Self-healing polyurethane resin containing disulfide bond and preparation method thereof

Abstract

The invention relates to self-healing polyurethane resin containing disulfide bond and a preparation method thereof. The polyurethane resin comprises, by weight parts, 10-30 parts of polyether or polyester polyol, 3-20 parts of polyisocyanates, 1-10 parts of chain extender containing the disulfide bond, 0.001-1 part of organic tin or tertiary amine catalyst and 50-80 parts of organic solvent. The method for preparing the self-healing polyurethane resin containing the disulfide bond comprises the steps of weighing raw materials, stirring, heating and performing dehydration for the polyether or polyester polyol under vacuum conditions, lowering the temperature to 85 DEG C or below, adding the polyisocyanates and the organic tin or tertiary amine catalyst, reacting, lowering the temperature to 50 DEG C or below, adding the organic solvent and the chain extender containing the disulfide bond, reacting and performing vacuum defoamation to obtain the self-healing polyurethane resin. The self-healing polyurethane resin heals by itself under the heating or ultraviolet (UV) light conditions, the required conditions are mild, the healing speed is high, the effect is good, the preparation method is simple and easy to control, and raw materials are goods of commercialized production and are cheap and easy to obtain.

Description

technical field

[0001] The invention belongs to the field of polyurethane resin and its preparation, in particular to a self-healing polyurethane resin containing disulfide bonds and its preparation method. Background technique

[0002] Like most polymer materials, polyurethane materials are inevitably vulnerable to external mechanical damage during use, which shortens their service life and greatly increases the maintenance and replacement costs of materials. To solve this problem, making polyurethane materials have self-healing ability is a very effective solution.

[0003] At present, there have been reports on self-healing polyurethane materials (Liu Xuanxuan. Research on self-healing linear polyurethane based on thermoreversible Diels-Alder reaction [D]. Shanghai: Shanghai Jiaotong University, 2013; JunLing, MinZhiRong, MingQiuZhang, Photo- stimulatedself-healingpolyurethanecontainingdihydroxylcoumarinderivatives[J].Polymer,2012,53,2691-2698;BiswajitGhosh,MarekW.Urban,...

Examples

Embodiment 1

[0029]Preparation of self-healing polyurethane resin: In parts by weight, add 23.4 parts of polytetrahydrofuran diol (Mn~1810) into a three-necked flask, stir and heat to 110°C, vacuumize and keep the vacuum of the reaction system at 0.08MPa Above, dehydrate for 2 hours, then lower the temperature to 70°C, add 4.6 parts of hexamethylene diisocyanate and 0.2 parts of dibutyltin dilaurate, continue to stir and react at 70°C under nitrogen protection for 2 hours, then cool down to 25°C , dropwise add a mixed solution of 2 parts of 2-hydroxyethyl disulfide and 70 parts of dimethylacetamide, continue to react for 2 hours under the protection of nitrogen, vacuum defoaming after completion, to obtain a mass fraction of 30% Polyurethane resin solution.

[0030] Preparation of self-healing polyurethane film: coating the obtained polyurethane resin solution on a glass plate, and heating in vacuum at 50° C. for 12 hours to obtain a polyurethane film with self-healing function.

[0031] ...

Embodiment 2

[0038] Preparation of self-healing polyurethane resin: In parts by weight, add 20.5 parts of polytetrahydrofuran diol (Mn~1810) into a three-necked flask, stir and heat to 110°C, vacuumize and keep the vacuum of the reaction system at 0.08MPa Above, dehydrate for 2 hours, then lower the temperature to 70°C, add 5.9 parts of hexamethylene diisocyanate and 0.2 parts of dibutyltin dilaurate, continue to stir and react at 70°C under nitrogen protection for 2 hours, then cool down to 25°C , dropwise add a mixed solution of 3.5 parts of 2-hydroxyethyl disulfide and 70 parts of dimethylacetamide, continue to react for 2 hours under the protection of nitrogen, vacuum defoaming after completion, to obtain a mass fraction of 30% Polyurethane resin solution.

[0039] Preparation of self-healing polyurethane film: coating the obtained polyurethane resin solution on a glass plate, and heating in vacuum at 50° C. for 12 hours to obtain a polyurethane film with self-healing function.

[004...

Embodiment 3

[0045] Preparation of self-healing polyurethane resin: In parts by weight, add 18.3 parts of polytetrahydrofuran diol (Mn~1810) into a three-necked flask, stir and heat to 110°C, vacuumize and keep the vacuum of the reaction system at 0.08MPa Above, dehydrate for 2 hours, then lower the temperature to 70°C, add 7 parts of hexamethylene diisocyanate and 0.2 parts of dibutyltin dilaurate, continue to stir and react for 2 hours at a temperature of 70°C under nitrogen protection, and then cool down to 25°C , dropwise add a mixed solution of 4.7 parts of 2-hydroxyethyl disulfide and 70 parts of dimethylacetamide, continue to react for 2 hours under the protection of nitrogen, vacuum defoaming after completion, to obtain a mass fraction of 30% Polyurethane resin solution.

[0046] Preparation of self-healing polyurethane film: coating the obtained polyurethane resin solution on a glass plate, and heating in vacuum at 50° C. for 12 hours to obtain a polyurethane film with self-healin...

technical field

[0001] The invention belongs to the field of polyurethane resin and its preparation, in particular to a self-healing polyurethane resin containing disulfide bonds and its preparation method. Background technique

[0002] Like most polymer materials, polyurethane materials are inevitably vulnerable to external mechanical damage during use, which shortens their service life and greatly increases the maintenance and replacement costs of materials. To solve this problem, making polyurethane materials have self-healing ability is a very effective solution.

[0003] At present, there have been reports on self-healing polyurethane materials (Liu Xuanxuan. Research on self-healing linear polyurethane based on thermoreversible Diels-Alder reaction [D]. Shanghai: Shanghai Jiaotong University, 2013; JunLing, MinZhiRong, MingQiuZhang, Photo- stimulatedself-healingpolyurethanecontainingdihydroxylcoumarinderivatives[J].Polymer,2012,53,2691-2698;BiswajitGhosh,MarekW.Urban,...

Examples

Embodiment 1

[0029]Preparation of self-healing polyurethane resin: In parts by weight, add 23.4 parts of polytetrahydrofuran diol (Mn~1810) into a three-necked flask, stir and heat to 110°C, vacuumize and keep the vacuum of the reaction system at 0.08MPa Above, dehydrate for 2 hours, then lower the temperature to 70°C, add 4.6 parts of hexamethylene diisocyanate and 0.2 parts of dibutyltin dilaurate, continue to stir and react at 70°C under nitrogen protection for 2 hours, then cool down to 25°C , dropwise add a mixed solution of 2 parts of 2-hydroxyethyl disulfide and 70 parts of dimethylacetamide, continue to react for 2 hours under the protection of nitrogen, vacuum defoaming after completion, to obtain a mass fraction of 30% Polyurethane resin solution.

[0030] Preparation of self-healing polyurethane film: coating the obtained polyurethane resin solution on a glass plate, and heating in vacuum at 50° C. for 12 hours to obtain a polyurethane film with self-healing function.

[0031] ...

Embodiment 2

[0038] Preparation of self-healing polyurethane resin: In parts by weight, add 20.5 parts of polytetrahydrofuran diol (Mn~1810) into a three-necked flask, stir and heat to 110°C, vacuumize and keep the vacuum of the reaction system at 0.08MPa Above, dehydrate for 2 hours, then lower the temperature to 70°C, add 5.9 parts of hexamethylene diisocyanate and 0.2 parts of dibutyltin dilaurate, continue to stir and react at 70°C under nitrogen protection for 2 hours, then cool down to 25°C , dropwise add a mixed solution of 3.5 parts of 2-hydroxyethyl disulfide and 70 parts of dimethylacetamide, continue to react for 2 hours under the protection of nitrogen, vacuum defoaming after completion, to obtain a mass fraction of 30% Polyurethane resin solution.

[0039] Preparation of self-healing polyurethane film: coating the obtained polyurethane resin solution on a glass plate, and heating in vacuum at 50° C. for 12 hours to obtain a polyurethane film with self-healing function.

[004...

Embodiment 3

[0045] Preparation of self-healing polyurethane resin: In parts by weight, add 18.3 parts of polytetrahydrofuran diol (Mn~1810) into a three-necked flask, stir and heat to 110°C, vacuumize and keep the vacuum of the reaction system at 0.08MPa Above, dehydrate for 2 hours, then lower the temperature to 70°C, add 7 parts of hexamethylene diisocyanate and 0.2 parts of dibutyltin dilaurate, continue to stir and react for 2 hours at a temperature of 70°C under nitrogen protection, and then cool down to 25°C , dropwise add a mixed solution of 4.7 parts of 2-hydroxyethyl disulfide and 70 parts of dimethylacetamide, continue to react for 2 hours under the protection of nitrogen, vacuum defoaming after completion, to obtain a mass fraction of 30% Polyurethane resin solution.

[0046] Preparation of self-healing polyurethane film: coating the obtained polyurethane resin solution on a glass plate, and heating in vacuum at 50° C. for 12 hours to obtain a polyurethane film with self-healin...

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