CN112979943A - Preparation method of recyclable and renewable all-bio-based non-isocyanate polyurethane - Google Patents
Preparation method of recyclable and renewable all-bio-based non-isocyanate polyurethane Download PDFInfo
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- CN112979943A CN112979943A CN202110208682.5A CN202110208682A CN112979943A CN 112979943 A CN112979943 A CN 112979943A CN 202110208682 A CN202110208682 A CN 202110208682A CN 112979943 A CN112979943 A CN 112979943A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses a preparation method of recyclable reprocessed full-bio-based non-isocyanate polyurethane, the non-isocyanate polyurethane is obtained by utilizing a curing reaction of grease-based cyclic carbonate and biogenic amines containing a rigid structure, a catalyst and highly toxic isocyanate are not needed in the reaction process, and the prepared material has excellent self-repairing, recycling and reprocessing, high biocompatibility, high mechanical strength and other properties. The problem that the existing polyurethane uses high-toxicity isocyanate is effectively solved, bio-based raw materials are used for replacing petrochemical products, the green sustainability of the material is further improved, and the recycling and reprocessing capability enables the damaged material to be recycled, so that the material has more excellent economic benefits and has wide development prospect in replacing the existing polyurethane material.
Description
Technical Field
The invention relates to a preparation method of recyclable and renewable full-bio-based non-isocyanate polyurethane, belonging to the technical field of bio-based high polymer materials.
Background
The polyurethane material has excellent performance, can be used as coating, adhesive, foam, elastomer and the like to be widely applied to the fields of buildings, aviation industry, shoe industry, automobiles, medical industry and the like, and is a polymer material with great development prospect in recent years. Conventional polyurethane materials are mostly obtained by reacting isocyanates with polyols. However, isocyanates have high toxicity, and phosgene used in the preparation process is also extremely toxic and fatal, so that the preparation and use thereof pose great risks to human health and the environment. With the advocation of "green chemistry", the preparation of polyurethane from nontoxic and highly biocompatible biomass materials has become a research hotspot at the present stage, and the preparation of non-isocyanate polyurethane from cyclic carbonate and amine by reaction has become a future development trend of the polyurethane industry.
Although the prior art also has reports related to the preparation of non-isocyanate polyurethane by using grease, only part of bio-based raw materials are used, and with the gradual depletion of petrochemical resources in recent years, the bio-based raw materials still have certain limitations and are not beneficial to sustainable development, so that the development and utilization of all-bio-based polymer materials are concerned more and more.
Disclosure of Invention
The invention provides a preparation method of recyclable and renewable all-bio-based non-isocyanate polyurethane, the used raw materials are all bio-based raw materials, the all-bio-based non-isocyanate polyurethane is obtained by one-step curing under the conditions of no catalyst and no solvent, the method has the advantages of no toxicity and high biocompatibility, the sustainable development concept is met, and the method is simple and easy to operate; the prepared recyclable and renewable all-bio-based non-isocyanate polyurethane has excellent mechanical properties, and meanwhile, the damaged material can be repaired under the external thermal stimulation, and the seriously damaged material can be recycled and reprocessed, so that the recyclable and renewable all-bio-based non-isocyanate polyurethane has wide application prospect in the field of replacing the traditional polyurethane material.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of recoverable and renewable all-biology-based non-isocyanate polyurethane comprises the steps of reacting grease-based cyclic carbonate with biogenic amine under the conditions of no catalyst and no solvent to prepare the recoverable and renewable all-biology-based non-isocyanate polyurethane; the biogenic amine is at least one of pinene derivative 1, 8-menthane diamine, amino modified cellulose, chitosan or amino modified grease derivative.
The biogenic amine is derived from pinene, rosin, cellulose, chitosan and the like in the nature, has unique chemical structures, is easy to realize chemical modification and introduce into a material structure, and enhances the mechanical property and the thermal stability of the material.
In order to take the performance and sustainability of the product into consideration, the grease used for preparing the grease-based cyclic carbonate is at least one of soybean oil, castor oil, tung oil, palm oil or rapeseed oil.
As a specific implementation scheme, the preparation method of the recyclable and renewable all-bio non-isocyanate polyurethane comprises the following steps:
(1) adding epoxidized oil into a pressure reaction kettle, adding a catalyst, introducing carbon dioxide into the reaction kettle, exhausting air in the reaction kettle, finally maintaining the pressure at 0.5-5 MPa, controlling the reaction temperature at 50-100 ℃, and stirring for reaction for 6-48 hours to obtain oil-based cyclic carbonate which is brown viscous liquid; preferably, the reaction temperature is 60-80 ℃, and the reaction time is 6-15 h.
(2) And (2) uniformly stirring the grease-based cyclic carbonate obtained in the step (1) and the biogenic amine at room temperature, pouring the mixture into a mold, and curing the mixture in an oven at the temperature of 50-150 ℃ for 4-60 hours to obtain the full-bio-based non-isocyanate polyurethane, wherein the curing temperature is preferably 70-140 ℃ and the curing time is preferably 8-48 hours.
In the step (2), no catalyst is required to be added, and the amine compound can provide catalytic activity.
The steps (1) to (2) do not need to use an organic solvent, so that the method is environment-friendly, safe and low in cost.
In order to ensure the reaction efficiency, in the step (1), the catalyst is at least one of N, N-dimethylaminopyridine, tetrabutylammonium bromide, 4-dimethylaminopyridine, tetrabutylammonium iodide or L-ascorbic acid, and the molar amount of the catalyst is 2-7% of the molar mass of the epoxy group in the epoxidized vegetable oil.
In order to further improve the reaction efficiency, the catalyst is a mixture of L-ascorbic acid and tetrabutylammonium iodide or tetrabutylammonium bromide in a mass ratio of 1 (3-4).
In order to further improve the product performance, in the step (2), the grease-based cyclic carbonate and the biogenic amine have the ratio of 1: 0.5-1: 1.25 mol ratio, and mixing uniformly.
In the step (2), the material of the mold is teflon or stainless steel.
The recyclable and renewable all-bio-based non-isocyanate polyurethane can be remolded by hot pressing for 2-6 hours at the temperature of 100-150 ℃ and under the pressure of 1-10 MPa. Namely, the damaged material can be repaired under the external thermal stimulation, so that the service life of the material is obviously prolonged.
According to the recyclable and renewable all-bio based non-isocyanate polyurethane prepared by the application, alcoholic hydroxyl groups in ethanol and carbamate groups are subjected to bond exchange reaction so as to be degraded into small molecules, and the renewable all-bio based non-isocyanate polyurethane is obtained after ethanol is removed, cured and recycled. Therefore, the seriously damaged materials or the waste materials can be cured and used again after being degraded by the ethanol, so that the recycling of the materials is realized, and the waste is avoided.
Preferably, the degradation temperature is 130-140 ℃, the degradation pressure is 0.2-2 MPa, and the degradation time is 3-5 h.
The recyclable and renewable all-bio-based non-isocyanate polyurethane prepared by the method has the performances of self-repairing, degradation reprocessing and the like, can be recycled, and can be used for coatings, adhesives and the like.
The prior art is referred to in the art for techniques not mentioned in the present invention.
According to the preparation method of the recyclable and renewable full-bio-based non-isocyanate polyurethane, the used raw materials are all bio-based raw materials, so that the preparation method has the advantages of no toxicity and high biocompatibility, and the material preparation process conforms to the concept of sustainable development; the used carbon dioxide, grease and other bio-based raw materials are all from the nature and are inexhaustible; meanwhile, as the cyclic carbonate reacts with amine to obtain carbamate and hydroxyl functional groups, the hydroxyl and the carbamate can carry out bond exchange reaction under the stimulation of external heat, so that the materials are endowed with the performances of self-repairing, degradation reprocessing and the like, the performance after the self-repairing can be recovered by more than 95 percent, and the performance after the degradation reprocessing can be recovered by more than 90 percent; in addition, because the introduced biology-based amines all contain rigid structures, compared with other grease-based polyurethane, the biology-based amines also have better mechanical properties and thermal stability.
Drawings
FIG. 1 is an infrared spectrum of epoxidized soybean oil, soybean oil based cyclic carbonate of example 1.
FIG. 2 is a first schematic diagram of hot press reprocessing of the non-isocyanate polyurethane of example 1.
FIG. 3 is a second schematic diagram of hot press reprocessing of the non-isocyanate polyurethane of example 1.
FIG. 4 is a schematic representation of the non-isocyanate polyurethane degradation reprocessing of example 4.
FIG. 5 is a diagram showing the state before and after degradation of the non-isocyanate polyurethane in example 4.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
Adding epoxidized soybean oil (95g, 97.4mmol) into a pressure reaction kettle, adding tetrabutylammonium iodide (6.325g) as a catalyst, introducing carbon dioxide into the pressure reaction kettle, staying for 2min, and then emptying, repeating the process for three times to exhaust air in the reaction kettle, finally maintaining the pressure at 2MPa, controlling the reaction temperature at 80 ℃, and stirring for 12h to obtain soybean oil-based cyclic carbonate; stirring and uniformly mixing soybean oil-based cyclic carbonate (6g) and pinene derivative 1, 8-menthane diamine (1.661g) at room temperature, pouring into a polytetrafluoroethylene mold, and curing in an oven at 150 ℃ for 48 hours to obtain the full-bio-based non-isocyanate polyurethane.
As shown in FIG. 1, epoxy group in epoxidized soybean oil is 822cm-1The characteristic absorption peak of (A) disappeared, while 1797cm in the soybean oil-based cyclic carbonate-1The occurrence of a new absorption peak confirms the successful preparation of the cyclic carbonate. The tensile strength of the obtained full-bio-based non-isocyanate polyurethane can reach 22.8 MPa. Meanwhile, the crushed sample was remolded after hot pressing at 150 ℃ for 4 hours under a pressure of 3MPa (as shown in FIGS. 2 to 3), and the tensile strength after remolding was 21.55 MPa.
Example 2
Adding epoxy tung oil (50g) into a pressure reaction kettle, adding tetrabutylammonium iodide (3g) and L-ascorbic acid (0.8g) as catalysts, introducing carbon dioxide into the reaction kettle, standing for 1min, emptying, repeating the process for three times, introducing carbon dioxide again, maintaining the pressure at 0.35MPa, controlling the reaction temperature at 80 ℃, stirring, and reacting for 8h to obtain soybean oil-based cyclic carbonate; uniformly stirring and mixing tung oil cyclic carbonate (6g) and 1, 8-menthane diamine (1.6g) at room temperature, pouring into a polytetrafluoroethylene mold, and curing in an oven at 140 ℃ for 36 hours to obtain the full-bio-based non-isocyanate polyurethane. The tensile strength of the resulting non-isocyanate polyurethane was 23.75MPa, and the crushed sample was remolded after hot pressing at 150 ℃ for 4 hours at a pressure of 3MPa, and the tensile strength after remolding was 22.8 MPa.
Example 3
Adding epoxidized soybean oil (60g) into a pressure reaction kettle, adding tetrabutylammonium bromide (3.8g) and L-ascorbic acid (1.1g) as catalysts, introducing carbon dioxide into the pressure reaction kettle, standing for 3min, emptying, repeating the process for three times to exhaust air in the reaction kettle, finally maintaining the pressure at 1.4MPa, controlling the reaction temperature at 80 ℃, stirring, and reacting for 8h to obtain soybean oil-based cyclic carbonate; stirring and uniformly mixing soybean oil-based cyclic carbonate (3g) and castor oil derivative decamethylene diamine (1.65g) at room temperature, pouring into a polytetrafluoroethylene mold, and curing in an oven at 150 ℃ for 48 hours to obtain the full-bio-based non-isocyanate polyurethane. The tensile strength of the resulting non-isocyanate polyurethane was 21.35MPa, and the crushed sample was remolded after hot pressing at 150 ℃ for 4 hours at a pressure of 3MPa, and the tensile strength after remolding was 20.68 MPa.
Example 4
Adding epoxidized soybean oil (95g, 97.4mmol) into a pressure reaction kettle, adding tetrabutylammonium iodide (6.325g) and L-ascorbic acid (1.6g) as catalysts, then introducing carbon dioxide into the pressure reaction kettle, standing for 2min, emptying, repeating the process for three times to exhaust the air in the reaction kettle, finally maintaining the pressure at 1.6MPa, controlling the reaction temperature at 80 ℃, stirring, and reacting for 8h to obtain soybean oil-based cyclic carbonate; stirring and uniformly mixing soybean oil-based cyclic carbonate (6g) and pinene derivative 1, 8-menthane diamine (1.661g) at room temperature, pouring into a polytetrafluoroethylene mold, and curing in an oven at 150 ℃ for 48 hours to obtain the full-bio-based non-isocyanate polyurethane. The tensile strength of the resulting non-isocyanate polyurethane was 22.76MPa, and the crushed sample was remoldable after hot pressing at 150 ℃ for 4h at a pressure of 3MPa, and the tensile strength after remoldability was 21.92 MPa.
The non-isocyanate polyurethane obtained in examples 1 to 4 was placed in a high pressure reactor, and ethanol was added, as shown in fig. 5, after reaction for 4 hours at 140 ℃ under a pressure of 0.3MPa, the sample was degraded, and then, after removing excess ethanol by rotary evaporation, the sample was poured into a teflon mold and cured again to obtain the non-isocyanate polyurethane, as shown in fig. 4, the performance of the non-isocyanate polyurethane in each example was recovered by more than 90%.
Application example 1
Adding epoxidized soybean oil (95g, 97.4mmol) into a pressure reaction kettle, adding tetrabutylammonium iodide (6.325g) as a catalyst, introducing carbon dioxide into the pressure reaction kettle, staying for 2min, and then emptying, repeating the process three times to exhaust air in the reaction kettle, finally maintaining the pressure at 2MPa, controlling the reaction temperature at 80 ℃, stirring, and reacting for 12h to obtain soybean oil-based cyclic carbonate; mixing soybean oil-based cyclic carbonate (6g) and pinene derivative 1, 8-menthane diamine (1.661g) under stirring at room temperature, and mixingThe mixed liquid is coated between two metal plates (aluminum plate, iron plate, stainless steel plate) (0.08-0.18 mg/mm)2) After curing for 12 hours at 120 ℃, the two metal plates can be bonded, and the bonding strength can reach 15-28 MPa. Meanwhile, the plate with the broken bonding part is placed at 100 ℃ and is pressed for 4 hours by a 500g weight for bonding again, and due to the existence of dynamic covalent bond exchange, the metal plates are bonded together again, so that the bonding strength can recover 95%.
Claims (10)
1. A preparation method of recyclable and renewable all-bio-based non-isocyanate polyurethane is characterized in that grease-based cyclic carbonate and biogenic amine react under the conditions of no catalyst and no solvent to prepare recyclable and renewable all-bio-based non-isocyanate polyurethane; the biogenic amine is at least one of pinene derivative 1, 8-menthane diamine, amino modified cellulose, chitosan or amino modified grease derivative.
2. The method according to claim 1, wherein the oil used for the preparation of the oil-based cyclic carbonate is at least one of soybean oil, castor oil, tung oil, palm oil, and rapeseed oil.
3. The method of claim 1 or 2, comprising the steps of:
(1) adding the epoxidized oil into a pressure reaction kettle, adding a catalyst, introducing carbon dioxide into the reaction kettle, exhausting air in the reaction kettle, finally maintaining the pressure at 0.5-5 MPa, controlling the reaction temperature at 50-100 ℃, and stirring for reaction for 6-48 hours to obtain oil-based cyclic carbonate;
(2) and (2) uniformly stirring the grease-based cyclic carbonate and the biogenic amine obtained in the step (1) at room temperature, pouring the mixture into a mold, and curing the mixture in an oven at the temperature of 50-150 ℃ for 4-60 hours to obtain the full-bio-based non-isocyanate polyurethane.
4. The method according to claim 3, wherein in the step (1), the catalyst is at least one of N, N-dimethylaminopyridine, tetrabutylammonium bromide, 4-dimethylaminopyridine, tetrabutylammonium iodide and L-ascorbic acid, and the molar amount of the catalyst is 2 to 7% by molar mass of the epoxy group in the epoxidized vegetable oil.
5. The method according to claim 4, wherein the catalyst is a mixture of tetrabutylammonium iodide and L-ascorbic acid in a mass ratio of (3-4): 1.
6. The method of claim 3, wherein in step (2), the aliphatic cyclic carbonate and the biogenic amine are reacted in a ratio of 1: 0.5-1: 1.25 mol ratio, and mixing uniformly.
7. The method according to claim 3, wherein in the step (2), the material of the mold is Teflon or stainless steel.
8. The preparation method of claim 1 or 2, wherein the prepared recyclable full-bio based non-isocyanate polyurethane is hot-pressed at a temperature of 140-150 ℃ and a pressure of 1-10 MPa for 2-6h and then remolded.
9. The preparation method of claim 1 or 2, wherein the prepared recyclable all-bio based non-isocyanate polyurethane is degraded into small molecules by bond exchange reaction between alcoholic hydroxyl groups and carbamate groups in ethanol, and the recycled all-bio based non-isocyanate polyurethane is obtained after ethanol is removed, and is solidified and recycled.
10. The preparation method of claim 9, wherein the degradation temperature is 130-140 ℃, the degradation pressure is 0.2-2 MPa, and the degradation time is 3-5 h.
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| CN114380994A (en) * | 2022-01-12 | 2022-04-22 | 中国科学技术大学 | Bio-based non-isocyanate polyurethane and preparation method thereof |
| CN114874436A (en) * | 2022-06-15 | 2022-08-09 | 石河子大学 | Preparation method of sulfydryl modified unsaturated fatty acid based non-isocyanate polyurethane |
| CN115305041A (en) * | 2022-09-14 | 2022-11-08 | 宁波锋成先进能源材料研究院有限公司 | Environment-friendly bio-based polyurethane adhesive and preparation method thereof |
| CN115386091A (en) * | 2022-08-29 | 2022-11-25 | 中国林业科学研究院林产化学工业研究所 | Preparation method, application and regeneration method of high-strength self-healing organic silicon elastomer |
| CN115403765A (en) * | 2022-10-05 | 2022-11-29 | 大连理工大学 | Chemically recyclable high-strength non-isocyanate polyurethane and preparation method thereof |
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| CN114874436A (en) * | 2022-06-15 | 2022-08-09 | 石河子大学 | Preparation method of sulfydryl modified unsaturated fatty acid based non-isocyanate polyurethane |
| CN114874436B (en) * | 2022-06-15 | 2024-03-12 | 石河子大学 | Preparation method of mercapto-modified unsaturated fatty acid based non-isocyanate polyurethane |
| WO2024041129A1 (en) * | 2022-08-23 | 2024-02-29 | 中国林业科学研究院林产化学工业研究所 | Method for preparing biodegradable water-resistant high-strength reprocessable plastic paper, and recycling and reuse method therefor |
| CN115418884A (en) * | 2022-08-23 | 2022-12-02 | 中国林业科学研究院林产化学工业研究所 | Preparation method and recycling method of degradable, waterproof, high-strength and recyclable paper plastic |
| CN115386091A (en) * | 2022-08-29 | 2022-11-25 | 中国林业科学研究院林产化学工业研究所 | Preparation method, application and regeneration method of high-strength self-healing organic silicon elastomer |
| CN115490851A (en) * | 2022-08-29 | 2022-12-20 | 湖北好口福食品有限公司 | Plant oil-based non-isocyanate polyurethane resin and preparation method thereof |
| CN115386091B (en) * | 2022-08-29 | 2023-10-24 | 中国林业科学研究院林产化学工业研究所 | Preparation method, application and regeneration method of high-strength self-healing organosilicon elastomer |
| CN115490851B (en) * | 2022-08-29 | 2024-01-26 | 湖北好口福食品有限公司 | Vegetable oil-based non-isocyanate polyurethane resin and preparation method thereof |
| CN115305041A (en) * | 2022-09-14 | 2022-11-08 | 宁波锋成先进能源材料研究院有限公司 | Environment-friendly bio-based polyurethane adhesive and preparation method thereof |
| CN115403765A (en) * | 2022-10-05 | 2022-11-29 | 大连理工大学 | Chemically recyclable high-strength non-isocyanate polyurethane and preparation method thereof |
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