross-linked structure. Monofunctional compounds can play a role in adjusting crosslink density, dynamics, mechanical strength and so on.

[0262] In the preparation embodiment described above, the reaction of other reactive groups can also be achieved by introducing organic boronic acid groups and / or organic boronic acid ester groups, silicon hydroxyl and / or silicon hydroxyl precursors, organic boric acid silicon ester bonds However, compound components containing other reactive groups can be achieved together. The compound containing only other reactive groups can be any suitable compound that can achieve the reaction with other reactive groups in organoboron compound (I) and / ...

Embodiment 1

[0412] A dynamic polymer with a dynamic cross-linking structure is prepared by using a small-molecule organoboron compound (I) containing four functional groups and a small-molecule silicon-containing compound (II) containing two functional groups.

[0413]

[0414] Weigh a certain amount of organoboron compound (a) (using AIBN as the initiator and triethylamine as the catalyst, using vinylboronic acid, vinylboronic acid dibutyl ester and 1,6-hexanedithiol through thiol-ene click reaction Prepared) dissolved in tetrahydrofuran solvent to prepare a 0.8mol / L solution; Measure 40ml of tetrahydrofuran solution dissolved with organoboron compound and pour it into a dry and clean flask, add 4ml of deionized water, drop a little acetic acid and mix evenly, Slowly add the silicon-containing compound (b) of 5.02g therein again (utilize dimethylallyl chlorosilane, 1,10-decanedithiol as raw material, take AIBN as initiator, triethylamine as catalyst, pass thiol-ene click reaction prep...

Embodiment 2

[0416] A dynamic polymer with a dynamic cross-linking structure is prepared by using a small-molecule organoboron compound (I) containing four functional groups and a macromolecular silicon-containing compound (II) containing two functional groups.

[0417]

[0418]Add 15ml of phenylboronic acid-terminated polyethylene glycol (a) into a dry and clean three-necked flask (with polyethylene glycol 400 and 2-bromopropionyl bromide as raw materials and triethylamine as a catalyst to prepare dibromo-terminated polyethylene glycol (a) diol, and then it and 2-aminomethylphenylboronic acid are obtained through alkylation reaction to obtain the final product), heated to 80°C, in which a small amount of deionized water and acetic acid are added dropwise, and then 42ml of acetic acid is added dropwise under stirring The methoxysilane-modified silicone oil (b) (made from dimethylvinylmethoxysilane and hydrogen-terminated silicone oil with a viscosity of about 2000mPa·s as raw materials, ...

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Abstract

A dynamic polymer with a dynamic cross-linked structure. The dynamic polymer contains an organoborate silicon ester bond on a polymer chain backbone and / or on a crosslinking backbone between polymer chains of a cross-linked network. The organoborate silicon ester bond is necessary for the formation and maintenance of a dynamic polymer structure. The dynamic polymer provides a class of polymers with diverse structures and properties. Through modulation of a reactant structure, dynamic polymers with different properties can be prepared. In addition, the organoborate silicon ester bond in a polymer provides a strong dynamic reversibility, thereby realizing functional properties such as stimuli responsiveness, self-repair, recyclability, and the like. The existence of the organoborate silicon ester bond also enables energy absorption in the polymer and can toughen a polymer material under specific structural configurations. The dynamic polymer can be used to make a shock absorbing material, anti-impact protection material, self-repairing material, high-toughness material, and the like.

Description

technical field [0001] The invention relates to the field of intelligent polymers, in particular to a dynamic polymer with a dynamic crosslinking structure composed of dynamic reversible covalent bonds. Background technique [0002] Dynamic chemistry is an interdisciplinary subject developed by combining supramolecular chemistry and dynamic covalent chemistry in covalent chemistry. Traditional molecular chemistry focuses on stable covalent interactions, while dynamic chemistry focuses on relatively weak non-covalent interactions and reversible covalent bonds. Among them, supramolecular chemistry is based on non-covalent intermolecular interactions. Compared with traditional covalent bonds, these non-covalent interactions generally have weaker bond energy and are greatly affected by thermodynamics. The formed supramolecular To some extent, the structure is not a stable system, and it is easy to be destroyed, which has caused many restrictions on its characterization, researc...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G77/22C08G65/336C08G69/42C08G79/08C08G69/48C08F236/08C08F8/34C08G81/02C08G81/00C08G77/398C08G83/00C08F8/42C08G59/14C08G77/44
CPCC08F8/34C08F8/42C08G59/1483C08G65/336C08G69/42C08G69/48C08G77/22C08G77/398C08G77/44C08G79/08C08G81/00C08G81/021C08G81/024C08G81/027C08G83/001C08F236/08C08F230/04C08G65/34C08L83/08C08L87/00
Inventor 不公告发明人
Owner 厦门天策材料科技有限公司
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