阅读说明：本技术 一种聚氨酯材料及其制备、回收与再生方法 (Polyurethane material and preparation, recovery and regeneration method thereof ) 是由 白静 史子兴 于 2021-09-08 设计创作，主要内容包括：本发明提出了一种聚氨酯材料及其制备、回收与再生方法,属于聚氨酯技术领域,将含羟基烯酮胺化合物、二元醇、二异氰酸酯及交联剂按照一定比例混合溶解在有机溶剂中,然后高温除去溶剂并反应成型。本发明通过制备含乙烯酮结构的小分子,与异氰酸酯构建动态反应键,添加到聚氨酯体系,使得聚氨酯具有动态可回收性能,相比于线性或交联结构,具有了二者的优点,在提高了耐溶剂性与力学性能的同时,保持了热塑性。这种方法原料易得、成本较低。得到的聚氨酯弹性体材料力学性能等提高的同时,没有损失热塑性,可再次加工使用。可广泛应用到日常生活和工业生产中。(The invention provides a polyurethane material and a preparation, recovery and regeneration method thereof, belonging to the technical field of polyurethane. According to the invention, the micromolecules containing the ketene structure are prepared, and the micromolecules and isocyanate construct a dynamic reaction bond and are added into a polyurethane system, so that the polyurethane has dynamic recoverable performance, and compared with a linear or cross-linked structure, the micromolecules have the advantages of both the linear and cross-linked structures, and the solvent resistance and the mechanical property are improved while the thermoplasticity is maintained. The method has the advantages of easily available raw materials and low cost. The obtained polyurethane elastomer material has improved mechanical properties and the like, does not lose thermoplasticity, and can be processed and used again. Can be widely applied to daily life and industrial production.)

1. A preparation method of a compound containing a hydroxyketene amine structure is characterized by comprising the following steps: the beta-diketone compound and the compound containing hydroxyl and amino are mixed and dissolved in an organic solvent according to a certain molar ratio, stirred and reacted for a certain time, and then the solvent is removed.

2. The method according to claim 1, wherein the β -diketone compound is at least one compound selected from the group consisting of acetylacetone, ethyl acetoacetate, methyl acetoacetate, stearoylbenzoylmethane, dibenzoylmethane, hexafluoroacetylacetone, benzoyl trifluoroacetone, 1-phenyl-1, 3-butanedione, dibenzoylmethane, diethyl malonate, tert-butyl acetoacetate, N-dimethyl-3-oxobutanamide, and N-methylacetoacetamide.

3. The method according to claim 1, wherein the compound having a hydroxyl group and an amino group is at least one selected from the group consisting of ethanolamine, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1-butanol, 3-amino-1-propanol, and diglycolamine.

4. The method according to claim 1, wherein the organic solvent is at least one of tetrahydrofuran, alcohols, ethers, chloroform, dichloromethane, dimethyl sulfoxide, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-pyrrolidone, benzene, toluene, or xylene.

5. The method according to claim 1, wherein the solvent is removed by at least one method selected from the group consisting of rotary evaporation, filtration, distillation under reduced pressure, and recrystallization.

6. A compound containing a hydroxyketene amine structure obtained by the production method according to any one of claims 1 to 5.

7. The preparation method of the polyurethane material is characterized by comprising the following steps: mixing the hydroxyketene amine compound, the diol, the diisocyanate and the crosslinking agent according to claim 6 in a certain proportion, dissolving in an organic solvent, removing the solvent at a high temperature, and reacting for molding.

8. The method according to claim 7, wherein the diol is at least one selected from the group consisting of polyether diol, polytetrahydrofuran diol, polycaprolactone diol, and alkyl diol.

9. The method according to claim 7, wherein the diisocyanate is at least one selected from the group consisting of 4, 4-diisocyanate dicyclohexylmethane, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and 4, 4' -diphenylmethane diisocyanate.

10. The method according to claim 7, wherein the organic solvent is at least one selected from tetrahydrofuran, chloroform, methylene chloride, dimethyl sulfoxide, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-pyrrolidone, benzene, toluene, and xylene.

11. The method according to claim 7, wherein the crosslinking agent is a trihydroxy compound or a triisocyanate ester compound selected from at least one of glycerol, triethanolamine, triphenylmethane triisocyanate, 1,3, 5-tris (6-isocyanatohexyl) -1,3, 5-triazine-2, 4,6(1h,3h,5h) -trione.

12. The production method according to claim 7, characterized in that the hydroxyketene amine compound: a dihydric alcohol: diisocyanate: the molar ratio of the crosslinking agents x: y: z: m satisfies 3 m-2 (x + y-z) or 3 m-2 (z-x-y).

13. The method of claim 7, wherein the high temperature solvent removal temperature is 40 to 100 ℃.

14. A polyurethane material obtained by the production method as claimed in any one of claims 7 to 13.

15. A process for recycling and remoulding polyurethane materials according to claim 14, comprising the steps of:

hot-pressing the polyurethane material chips of claim 14 at high temperature to achieve a re-molding process;

alternatively, the first and second electrodes may be,

dissolving the polyurethane material of claim 14 in a solvent, subjecting the solution to a reverse reaction at a high temperature to obtain a homogeneous solution, and drying the solution to obtain a polyurethane film.

16. The recycling and remolding process as set forth in claim 15, wherein said hot pressing is carried out at a temperature greater than 140 ℃ and a pressure greater than 5 MPa.

17. The recycling and reprofiling process of claim 15, wherein the elevated temperature is above 140 ℃.

18. The recycling and remolding process as set forth in claim 15, wherein the drying reaction temperature is from 40 ℃ to 100 ℃.

19. A method for recycling and regenerating the polyurethane material according to claim 14, characterized in that it comprises the following steps:

(1) dissolving the compound of claim 14 in a solvent and adding a compound containing a hydroxyl group and an amino group simultaneously, and pyrolyzing and crosslinking;

(2) adding diisocyanate into the solution obtained in the step (1), removing the solvent at high temperature, and reacting and forming.

20. The recovery and regeneration method according to claim 19, wherein the compound having hydroxyl group and amino group is at least one selected from the group consisting of ethanolamine, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1-butanol, 3-amino-1-propanol, diglycolamine.

21. The recovery and regeneration process of claim 19, wherein the high temperature decrosslinking temperature is greater than 140 ℃.

22. The recovery and regeneration process according to claim 15 or 19, wherein the solvent is at least one selected from the group consisting of dimethyl sulfoxide, N '-dimethylformamide, N' -dimethylacetamide, and N-methyl-pyrrolidone.

23. The recycling and regenerating process according to claim 19, characterized in that said diisocyanate is selected from at least one of 4, 4-diisocyanate dicyclohexylmethane, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 4' -diphenylmethane diisocyanate.

24. The recycling and regenerating process according to claim 19, characterized in that the temperature for the high temperature solvent removal and reaction forming is 40-100 ℃.

Technical Field

The invention relates to the technical field of polyurethane, in particular to a polyurethane material and a preparation, recovery and regeneration method thereof.

Background

The polyurethane elastomer has the performance between that of plastic and rubber, is resistant to oil, wear, low temperature, aging, high in hardness and good in elasticity, and is widely explored as an essential important polymer in various applications. The water-based coating is widely applied to multiple fields in daily life, such as the fields of home furnishing, buildings, daily necessities, traffic, household appliances and the like. Despite the many advantages of PU, PU and its materials of conventional design have disadvantages in terms of self-healing, reworkability and recyclability due to their irreversible chemical bonds. Since a large amount of use and consumption are not environmentally friendly, recycling and self-healing properties thereof have been studied in recent years.

The preparation method of the CN104558498B polyurethane elastomer discloses that the component A and the component B are mixed and poured into a mould, demoulded and vulcanized at normal temperature, the method integrates the characteristics of polyether polyol and polyester polyol products, so that the products have the advantages of the polyether polyol and the polyester polyol, and the method of gradually polymerizing ester ether is adopted to obtain the ester ether blending polyurethane elastomer in a simple way. However, the polyurethane elastomer prepared by the method is difficult to recycle and is not beneficial to sustainable development.

CN101134843A discloses a preparation method of a high-elasticity polyurethane elastomer, PTMG2000 or PPG3000 is mixed with BDO, a catalyst and an anti-aging agent to be used as a polymer component, isocyanate in a prepolymer component is selected from MDI, carbodiimide modified MDI and a mixture thereof, and the prepared high-elasticity elastomer has narrow hardness range (Shore A80 +/-2) and poor resilience.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a polyurethane material and a preparation, recovery and regeneration method thereof. The method can prepare a recyclable polyurethane material, and can realize the recycling and regeneration of the polyurethane material by adding a proper amount of functional micromolecules into the original mature synthetic route and formula. Strong universality, low cost, simple synthesis and low raw material cost.

The invention firstly synthesizes ketene molecules containing hydroxyl, and then the ketene molecules are added into a polyurethane synthesis system according to a certain proportion to replace diol to synthesize the polyurethane material. The polyurethane material obtained by the method has dynamic bonds on molecular chains, and can be broken at high temperature, so that the recovery and the recycling of the material are realized. Meanwhile, the performance of the material can be designed by adjusting the structure and the adding amount of the small hydroxyl ketene molecules. Further, by utilizing the depolymerization reaction at high temperature, the extension of molecular chains and the redesign of the structure can be realized, and the performance of the recycled material is designed and improved.

The technical scheme of the invention is realized as follows:

the invention provides a preparation method of a compound containing a hydroxyl ketene amine structure, which comprises the following steps: the beta-diketone compound and the compound containing hydroxyl and amino are mixed and dissolved in an organic solvent according to a certain molar ratio, stirred and reacted for a certain time, and then the solvent is removed.

As a further improvement of the invention, the beta-diketone compound is at least one of acetylacetone, ethyl acetoacetate, methyl acetoacetate, stearoylbenzoylmethane, dibenzoylmethane, hexafluoroacetylacetone, benzoyl trifluoroacetone, 1-phenyl-1, 3-butanedione, dibenzoylmethane, diethyl malonate, tert-butyl acetoacetate, N-dimethyl-3-oxobutanamide and N-methylacetoacetamide.

As a further improvement of the invention, the compound containing hydroxyl and amino groups is at least one selected from the group consisting of ethanolamine, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1-butanol, 3-amino-1-propanol, and diglycolamine.

In a further improvement of the present invention, the organic solvent is at least one of tetrahydrofuran, alcohols, ethers, chloroform, dichloromethane, dimethylsulfoxide, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-pyrrolidone, benzene, toluene, or xylene.

As a further improvement of the invention, the method for removing the solvent is at least one selected from the group consisting of rotary evaporation, filtration, distillation under reduced pressure and recrystallization.

The invention further protects a compound containing a hydroxy ketene amine structure prepared by the preparation method.

The invention further provides a preparation method of the polyurethane material, which comprises the following steps: mixing the hydroxyl ketene amine compound, dihydric alcohol, diisocyanate and a cross-linking agent according to a certain proportion, dissolving in an organic solvent, removing the solvent at high temperature, and reacting and forming.

As a further improvement of the invention, the diol is at least one selected from the group consisting of polyether diol, polytetrahydrofuran diol, polycaprolactone diol, and alkyl diol.

As a further improvement of the invention, the diisocyanate is selected from at least one of 4, 4-diisocyanate dicyclohexylmethane, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and 4, 4' -diphenylmethane diisocyanate.

As a further improvement of the present invention, the organic solvent is at least one selected from tetrahydrofuran, chloroform, dichloromethane, dimethylsulfoxide, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-pyrrolidone, benzene, toluene, or xylene.

In a further improvement of the present invention, the crosslinking agent is a trihydroxy compound or a triisocyanate ester compound, and is at least one selected from glycerol, triethanolamine, triphenylmethane triisocyanate, and 1,3, 5-tris (6-isocyanatohexyl) -1,3, 5-triazine-2, 4,6(1h,3h,5h) -trione.

As a further improvement of the present invention, the hydroxyketene amine compound: a dihydric alcohol: diisocyanate: the molar ratio of the crosslinking agents x: y: z: m satisfies 3 m-2 (x + y-z) or 3 m-2 (z-x-y).

As a further improvement of the invention, the temperature for removing the solvent at high temperature is 40-100 ℃.

The invention further protects the polyurethane material prepared by the preparation method.

The invention further provides a method for recovering and remolding the polyurethane material, which comprises the following steps:

hot-pressing the polyurethane material fragments at high temperature to realize secondary molding processing;

alternatively, the first and second electrodes may be,

dissolving the polyurethane material in a solvent, carrying out reverse reaction at high temperature to obtain a uniform solution, and drying the solution for reaction to obtain the polyurethane film.

As a further improvement of the invention, the hot pressing condition is that the temperature is higher than 140 ℃ and the pressure is more than 5 MPa.

As a further development of the invention, the high temperature is such that the temperature at which the reverse reaction takes place is above 140 ℃.

As a further improvement of the invention, the drying reaction temperature is 40-100 ℃.

The invention further provides a regeneration method of the polyurethane material, which comprises the following steps:

(1) the polyurethane material is put into a solvent, and a compound containing hydroxyl and amino is added at the same time, and the crosslinking is carried out at high temperature,

(2) adding diisocyanate into the solution obtained in the step (1), removing the solvent at high temperature, and reacting and forming.

As a further improvement of the invention, the compound containing hydroxyl and amino groups is at least one selected from the group consisting of ethanolamine, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1-butanol, 3-amino-1-propanol, and diglycolamine.

As a further development of the invention, the pyrolysis crosslinking temperature is above 140 ℃.

As a further improvement of the present invention, the solvent is at least one selected from the group consisting of dimethyl sulfoxide, N '-dimethylformamide, N' -dimethylacetamide, and N-methyl-pyrrolidone.

As a further improvement of the invention, the diisocyanate is selected from at least one of 4, 4-diisocyanate dicyclohexylmethane, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and 4, 4' -diphenylmethane diisocyanate.

As a further improvement of the invention, the temperature for removing the solvent and performing reaction forming at high temperature is 40-100 ℃.

The invention has the following beneficial effects: according to the invention, the micromolecules containing the ketene structure are prepared, and the micromolecules and isocyanate construct a dynamic reaction bond and are added into a polyurethane system, so that the polyurethane has dynamic recoverable performance, and compared with a linear or cross-linked structure, the micromolecules have the advantages of both the linear and cross-linked structures, and the solvent resistance and the mechanical property are improved while the thermoplasticity is maintained. The method has the advantages of easily available raw materials and low cost. The obtained polyurethane elastomer material has improved mechanical properties and the like, does not lose thermoplasticity, and can be processed and used again. Can be widely applied to daily life and industrial production.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a nuclear magnetic diagram of 4- ((2-hydroxyethyl) amino) pent-3-en-2-one prepared in example 1;

FIG. 2 is a nuclear magnetic map of ethyl 3- ((2-hydroxyethyl) amino) but-2-enoate prepared in example 2;

FIG. 3 is a stress-strain plot of the polyurethane for different 4- ((2-hydroxyethyl) amino) pent-3-en-2-one contents in examples 3-5;

FIG. 4 is a stress-strain graph of the recycled new polyurethanes prepared in examples 6-10.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

In 5mL of tetrahydrofuran, 1.001 g of acetylacetone and 0.61 g of ethanolamine were dissolved and reacted at 45 ℃ for 12 hours. Removing the solvent by rotary evaporation, and drying for 12 hours in a vacuum oven at 40 ℃ to obtain the 4- ((2-hydroxyethyl) amino) pent-3-en-2-one. FIG. 1 is a nuclear magnetic diagram of the 4- ((2-hydroxyethyl) amino) pent-3-en-2-one produced.

Example 2

1.3014 g of ethyl acetoacetate and 0.61 g of ethanolamine were dissolved in 5mL of ethanol and reacted at 45 ℃ for 12 hours. Removing the solvent by rotary evaporation, and drying for 12 hours in a vacuum oven at 40 ℃ to obtain the 3- ((2-hydroxyethyl) amino) butyl-2-ethyl enoate. FIG. 2 is a nuclear magnetic diagram of the resulting ethyl 3- ((2-hydroxyethyl) amino) but-2-enoate.

Example 3

PTMEG 4 g, IPDI 1.02 g and triethanolamine 0.03 g were dissolved in 20ml of tetrahydrofuran, heated at 50 ℃ for 24 hours, and the solvent was removed at 100 ℃ to carry out reaction molding.

Example 4

PTMEG 2 g, 4- ((2-hydroxyethyl) amino) pent-3-en-2-one (content: 50% of the total amount of PTMEG in example 3) 0.2864 g obtained in example 1, IPDI 1.02 g and triethanolamine 0.03 g were dissolved in 20ml of tetrahydrofuran, heated at 50 ℃ for 24 hours, and the solvent was removed at 100 ℃ to carry out reaction molding.

Example 5

PTMEG 3 g, 0.1432 g of 4- ((2-hydroxyethyl) amino) pent-3-en-2-one (content: 25% of the total amount of PTMEG in example 3) obtained in example 1, IPDI 1.02 g and triethanolamine 0.03 g were dissolved in 20ml of tetrahydrofuran, heated at 50 ℃ for 24 hours, and then the solvent was removed at 100 ℃ to carry out reaction molding.

Example 6

PTMEG 3.4 g, 4- ((2-hydroxyethyl) amino) pent-3-en-2-one (content: 15% of the total amount of PTMEG in example 3) 0.086 g obtained in example 1, IPDI 1.02 g and triethanolamine 0.03 g were dissolved in 20ml of tetrahydrofuran, heated at 50 ℃ for 24 hours, and the solvent was removed at 100 ℃ to carry out reaction molding.

FIG. 3 is a stress-strain plot of the polyurethanes for different 4- ((2-hydroxyethyl) amino) pent-3-en-2-one contents in examples 3-6.

Example 7

2 g of the polyurethane material obtained in example 4 and 0.3 g of ethanolamine were added to 20ml of DMAc, and heated at 160 ℃ for 20 minutes to obtain a homogeneous solution, and the homogeneous solution was reacted with 0.826 g of HDI, the solvent was removed at 100 ℃ and reaction was carried out for formation to obtain a novel polyurethane.

Example 8

2 g of the polyurethane material obtained in example 4 and 0.3 g of ethanolamine were added to 20ml of DMAc, and heated at 160 ℃ for 20 minutes to give a homogeneous solution, and the homogeneous solution was reacted with 1.229 g of MDI, and the solvent was removed at 100 ℃ to give a new polyurethane.

Example 9

2 g of the polyurethane material obtained in example 4 and 0.3 g of ethanolamine were added to 20ml of DMAc, and heated at 160 ℃ for 20 minutes to obtain a homogeneous solution, and the homogeneous solution was reacted with 0.855 g of TDI, and then the solvent was removed at 100 ℃ to carry out reaction molding to obtain a novel polyurethane.

Example 10

2 g of the polyurethane material prepared in example 4 and 0.3 g of ethanolamine were added to 20ml of DMAc, and heated at 160 ℃ for 20 minutes to give a homogeneous solution, and the homogeneous solution was reacted with 1.092 g of IPDI, and the solvent was removed at 100 ℃ to give a new polyurethane.

Example 11

2 g of the polyurethane material prepared in example 4 and 0.3 g of ethanolamine were added to 20ml of DMAc, and heated at 160 ℃ for 20 minutes to give a homogeneous solution, and the homogeneous solution was reacted with 1.289 g of HMDI, and the solvent was removed at 100 ℃ to give a new polyurethane.

FIG. 4 is a stress-strain graph of the new polyurethanes after recycling obtained in examples 7-11.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.