Dynamic polymer having non-covalent crosslinking structure and application thereof

Abstract

The invention discloses a dynamic polymer having a non-covalent crosslinking structure. The dynamic polymer contains organic boric acid silicon ester bonds on polymer chain backbone; wherein the organic boric acid silicon ester bonds are existed as polymeric chain contacts of the dynamic polymer, and are the necessary condition for forming or maintaining a dynamic polymer structure. The dynamic polymer has energy dissipation performance by means of the organic boric acid silicon ester bonds having strong dynamic reversibility, embodies functional characteristics of stimulation responsiveness and self-repairability, and has a wide application prospect in the fields of sport protection, a functional coating, and a bionic material.

Description

Technical field

[0001] The invention relates to the field of smart polymers, in particular to a dynamic polymer with a non-covalent cross-linked structure composed of dynamic reversible covalent bonds. Background technique

[0002] Dynamic chemistry is a cross-discipline 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 have weaker bond energy and are greatly affected by thermodynamics. The resulting supramolecular structure To some extent, it is not a dynamically stable system. For dynamic covalent chemistry, it has some characteristics similar to supramolecular chemistry, and reversibl...

Examples

preparation example Construction

[0157] In the preparation process of dynamic polymers, after the compounds as raw materials participate in the reaction with each other, the raw material components can be polymerized with organoborate silicate bonds or common covalent bonds as link points to obtain dynamic polymers with higher molecular weight . Among them, the functional groups contained in the raw material components can be completely reacted or partially reacted, and it is not required that all the organic boronic acid groups and / or organic boronic acid ester groups and the silanol and / or silanol precursors completely react with each other to form The organoborate silicate bond, as long as the organoborate silicate bond formed is sufficient to maintain the dynamic polymer structure.

[0158] In the present invention, the preparation process of the dynamic polymer prepared by the above two embodiments is simple, easy to operate, and highly controllable, so it is a preferred embodiment of the present invention....

Embodiment 1

[0265] A linear structure dynamic polymer is prepared by using a small molecule organoboron compound (I) containing a bifunctional group and a small molecule silicon-containing compound (II) containing a bifunctional group.

[0266]

[0267] Weigh a certain amount of organoboron compound (a) (Methyl vinyl boric acid is prepared by the reaction of methyl lithium, vinyl lithium and trimethyl borate; AIBN is used as initiator, triethylamine is used as catalyst, and methyl ethylene is used. Boronic acid and 1,6-hexanedithiol are prepared by thiol-ene click reaction) dissolved in tetrahydrofuran solvent to prepare a 0.8mol / L solution; weigh a certain amount of silicon-containing compound (b) (using dimethyl Allyl chlorosilane, 1,10-decanedithiol as raw materials, AIBN as initiator, triethylamine as catalyst, prepared by thiol-ene click reaction) dissolved in tetrahydrofuran solvent to prepare 0.8mol / L Solution: Take 20ml of tetrahydrofuran solution with organic boron compound dissolve...

Embodiment 2

[0269] The macromolecular organoboron compound (I) containing bifunctional groups and the macromolecular silicon-containing compound (II) containing bifunctional groups are used to prepare linear structure dynamic polymers.

[0270]

[0271] Weigh 7.5 g of boric acid-terminated polyether (a) in a dry and clean beaker (using 1-hydroxyborole-3-ene as a raw material, and reacting it with hydrobromic acid to obtain 3-bromo- 1-Hydroxyborolane is prepared by hydrocarbylation reaction with polyetheramine using potassium carbonate as a catalyst), 60ml of deionized water is added to it, and it is continuously stirred and dissolved at 50°C. After the dissolution is complete, add a small amount of 1mol / L NaOH solution dropwise; weigh 5.2g of silane-terminated polyether (b) (using dihydroxy-terminated polyethylene glycol as raw material, and esterify it with acrylic acid After the intermediate product is prepared, it is then slowly added to the boric acid-terminated polyether solution with m...

Technical field

[0001] The invention relates to the field of smart polymers, in particular to a dynamic polymer with a non-covalent cross-linked structure composed of dynamic reversible covalent bonds. Background technique

[0002] Dynamic chemistry is a cross-discipline 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 have weaker bond energy and are greatly affected by thermodynamics. The resulting supramolecular structure To some extent, it is not a dynamically stable system. For dynamic covalent chemistry, it has some characteristics similar to supramolecular chemistry, and reversibl...

Examples

preparation example Construction

[0157] In the preparation process of dynamic polymers, after the compounds as raw materials participate in the reaction with each other, the raw material components can be polymerized with organoborate silicate bonds or common covalent bonds as link points to obtain dynamic polymers with higher molecular weight . Among them, the functional groups contained in the raw material components can be completely reacted or partially reacted, and it is not required that all the organic boronic acid groups and / or organic boronic acid ester groups and the silanol and / or silanol precursors completely react with each other to form The organoborate silicate bond, as long as the organoborate silicate bond formed is sufficient to maintain the dynamic polymer structure.

[0158] In the present invention, the preparation process of the dynamic polymer prepared by the above two embodiments is simple, easy to operate, and highly controllable, so it is a preferred embodiment of the present invention....

Embodiment 1

[0265] A linear structure dynamic polymer is prepared by using a small molecule organoboron compound (I) containing a bifunctional group and a small molecule silicon-containing compound (II) containing a bifunctional group.

[0266]

[0267] Weigh a certain amount of organoboron compound (a) (Methyl vinyl boric acid is prepared by the reaction of methyl lithium, vinyl lithium and trimethyl borate; AIBN is used as initiator, triethylamine is used as catalyst, and methyl ethylene is used. Boronic acid and 1,6-hexanedithiol are prepared by thiol-ene click reaction) dissolved in tetrahydrofuran solvent to prepare a 0.8mol / L solution; weigh a certain amount of silicon-containing compound (b) (using dimethyl Allyl chlorosilane, 1,10-decanedithiol as raw materials, AIBN as initiator, triethylamine as catalyst, prepared by thiol-ene click reaction) dissolved in tetrahydrofuran solvent to prepare 0.8mol / L Solution: Take 20ml of tetrahydrofuran solution with organic boron compound dissolve...

Embodiment 2

[0269] The macromolecular organoboron compound (I) containing bifunctional groups and the macromolecular silicon-containing compound (II) containing bifunctional groups are used to prepare linear structure dynamic polymers.

[0270]

[0271] Weigh 7.5 g of boric acid-terminated polyether (a) in a dry and clean beaker (using 1-hydroxyborole-3-ene as a raw material, and reacting it with hydrobromic acid to obtain 3-bromo- 1-Hydroxyborolane is prepared by hydrocarbylation reaction with polyetheramine using potassium carbonate as a catalyst), 60ml of deionized water is added to it, and it is continuously stirred and dissolved at 50°C. After the dissolution is complete, add a small amount of 1mol / L NaOH solution dropwise; weigh 5.2g of silane-terminated polyether (b) (using dihydroxy-terminated polyethylene glycol as raw material, and esterify it with acrylic acid After the intermediate product is prepared, it is then slowly added to the boric acid-terminated polyether solution with m...

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