CN112225876A - Preparation method of rosin-based self-repairing polyurethane based on Diels-Alder reaction - Google Patents
Preparation method of rosin-based self-repairing polyurethane based on Diels-Alder reaction Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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Abstract
The invention discloses a preparation method of rosin-based self-repairing polyurethane based on Diels-Alder reaction, belonging to the technical field of high polymer materials. The preparation method comprises the steps of uniformly stirring the rosin-based polyol and the diisocyanate, adding the catalyst, heating in a water bath, uniformly stirring, and reacting to obtain a prepolymer; and then adding a furan structure derivative, reacting to obtain a furan-terminated polyurethane prepolymer, adding a maleic amide derivative, reacting in a water bath, pouring into a polytetrafluoroethylene template after the reaction is finished, curing, and removing the solvent to obtain the rosin-based self-repairing polyurethane. The rosin is sourced from forestry biomass resources, the cost is low, the reaction condition is mild, and the operation is simple.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of rosin-based self-repairing polyurethane based on Diels-Alder reaction.
Background
Polyurethane (PU) is a polymer synthesized by simple polyaddition of a polyol, an isocyanate and a chain extender, and polyurethanes made by different processes, such as from soft sponges to elastomers, from elastic fibers to shoe sole pastes, are one of the most common engineering materials, and are widely used in the fields of coatings, electronics, automotive industry, medical supplies, sports equipment, and the like. However, the combined effects of internal and external factors tend to cause microscopic or macroscopic damage to the material during processing, transportation, storage and use, resulting in a reduction in the mechanical properties of the material. Polymers are susceptible to deep fracture damage, however, it is extremely difficult to detect and repair deep internal fractures. Inspired by the fact that organisms can automatically repair damage, researchers invent various methods to eliminate micro-damage in materials, avoid damage expansion, improve the safety and durability of the materials and prolong the service life of the materials.
According to the self-repairing principle, two self-repairing systems exist at present. One is external-aid self-repairing, and the microcapsules containing the repairing agent are preset in the material, so that the microcapsules are broken when the material is damaged, and the repairing agent flows out to realize self-repairing; one is intrinsic self-repairing, which is realized by utilizing intermolecular or intramolecular interaction in the material and can be divided into covalent bond action and non-covalent bond action. Non-covalent interactions include hydrogen bonding, pi-pi conjugation, metal coordination, and the like, and covalent interactions include Diels-alder (da) reactions, dynamic disulfide bonds, dynamic transesterification, dynamic siloxane equilibration, transamidation reactions, imine and acylhydrazone bond exchanges, and the like. The intrinsic self-repairing polyurethane does not need an additional reagent, only depends on intramolecular or intermolecular bonding, is reversible repair, has the advantages of being capable of repairing for many times and the like, and is increasingly concerned by people. CN102153856A discloses a photo-induced reversible self-repairing polyurethane film, a preparation method and a repairing method thereof, wherein the preparation method is complex, the obtained molecular weight is small, the molecular weight distribution is wide, and the polyurethane has poor mechanical properties and low resilience. CN109111562A discloses a self-repairing polyurethane, a preparation method and a self-repairing method thereof, wherein the obtained polyurethane has narrow molecular division, good mechanical property and tensile strength of 17-28MPa, but the self-repairing efficiency is low and is only 55%. Therefore, it is necessary to develop a polyurethane material having better mechanical properties and also higher self-healing efficiency.
Rosin is one of the important natural resources in China, and the area of pine forest in China is about 2500km2The grease collecting amount can be more than 200 ten thousand tons every year. Rosin is an important chemical raw material in China, and the current yield is about 50 ten thousand tons/year, which is the first in the world. However, more than 50% of rosin is directly exported to other countries, and export products are mainly processed simply, so that the speaking right of international market price is difficult to master. By developing and producing rosin deep processing products in developed countries in Europe and America, the added value of the products can be improved by 2-20 times compared with the raw materials, the deep processing utilization rate is close to 100%, and the economic benefit of the rosin is far from being fully exerted only by about 40% in China. Therefore, the development and utilization of a new way is a problem which needs to be solved urgently in the deep processing research of rosin resources, and meanwhile, the development of high-added-value high polymer materials by using abundant rosin to replace expensive petrochemical raw materials has an obvious promotion effect on the change of the ecological environment.
The rosin phenanthrene ring has a good enhancing effect on the mechanical and thermal stability of the polyurethane material, but the research on the structural design, preparation and performance of the rosin-based self-repairing polyurethane material is not reported in documents. Therefore, the invention tries to introduce a rosin structure on the main chain of polyurethane and carry out thermal reversible DA reaction to prepare the self-repairing polyurethane material with high self-repairing rate and excellent mechanical property.
Disclosure of Invention
The technical problem to be solved is as follows: the invention provides a preparation method of rosin-based self-repairing polyurethane based on Diels-Alder reaction, the preparation process is simple and efficient, the prepared material has excellent mechanical property, the tensile strength is 12.7-18.8 MPa, the elongation at break is 48-74%, the self-repairing efficiency can reach 94.6% at most, the rosin has excellent mechanical property and self-repairing property, the special structure of forest product characteristic resource rosin is effectively utilized, the application field of rosin is widened, and the additional value of rosin is improved.
The technical scheme is as follows: a preparation method of rosin-based self-repairing polyurethane based on Diels-Alder reaction comprises the following steps: uniformly stirring rosin-based polyol and diisocyanate, wherein the molar ratio of the rosin-based polyol to the diisocyanate is 1: 1-4, adding a catalyst, heating and uniformly stirring in a water bath at the temperature of 40-80 ℃, and reacting for 2-10 hours to obtain a prepolymer; and then adding a furan ring derivative, reacting for 2-10 h at 0-60 ℃ to obtain a furan-terminated polyurethane prepolymer, adding a maleic amide derivative, reacting for 2-24 h in a water bath at 40-80 ℃, pouring into a polytetrafluoroethylene template after the reaction is finished, curing, and removing the solvent to obtain the rosin-based self-repairing polyurethane.
The rosin-based polyol is at least one of acrylic pimaric acid polyester polyol, diacrylpimaric acid polyester polyol, maleopimaric acid polyester polyol, bismalepimaric acid polyester polyol and acrylic pimaric acid polyether polyol.
The diisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
The molar ratio of the rosin-based polyol to the diisocyanate reaction group is 1: 2; the reaction temperature of the rosin-based polyol and the diisocyanate is 60 ℃, and the reaction time is 8 h.
The catalyst is dibutyltin dilaurate or stannous octoate.
The furan ring derivative is at least one of furfuryl amine, furfuryl alcohol, 2, 5-furandimethanol and trifuryl glycol.
The reaction temperature of the furan structure derivative is 20 ℃, the reaction time is 8 hours, and the molar ratio of the furan structure derivative to diisocyanate is 1: 5.
The maleic amide derivative is at least one of bismaleimide, N-hydroxyethyl maleimide, M-600-maleic amide, D-400-maleic amide and T-403-maleic amide.
The reaction temperature of the maleic amide derivatives is 60 ℃, the reaction time is 24 hours, and the molar ratio of the maleic amide derivatives to the furan structure derivatives is 1: 1.
The rosin-based self-repairing polyurethane prepared by the preparation method based on the Diels-Alder reaction.
Has the advantages that: 1. the forest product special resource rosin is used as a raw material to synthesize the self-repairing polyurethane material, and the self-repairing polyurethane material has the advantages of wide raw material source, rich yield, low cost and the like.
2. The rosin phenanthrene ring is used for enhancing the mechanical and thermal stability of the polyurethane material, the tensile strength of the prepared self-repairing polyurethane material is 12.7-18.8 MPa, and meanwhile, abundant rosin is used for replacing expensive petrochemical raw materials to develop high-added-value high polymer materials, so that the change of the ecological environment is obviously promoted.
Drawings
FIG. 1 is an IR spectrum of a rosin-based self-healing polyurethane based on the Diels-Alder reaction of example 1.
The infrared spectrum of the rosin-based self-repairing polyurethane based on the Diels-Alder reaction in FIG. 1 shows that: 3375cm-1The position is a stretching vibration peak of an N-H bond in carbamate, a characteristic absorption peak of a DA addition product is at 1773cm-1, a stretching vibration peak of-NHCOO-in which C is equal to O is at 1706cm-1, and a characteristic absorption peak of-NCO does not appear at 2270cm-1, which indicates that the rosin-based self-repairing polyurethane is successfully synthesized.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and substance of the invention.
In the following examples, the raw materials are in parts by mass unless otherwise specified.
A preparation method of rosin-based self-repairing polyurethane based on Diels-Alder reaction comprises the following steps: dissolving rosin-based polyol and diisocyanate in a molar ratio of 1: 1-1: 4, uniformly stirring, adding a catalyst, heating in a water bath at 40-80 ℃, uniformly stirring, and reacting for 2-10 hours to obtain a prepolymer; and then adding a furan ring derivative, reacting for 2-10 h at 0-60 ℃ to obtain a furan-terminated polyurethane prepolymer, adding a maleic amide derivative, reacting for 2-24 h in a water bath at 40-80 ℃, pouring into a polytetrafluoroethylene template after the reaction is finished, curing, and removing the solvent to obtain the rosin-based self-repairing polyurethane.
The rosin-based polyol is at least one of acrylic pimaric acid polyester polyol, diacrylpimaric acid polyester polyol, maleopimaric acid polyester polyol, bismalepimaric acid polyester polyol and acrylic pimaric acid polyether polyol, and is preferably maleopimaric acid polyester polyol.
The diisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate, preferably isophorone diisocyanate.
Preferably, the molar ratio of the rosin-based polyol to the diisocyanate-reactive groups is 1: 2.
The catalyst used is dibutyltin dilaurate or stannous octoate, preferably dibutyltin dilaurate.
Preferably, the reaction temperature of the rosin-based polyol and the diisocyanate is 60 ℃, and the reaction time is 8 hours.
The furan structural derivative is at least one of furfuryl amine, furfuryl alcohol, 2, 5-furandimethanol, 1, 6-hexamethylene-bis (2-furylmethyl carbamate) and tri-furyldiglycol, and preferably furfuryl amine.
Preferably, the reaction temperature of the furan structure derivative is 20 ℃, the reaction time is 8 hours, and the molar ratio of the furan structure derivative to diisocyanate is 1: 5.
The maleic amide derivatives are at least one of bismaleimide, N-hydroxyethyl maleimide, M-600-maleimide, D-400-maleimide and T-403-maleimide, preferably bismaleimide.
Preferably, the reaction temperature of the maleic amide derivatives is 60 ℃, the reaction time is 24 hours, and the molar ratio of the maleic amide derivatives to the furan structure derivatives is 1: 1.
A rosin-based self-repairing polyurethane material based on Diels-Alder reaction is prepared by the preparation method, and according to GB/T528-1998 test, the tensile strength of the self-repairing polyurethane material is 12.7-18.8 MPa, the elongation at break is 48-74%, and the self-repairing efficiency is 87.5-94.6%;
the self-repairing test method comprises the following steps: and cutting a standard dumbbell-shaped test sample from the middle by using a knife, completely butting two fracture surfaces together, carrying out heat treatment at 120 ℃ for 30min, carrying out heat treatment at 60 ℃ for 24h, then cooling to room temperature, and retesting the tensile strength of the repaired sample, wherein the repair efficiency is defined as the ratio of the repaired sample to the original tensile strength.
Example 1
Adding 7 parts of maleopimaric acid ester polyol and 12 parts of toluene diisocyanate into a reaction bottle, adding dibutyltin dilaurate, heating and stirring uniformly in an oil bath at 60 ℃, and reacting for 8 hours to obtain a prepolymer; and then adding 5 parts of furfuryl alcohol, reacting for 8 hours at 20 ℃ to obtain a furan-terminated polyurethane prepolymer, adding 12 parts of bismaleimide, reacting for 24 hours in an oil bath at 60 ℃, pouring into a polytetrafluoroethylene template after the reaction is finished, curing, and removing the solvent to obtain the rosin-based self-repairing polyurethane.
Example 2
Adding 7 parts of maleopimaric acid ester polyol and 12 parts of isophorone diisocyanate into a reaction bottle, adding dibutyltin dilaurate into the reaction bottle, heating the mixture in an oil bath at the temperature of 60 ℃, uniformly stirring the mixture, and reacting the mixture for 8 hours to obtain a prepolymer; and then adding 5 parts of furfuryl amine, reacting for 8 hours at 20 ℃ to obtain a furan-terminated polyurethane prepolymer, adding 12 parts of bismaleimide, reacting for 24 hours in an oil bath at 60 ℃, pouring into a polytetrafluoroethylene template after the reaction is finished, curing, and removing the solvent to obtain the rosin-based self-repairing polyurethane.
Example 3
Adding 7 parts of maleopimaric acid ester polyol and 12 parts of diphenylmethane diisocyanate into a reaction bottle, adding dibutyltin dilaurate, heating and stirring uniformly in an oil bath at 60 ℃, and reacting for 8 hours to obtain a prepolymer; and then adding 5 parts of furfuryl amine, reacting for 8 hours at 20 ℃ to obtain a furan-terminated polyurethane prepolymer, adding 12 parts of bismaleimide, reacting for 24 hours in an oil bath at 60 ℃, pouring into a polytetrafluoroethylene template after the reaction is finished, curing, and removing the solvent to obtain the rosin-based self-repairing polyurethane.
Example 4
Adding 7 parts of acrylic pimaric acid polyester polyol and 12 parts of isophorone diisocyanate into a reaction bottle, adding dibutyltin dilaurate, heating and stirring uniformly in an oil bath at 60 ℃, and reacting for 8 hours to obtain a prepolymer; and then adding 5 parts of 2, 5-furandimethanol, reacting for 8 hours at 20 ℃ to obtain a furan-terminated polyurethane prepolymer, adding 12 parts of N-hydroxyethyl maleimide, reacting for 24 hours in an oil bath at 60 ℃, pouring into a polytetrafluoroethylene template after the reaction is finished, curing, and removing the solvent to obtain the rosin-based self-repairing polyurethane.
Example 5
Adding 7 parts of maleopimaric acid ester polyol and 12 parts of hexamethylene diisocyanate into a reaction bottle, adding dibutyltin dilaurate into the reaction bottle, heating the mixture in an oil bath at the temperature of 60 ℃, uniformly stirring the mixture, and reacting the mixture for 8 hours to obtain a prepolymer; and then adding 5 parts of furfuryl alcohol, reacting for 8 hours at 20 ℃ to obtain a furan-terminated polyurethane prepolymer, adding 12 parts of bismaleimide, reacting for 24 hours in an oil bath at 60 ℃, pouring into a polytetrafluoroethylene template after the reaction is finished, curing, and removing the solvent to obtain the rosin-based self-repairing polyurethane.
Example 6
Adding 7 parts of maleopimaric acid ester polyol and 12 parts of isophorone diisocyanate into a reaction bottle, adding dibutyltin dilaurate into the reaction bottle, heating the mixture in an oil bath at the temperature of 80 ℃, uniformly stirring the mixture, and reacting the mixture for 8 hours to obtain a prepolymer; then adding 10 parts of trifuryl glycol (Duxiucai, cross-linked polyurethane preparation based on Diels-Alder reaction and self-repairing performance research [ M ]. Qingdao science and technology university, 2016.), reacting for 8h at 20 ℃ to obtain a furan-terminated polyurethane prepolymer, adding 12 parts of M-600-maleic amide, reacting for 24h in an oil bath at 60 ℃, pouring into a polytetrafluoroethylene template after the reaction is finished, curing, and removing the solvent to obtain the rosin-based self-repairing polyurethane.
Table 1 examples 1-6 material performance test results
The invention uses the forest product special resource rosin to replace expensive petrochemical raw materials to synthesize the self-repairing polyurethane material, has the advantages of wide raw material sources, rich yield, low cost and the like, simultaneously utilizes the rosin phenanthrene ring to enhance the mechanical and thermal stability of the polyurethane material to prepare the self-repairing polyurethane material with the tensile strength of up to 15.8MPa and the self-repairing efficiency of up to 94.6 percent, and has excellent mechanical properties and good self-repairing performance.
Claims (10)
1. A preparation method of rosin-based self-repairing polyurethane based on Diels-Alder reaction is characterized by comprising the following steps: uniformly stirring rosin-based polyol and diisocyanate, wherein the molar ratio of the rosin-based polyol to the diisocyanate is 1: 1-4, adding a catalyst, heating and uniformly stirring in a water bath at the temperature of 40-80 ℃, and reacting for 2-10 hours to obtain a prepolymer; and then adding a furan ring derivative, reacting for 2-10 h at 0-60 ℃ to obtain a furan-terminated polyurethane prepolymer, adding a maleic amide derivative, reacting for 2-24 h in a water bath at 40-80 ℃, pouring into a polytetrafluoroethylene template after the reaction is finished, curing, and removing the solvent to obtain the rosin-based self-repairing polyurethane.
2. The method for preparing rosin-based self-repairing polyurethane according to claim 1, wherein the rosin-based polyol is at least one of acrylpimaric acid polyester polyol, diacrylpimaric acid ester polyol, maleopimaric acid ester polyol, bismalepimaric acid ester polyol and acrylpimaric acid polyether polyol.
3. The method for preparing rosin-based self-repairing polyurethane according to claim 1, wherein the diisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
4. The method for preparing the rosin-based self-repairing polyurethane based on the Diels-Alder reaction of claim 1, wherein the molar ratio of the rosin-based polyol to the diisocyanate reactive group is 1: 2; the reaction temperature of the rosin-based polyol and the diisocyanate is 60 ℃, and the reaction time is 8 h.
5. The method for preparing the rosin-based self-repairing polyurethane based on the Diels-Alder reaction according to claim 1, wherein the catalyst is dibutyltin dilaurate or stannous octoate.
6. The method for preparing rosin-based self-healing polyurethane according to claim 1, wherein the furan ring derivative is at least one of furfuryl amine, furfuryl alcohol, 2,5 furandimethanol, and trifuranyl diol.
7. The preparation method of the rosin-based self-repairing polyurethane based on the Diels-Alder reaction according to claim 1, wherein the reaction temperature of the furan structure derivative is 20 ℃, the reaction time is 8h, and the molar ratio of the furan structure derivative to diisocyanate is 1: 5.
8. The method for preparing rosin-based self-repairing polyurethane according to claim 1, wherein the maleimide derivative is at least one of bismaleimide, N-hydroxyethyl maleimide, M-600-maleimide, D-400-maleimide, and T-403-maleimide.
9. The preparation method of the rosin-based self-repairing polyurethane based on the Diels-Alder reaction according to claim 1, wherein the reaction temperature of the maleic amide derivative is 60 ℃, the reaction time is 24 hours, and the molar ratio of the maleic amide derivative to the furan structure derivative is 1: 1.
10. Rosin-based self-healing polyurethane based on the Diels-Alder reaction, obtainable by the process according to any one of claims 1 to 10.
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Cited By (6)
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| CN111471154A (en) * | 2020-05-11 | 2020-07-31 | 中国科学院深圳先进技术研究院 | Light or heat induced self-repairing elastomer and preparation method and application thereof |
| CN112979908A (en) * | 2021-02-25 | 2021-06-18 | 中国林业科学研究院林产化学工业研究所 | Rosin-based self-repairing polymer and synthetic method and application thereof |
| CN112979919A (en) * | 2021-02-25 | 2021-06-18 | 中国林业科学研究院林产化学工业研究所 | Preparation method of bio-based self-repairing polyurethane elastomer |
| CN114133517A (en) * | 2021-12-02 | 2022-03-04 | 无锡杰夫电声股份有限公司 | Rosin-based polyurethane and synthetic method thereof |
| CN114349924A (en) * | 2021-12-08 | 2022-04-15 | 南京工业大学 | Self-repairing polyurethane and preparation method thereof |
| CN115109225A (en) * | 2022-08-16 | 2022-09-27 | 青岛大学 | High-performance self-repairing polyurethane elastomer and preparation method thereof |
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| CN111471154A (en) * | 2020-05-11 | 2020-07-31 | 中国科学院深圳先进技术研究院 | Light or heat induced self-repairing elastomer and preparation method and application thereof |
| CN111471154B (en) * | 2020-05-11 | 2022-05-10 | 中国科学院深圳先进技术研究院 | Light or heat initiated self-repairing elastomer and preparation method and application thereof |
| CN112979908A (en) * | 2021-02-25 | 2021-06-18 | 中国林业科学研究院林产化学工业研究所 | Rosin-based self-repairing polymer and synthetic method and application thereof |
| CN112979919A (en) * | 2021-02-25 | 2021-06-18 | 中国林业科学研究院林产化学工业研究所 | Preparation method of bio-based self-repairing polyurethane elastomer |
| CN114133517A (en) * | 2021-12-02 | 2022-03-04 | 无锡杰夫电声股份有限公司 | Rosin-based polyurethane and synthetic method thereof |
| CN114133517B (en) * | 2021-12-02 | 2023-09-01 | 无锡杰夫电声股份有限公司 | Rosin-based polyurethane and synthetic method thereof |
| CN114349924A (en) * | 2021-12-08 | 2022-04-15 | 南京工业大学 | Self-repairing polyurethane and preparation method thereof |
| CN115109225A (en) * | 2022-08-16 | 2022-09-27 | 青岛大学 | High-performance self-repairing polyurethane elastomer and preparation method thereof |
| CN115109225B (en) * | 2022-08-16 | 2023-11-03 | 青岛大学 | High-performance self-repairing polyurethane elastomer and preparation method thereof |
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