阅读说明：本技术 一种自修复、可回收的生物基聚氨酯材料及其制备方法与应用 (Self-repairing and recyclable bio-based polyurethane material and preparation method and application thereof ) 是由 刘承果 张金帅 周永红 尚倩倩 胡云 胡立红 钟东南 朱国强 余希希 黄佳 于 2021-09-14 设计创作，主要内容包括：一种自修复、可回收的生物基聚氨酯材料及其制备方法与应用。本发明首先利用1H-吡唑-4-甲酸和乙烯基单体在催化剂的作用下发生酯化反应得到乙烯基吡唑酯单体；接着利用植物油和二异氰酸酯在催化剂的作用下发生反应,得到植物油基聚氨酯中间产物；随后将合成的乙烯基吡唑酯单体加入到植物油基聚氨酯中间产物中,得到植物油基聚氨酯树脂,经热压处理后,得到植物油基聚氨酯材料。所得到的聚氨酯材料不但具有优良的力学与热学性能,还具有自修复、可回收加工等性能,可用于胶黏剂、导电复合材料等。本发明工艺简单、环保,且原料部分来自于可再生资源,因此对促进聚氨酯材料产业的可持续发展具有重大的意义。(A self-repairing and recyclable bio-based polyurethane material, a preparation method and application thereof. Firstly, carrying out esterification reaction on 1H-pyrazole-4-formic acid and a vinyl monomer under the action of a catalyst to obtain a vinyl pyrazole ester monomer; then vegetable oil and diisocyanate are reacted under the action of a catalyst to obtain a vegetable oil-based polyurethane intermediate product; and then adding the synthesized vinyl pyrazole ester monomer into the vegetable oil-based polyurethane intermediate product to obtain vegetable oil-based polyurethane resin, and carrying out hot pressing treatment to obtain the vegetable oil-based polyurethane material. The obtained polyurethane material not only has excellent mechanical and thermal properties, but also has the properties of self-repairing, recycling, processing and the like, and can be used for adhesives, conductive composite materials and the like. The method has simple process and environmental protection, and the raw materials are partially from renewable resources, so the method has great significance for promoting the sustainable development of the polyurethane material industry.)

1. A self-repairing and recyclable bio-based polyurethane material is characterized in that 1H-pyrazole-4-formic acid and a vinyl monomer are subjected to esterification reaction under the action of a catalyst to obtain a vinyl pyrazole ester monomer; then vegetable oil and diisocyanate are reacted under the action of a catalyst to obtain a vegetable oil-based polyurethane intermediate product; and then adding the synthesized vinyl pyrazole ester monomer into the vegetable oil-based polyurethane intermediate product to obtain vegetable oil-based polyurethane resin, and carrying out hot pressing treatment to obtain the vegetable oil-based polyurethane material.

2. The self-healing recyclable biobased polyurethane material of claim 1, wherein the vinyl monomer is at least one of allyl alcohol, methallyl alcohol, hydroxyethyl acrylate, and hydroxyethyl methacrylate.

3. The self-healing recyclable biobased polyurethane material as claimed in claim 1, wherein the vegetable oil is at least one of castor oil, tung oil, linseed oil, rubber seed oil, dehydrated castor oil, rapeseed oil, cornus wilsoniana seed oil, sunflower seed oil, cotton seed oil, soybean oil, corn oil; the diisocyanate is at least one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.

4. The preparation method of the self-repairing recyclable bio-based polyurethane material as claimed in any one of claims 1 to 3, characterized by comprising the following steps:

(1) adding 1H-pyrazole-4-formic acid, a vinyl monomer and a catalyst into a reactor, uniformly stirring, heating to 20-100 ℃, and reacting for 5-30H to obtain a vinyl pyrazole ester monomer;

(2) adding vegetable oil, diisocyanate and a catalyst into the other reactor, uniformly stirring, heating to 20-100 ℃, and reacting for 1-10 hours to obtain a vegetable oil-based polyurethane intermediate product;

(3) adding the synthesized vinyl pyrazole ester monomer into the vegetable oil-based polyurethane intermediate product, and uniformly stirring to obtain vegetable oil-based polyurethane resin;

(4) and carrying out hot-pressing treatment on the synthesized vegetable oil-based polyurethane resin at the hot-pressing temperature of 60-200 ℃, under the applied pressure of 0.5-20 MPa and for 0.5-2 h to obtain the vegetable oil-based polyurethane material.

5. The preparation method of the self-repairing and recyclable bio-based polyurethane material as claimed in claim 4, wherein the catalyst in the step (1) is at least one of p-toluenesulfonic acid, DCC/DMAP, EDCI/DMAP, N-dimethylbenzylamine, triphenylphosphine, 1-methylimidazole, tetrabutyl titanate and 4-dimethylaminopyridine.

6. The preparation method of the self-repairing and recyclable bio-based polyurethane material as claimed in claim 4, wherein the molar ratio of the vinyl monomer to the 1H-pyrazole-4-carboxylic acid is 0.8-1.5: 1, the molar ratio of the diisocyanate to the vegetable oil is 1-10: 1, the amount of the catalyst is 0.5-2% of the total weight of the raw materials, and the molar ratio of the vinyl pyrazole ester monomer to the vegetable oil-based polyurethane intermediate product is 1-10: 1.

7. The preparation method of the self-repairing recyclable biobased polyurethane material as claimed in claim 4, wherein the catalyst in the step (2) is at least one of dibutyltin dilaurate and 1, 4-diazabicyclo [2.2.2] octane.

8. Use of the self-healing recyclable biobased polyurethane material as claimed in any one of claims 1 to 3 in adhesives, electrically conductive composites.

Technical Field

The invention belongs to the field of polyurethane materials, and particularly relates to a self-repairing and recyclable bio-based polyurethane material as well as a preparation method and application thereof.

Background

High molecular polymers, especially Polyurethane (PU) materials, play an important role in modern life, and are spread in various fields of life, from daily necessities to communications, aerospace, medicine, and the like. However, most of these materials are derived from non-renewable petrochemical products. In view of environmental pollution and the constantly fluctuating prices of oil due to changes in international policy, researchers have made great efforts in the past few decades to replace non-renewable fossil energy sources with renewable resources. Vegetable oil is a natural renewable resource, has wide sources and low price, and is widely applied to the preparation of polyurethane materials. Synthetic thermoset polyurethanes generally have the advantage of excellent dimensional stability, thermal stability, and chemical resistance due to the multiple crosslinking sites contained in the vegetable oil structure. However, the existence of a stable cross-linked structure in the material also limits the material to be incapable of being reprocessed by melting like thermoplastic polymers, thereby causing material waste and environmental pollution.

One effective strategy to achieve polyurethane material recyclability is to incorporate dynamic bonds into the polymer network to produce a dynamically reversible crosslinked polymer. The polymer has the characteristics of both thermosetting materials and thermoplastic materials, can show the characteristics of the thermosetting materials in a certain range, and can also realize recovery and reprocessing under special conditions. Dynamic covalent polymers have a long history and it has been found as early as 1946 that the disulfide bonds in vulcanized rubber are always in a dynamic equilibrium of broken bonds and formed bonds, but this has not been appreciated. Until 2011, scientists introduced the concept of "Vitrimer" and dynamic covalent polymers were not rapidly developed. Vitrimer refers to a class of dynamically crosslinked polymers based on associative exchange reactions that undergo reversible chemical bond exchange in a dynamic manner when heated while maintaining a permanent crosslinked network structure. Heretofore, a number of dynamic covalent bonds including hindered urea bonds (Naturecommunications,2014,5,3218), disulfide bonds (Angewandable Chemie International edition, 2021,60, 4289-. From the results, although the above approaches overcome the problems of non-recyclability and reprocessing of polyurethane materials, the obtained materials have high post-treatment temperature and generally low mechanical properties.

Disclosure of Invention

The technical problem to be solved is as follows: the invention provides a preparation method of a recoverable and repairable vegetable oil-based polyurethane material with excellent mechanical property and thermal property, aiming at overcoming the defect that the existing vegetable oil-based polyurethane material can not be recovered and reprocessed.

The technical scheme is as follows: a self-repairing and recyclable bio-based polyurethane material is prepared by firstly carrying out esterification reaction on 1H-pyrazole-4-formic acid and a vinyl monomer under the action of a catalyst to obtain a vinyl pyrazole ester monomer; then vegetable oil and diisocyanate are reacted under the action of a catalyst to obtain a vegetable oil-based polyurethane intermediate product; and then adding the synthesized vinyl pyrazole ester monomer into the vegetable oil-based polyurethane intermediate product to obtain vegetable oil-based polyurethane resin, and carrying out hot pressing treatment to obtain the vegetable oil-based polyurethane material.

The vinyl monomer is at least one of allyl alcohol, methallyl alcohol, hydroxyethyl acrylate and hydroxyethyl methacrylate.

The vegetable oil is at least one of castor oil, tung oil, linseed oil, rubber seed oil, dehydrated castor oil, rapeseed oil, cornus wilsoniana seed oil, sunflower seed oil, cottonseed oil, soybean oil and corn oil; the diisocyanate is at least one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.

The preparation method of any one of the self-repairing and recyclable bio-based polyurethane materials comprises the following preparation steps:

(1) adding 1H-pyrazole-4-formic acid, a vinyl monomer and a catalyst into a reactor, uniformly stirring, heating to 20-100 ℃, and reacting for 5-30H to obtain a vinyl pyrazole ester monomer;

(2) adding vegetable oil, diisocyanate and a catalyst into the other reactor, uniformly stirring, heating to 20-100 ℃, and reacting for 1-10 hours to obtain a vegetable oil-based polyurethane intermediate product;

(3) adding the synthesized vinyl pyrazole ester monomer into the vegetable oil-based polyurethane intermediate product, and uniformly stirring to obtain vegetable oil-based polyurethane resin;

(4) and carrying out hot-pressing treatment on the synthesized vegetable oil-based polyurethane resin at the hot-pressing temperature of 60-200 ℃, under the applied pressure of 0.5-20 MPa and for 0.5-2 h to obtain the vegetable oil-based polyurethane material.

The catalyst in the step (1) is at least one of p-toluenesulfonic acid, DCC/DMAP, EDCI/DMAP, N-dimethylbenzylamine, triphenylphosphine, 1-methylimidazole, tetrabutyl titanate and 4-dimethylaminopyridine.

The molar ratio of the vinyl monomer to the 1H-pyrazole-4-formic acid is 0.8-1.5: 1, the molar ratio of the diisocyanate to the vegetable oil is 1-10: 1, the using amount of the catalyst is 0.5-2% of the total weight of the raw materials, and the molar ratio of the vinyl pyrazole ester monomer to the vegetable oil-based polyurethane intermediate product is 1-10: 1.

The catalyst in the step (2) is at least one of dibutyltin dilaurate and 1, 4-diazabicyclo [2.2.2] octane.

The self-repairing and recyclable bio-based polyurethane material is applied to adhesives and conductive composite materials.

Has the advantages that:

(1) the vegetable oil-based polyurethane material synthesized by the method has excellent mechanical, thermal, adhesion, self-repairing and recycling properties, and can be used for reversible cross-linking agents, conductive composite materials and the like;

(2) the synthesis method used in the invention is easy to operate and simple in process.

Drawings

FIG. 1 is a FT-IR spectrum of a vinylpyrazole ester monomer;

fig. 2 is a FT-IR spectrum of a castor oil based polyurethane intermediate.

Fig. 3 is a FT-IR spectrum of a castor oil-based polyurethane resin.

Detailed Description

The following examples are provided as further illustration of the invention and are not to be construed as limitations or limitations of the invention. The present invention will be described in more detail with reference to examples.

A self-repairing and recyclable bio-based polyurethane material and a preparation method and application thereof are disclosed, and the preparation steps are as follows: (1) adding 1H-pyrazole-4-formic acid, a vinyl monomer and a catalyst into a reactor, wherein the molar ratio of the vinyl monomer to the 1H-pyrazole-4-formic acid is (0.8-1.5): 1, the addition amount of the catalyst is 0.5-2% of the total weight of reaction materials, uniformly stirring, heating to 20-100 ℃, and reacting for 5-30H to obtain a vinyl pyrazole ester monomer; (2) adding vegetable oil, diisocyanate and a catalyst into the other reactor, wherein the molar ratio of the diisocyanate to the vegetable oil is (1-10): 1, the addition amount of the catalyst is 0.5-2% of the total weight of the reaction materials, uniformly stirring, heating to 20-100 ℃, and reacting for 1-10 hours to obtain a vegetable oil-based polyurethane intermediate product; (3) adding the synthesized vinyl pyrazole ester monomer into a vegetable oil-based polyurethane intermediate product, wherein the molar ratio of the vinyl pyrazole ester monomer to the vegetable oil-based intermediate product is (1-10): 1, and uniformly stirring to obtain a vegetable oil-based polyurethane resin; (4) and carrying out hot-pressing treatment on the synthesized vegetable oil-based polyurethane resin at the hot-pressing temperature of 60-200 ℃, under the applied pressure of 0.5-20 MPa and for 0.5-2 h to obtain the vegetable oil-based polyurethane material.

Preferably, the vinyl monomer in step (1) is at least one of allyl alcohol, methallyl alcohol, hydroxyethyl acrylate and hydroxyethyl methacrylate; the molar ratio of the vinyl monomer to the 1H-pyrazole-4-formic acid is 1: 1.

Preferably, the catalyst in the step (1) is at least one of p-toluenesulfonic acid, DCC/DMAP, EDCI/DMAP, N-dimethylbenzylamine, triphenylphosphine, 1-methylimidazole, tetrabutyl titanate and 4-dimethylaminopyridine, and the dosage of the catalyst is 0.5 percent of the total weight of the raw materials.

Preferably, the vegetable oil in step (2) is at least one of castor oil, tung oil, linseed oil, rubber seed oil, dehydrated castor oil, rapeseed oil, cornus wilsoniana seed oil, sunflower seed oil, cotton seed oil, soybean oil and corn oil; the diisocyanate is at least one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate, and the molar ratio of the diisocyanate to the vegetable oil is 3: 1.

Preferably, the catalyst in the step (2) is at least one of dibutyltin dilaurate and 1, 4-diazabicyclo [2.2.2] octane, and the amount of the catalyst is 0.5% of the total weight of the raw materials.

Preferably, the molar ratio of the vinyl pyrazole ester monomer to the vegetable oil-based intermediate product in the step (3) is 1: 1.

The vegetable oil-based polyurethane material prepared by the method.

Example 1

(1) Adding castor oil, isophorone diisocyanate (the molar ratio of isophorone diisocyanate to castor oil is 1.5:1) and a catalyst dibutyltin dilaurate (the adding amount of the catalyst is 0.5 percent of the total weight of reaction materials) into a reactor, uniformly stirring, heating to 50 ℃ and reacting for 2 hours to obtain castor oil-based polyurethane resin PPU 1;

(2) and carrying out hot pressing (the hot pressing temperature is 150 ℃, the applied pressure is 10MPa, and the hot pressing time is 1h) treatment on the obtained product to obtain the castor oil-based polyurethane material.

Example 2

(1) Adding 1H-pyrazole-4-formic acid, hydroxyethyl methacrylate (the molar ratio of the hydroxyethyl methacrylate to the 1H-pyrazole-4-formic acid is 1:1) and a catalyst p-toluenesulfonic acid (the addition of the catalyst is 0.5 percent of the total weight of reaction materials) into a reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a pyrazole methacrylate monomer PCM;

(2) adding castor oil, isophorone diisocyanate (the molar ratio of isophorone diisocyanate to castor oil is 2:1) and a catalyst dibutyltin dilaurate (the adding amount of the catalyst is 0.5 percent of the total weight of reaction materials) into another reactor, uniformly stirring, heating to 50 ℃ and reacting for 2 hours to obtain a castor oil-based polyurethane intermediate product CTI;

(3) uniformly mixing the synthesized pyrazole methacrylate monomer and a castor oil-based polyurethane intermediate product (the molar ratio of the castor oil-based polyurethane intermediate product to the pyrazole methacrylate monomer is 1:1) to obtain castor oil-based polyurethane resin PPU 2;

(4) and carrying out hot pressing (the hot pressing temperature is 150 ℃, the applied pressure is 10MPa, and the hot pressing time is 1h) treatment on the obtained product to obtain the castor oil-based polyurethane material.

Example 3

(1) Adding 1H-pyrazole-4-formic acid, hydroxyethyl methacrylate (the molar ratio of the hydroxyethyl methacrylate to the 1H-pyrazole-4-formic acid is 1:1) and a catalyst p-toluenesulfonic acid (the addition of the catalyst is 0.5 percent of the total weight of reaction materials) into a reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a pyrazole methacrylate monomer PCM;

(2) adding castor oil, isophorone diisocyanate (the molar ratio of isophorone diisocyanate to castor oil is 3:1) and a catalyst dibutyltin dilaurate (the adding amount of the catalyst is 0.5 percent of the total weight of reaction materials) into another reactor, uniformly stirring, heating to 50 ℃ and reacting for 2 hours to obtain a castor oil-based polyurethane intermediate product CTI;

(3) uniformly mixing the synthesized pyrazole methacrylate monomer and a castor oil-based polyurethane intermediate product (the molar ratio of the castor oil-based polyurethane intermediate product to the pyrazole methacrylate monomer is 1:3) to obtain castor oil-based polyurethane resin PPU 3;

(4) and carrying out hot pressing (the hot pressing temperature is 150 ℃, the applied pressure is 10MPa, and the hot pressing time is 1h) treatment on the obtained product to obtain the castor oil-based polyurethane material.

Example 4

(1) Adding 1H-pyrazole-4-formic acid, hydroxyethyl methacrylate (the molar ratio of the hydroxyethyl methacrylate to the 1H-pyrazole-4-formic acid is 1:1) and a catalyst p-toluenesulfonic acid (the addition of the catalyst is 0.5 percent of the total weight of reaction materials) into a reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a pyrazole methacrylate monomer PCM;

(2) adding castor oil, isophorone diisocyanate (the molar ratio of isophorone diisocyanate to castor oil is 6:1) and a catalyst dibutyltin dilaurate (the adding amount of the catalyst is 0.5 percent of the total weight of reaction materials) into another reactor, uniformly stirring, heating to 50 ℃ and reacting for 2 hours to obtain a castor oil-based polyurethane intermediate product CTI;

(3) uniformly mixing the synthesized pyrazole methacrylate monomer and a castor oil-based polyurethane intermediate product (the molar ratio of the castor oil-based polyurethane intermediate product to the pyrazole methacrylate monomer is 1:9) to obtain castor oil-based polyurethane resin PPU 4;

(4) and carrying out hot pressing (the hot pressing temperature is 150 ℃, the applied pressure is 10MPa, and the hot pressing time is 1h) treatment on the obtained product to obtain the castor oil-based polyurethane material.

Example 5

(1) Adding 1H-pyrazole-4-formic acid, hydroxyethyl methacrylate (the molar ratio of the hydroxyethyl methacrylate to the 1H-pyrazole-4-formic acid is 1:1) and a catalyst p-toluenesulfonic acid (the addition of the catalyst is 0.5 percent of the total weight of reaction materials) into a reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a pyrazole methacrylate monomer PCM;

(2) adding isophorone diisocyanate (the molar ratio of isophorone diisocyanate to pyrazole methacrylate monomer is 1:2) and a catalyst dibutyltin dilaurate (the adding amount of the catalyst is 0.5 percent of the total weight of the reaction materials) into the synthesized pyrazole methacrylate monomer, uniformly stirring, heating to 50 ℃ and reacting for 2 hours to obtain polyurethane resin PPU 5;

(3) and carrying out hot pressing (the hot pressing temperature is 150 ℃, the applied pressure is 10MPa, and the hot pressing time is 1h) treatment on the obtained product to obtain the polyurethane material.

Example 6

(1) Adding 1H-pyrazole-4-formic acid, hydroxyethyl acrylate (the molar ratio of the hydroxyethyl acrylate to the 1H-pyrazole-4-formic acid is 1:1) and a catalyst p-toluenesulfonic acid (the addition of the catalyst is 0.5 percent of the total weight of reaction materials) into a reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a pyrazole acrylate monomer PCM 1;

(2) adding castor oil, isophorone diisocyanate (the molar ratio of isophorone diisocyanate to castor oil is 3:1) and a catalyst dibutyltin dilaurate (the adding amount of the catalyst is 0.5 percent of the total weight of reaction materials) into another reactor, uniformly stirring, heating to 50 ℃ and reacting for 2 hours to obtain a castor oil-based polyurethane intermediate product CTI;

(3) uniformly mixing the synthesized pyrazole acrylate monomer and a castor oil-based polyurethane intermediate product (the molar ratio of the castor oil-based polyurethane intermediate product to the pyrazole acrylate monomer is 1:3) to obtain castor oil-based polyurethane resin PPU 6;

(4) and carrying out hot pressing (the hot pressing temperature is 150 ℃, the applied pressure is 10MPa, and the hot pressing time is 1h) treatment on the obtained product to obtain the castor oil-based polyurethane material.

Example 7

(1) Adding 1H-pyrazole-4-formic acid, hydroxyethyl methacrylate (the molar ratio of the hydroxyethyl methacrylate to the 1H-pyrazole-4-formic acid is 1:1) and a catalyst DCC/DMAP (the adding amount of the catalyst is 0.5 percent of the total weight of reaction materials) into a reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a pyrazole methacrylate monomer PCM 2;

(2) adding castor oil, isophorone diisocyanate (the molar ratio of isophorone diisocyanate to castor oil is 3:1) and a catalyst dibutyltin dilaurate (the adding amount of the catalyst is 0.5 percent of the total weight of reaction materials) into another reactor, uniformly stirring, heating to 50 ℃ and reacting for 2 hours to obtain a castor oil-based polyurethane intermediate product CTI;

(3) uniformly mixing the synthesized pyrazole methacrylate monomer and a castor oil-based polyurethane intermediate product (the molar ratio of the castor oil-based polyurethane intermediate product to the pyrazole methacrylate monomer is 1:3) to obtain castor oil-based polyurethane resin PPU 7;

(4) and carrying out hot pressing (the hot pressing temperature is 150 ℃, the applied pressure is 10MPa, and the hot pressing time is 1h) treatment on the obtained product to obtain the castor oil-based polyurethane material.

Example 8

(1) Adding 1H-pyrazole-4-formic acid, hydroxyethyl methacrylate (the molar ratio of the hydroxyethyl methacrylate to the 1H-pyrazole-4-formic acid is 1:1) and triphenylphosphine catalyst (the addition of the triphenylphosphine catalyst is 0.5 percent of the total weight of the reaction materials) into a reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain pyrazole methacrylate monomer PCM 3;

(2) adding castor oil, isophorone diisocyanate (the molar ratio of isophorone diisocyanate to castor oil is 3:1) and a catalyst dibutyltin dilaurate (the adding amount of the catalyst is 0.5 percent of the total weight of reaction materials) into another reactor, uniformly stirring, heating to 50 ℃ and reacting for 2 hours to obtain a castor oil-based polyurethane intermediate product CTI;

(3) uniformly mixing the synthesized pyrazole methacrylate monomer and a castor oil-based polyurethane intermediate product (the molar ratio of the castor oil-based polyurethane intermediate product to the pyrazole methacrylate monomer is 1:3) to obtain castor oil-based polyurethane resin PPU 8;

(4) and carrying out hot pressing (the hot pressing temperature is 150 ℃, the applied pressure is 10MPa, and the hot pressing time is 1h) treatment on the obtained product to obtain the castor oil-based polyurethane material.

Example 9

(1) Adding 1H-pyrazole-4-formic acid, hydroxyethyl methacrylate (the molar ratio of the hydroxyethyl methacrylate to the 1H-pyrazole-4-formic acid is 1:1) and a catalyst p-toluenesulfonic acid (the addition of the catalyst is 0.5 percent of the total weight of reaction materials) into a reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a pyrazole methacrylate monomer PCM;

(2) adding castor oil, dicyclohexylmethane diisocyanate (the molar ratio of the dicyclohexylmethane diisocyanate to the castor oil is 3:1) and a catalyst dibutyltin dilaurate (the adding amount of the catalyst is 0.5 percent of the total weight of the reaction materials) into another reactor, uniformly stirring, heating to 50 ℃ and reacting for 2 hours to obtain a castor oil-based polyurethane intermediate product CTI 1;

(3) uniformly mixing the synthesized pyrazole methacrylate monomer and a castor oil-based polyurethane intermediate product (the molar ratio of the castor oil-based polyurethane intermediate product to the pyrazole methacrylate monomer is 1:3) to obtain castor oil-based polyurethane resin PPU 9;

(4) and carrying out hot pressing (the hot pressing temperature is 150 ℃, the applied pressure is 10MPa, and the hot pressing time is 1h) treatment on the obtained product to obtain the castor oil-based polyurethane material.

Example 10

(1) Adding 1H-pyrazole-4-formic acid, hydroxyethyl methacrylate (the molar ratio of the hydroxyethyl methacrylate to the 1H-pyrazole-4-formic acid is 1:1) and a catalyst p-toluenesulfonic acid (the addition of the catalyst is 0.5 percent of the total weight of reaction materials) into a reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a pyrazole methacrylate monomer PCM;

(2) adding castor oil, isophorone diisocyanate (the molar ratio of isophorone diisocyanate to castor oil is 3:1) and a catalyst 1, 4-diazabicyclo [2.2.2] octane into another reactor (the adding amount of the catalyst is 0.5 percent of the total weight of reaction materials), uniformly stirring, heating to 50 ℃ and reacting for 2 hours to obtain a castor oil-based polyurethane intermediate product CTI 2;

(3) uniformly mixing the synthesized pyrazole methacrylate monomer and a castor oil-based polyurethane intermediate product (the molar ratio of the castor oil-based polyurethane intermediate product to the pyrazole methacrylate monomer is 1:3) to obtain castor oil-based polyurethane resin PPU 10;

(4) and carrying out hot pressing (the hot pressing temperature is 150 ℃, the applied pressure is 10MPa, and the hot pressing time is 1h) treatment on the obtained product to obtain the castor oil-based polyurethane material.

Example 11

(1) Adding 1H-pyrazole-4-formic acid, hydroxyethyl methacrylate (the molar ratio of the hydroxyethyl methacrylate to the 1H-pyrazole-4-formic acid is 1:1) and a catalyst p-toluenesulfonic acid (the addition of the catalyst is 0.5 percent of the total weight of reaction materials) into a reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a pyrazole methacrylate monomer PCM;

(2) adding rubber seed oil, isophorone diisocyanate (the molar ratio of isophorone diisocyanate to rubber seed oil is 3:1) and a catalyst dibutyltin dilaurate (the adding amount of the catalyst is 0.5 percent of the total weight of the reaction materials) into another reactor, uniformly stirring, heating to 50 ℃ and reacting for 2 hours to obtain a rubber seed oil-based polyurethane intermediate product RTI;

(3) uniformly mixing the synthesized pyrazole methacrylate monomer and a rubber seed oil-based polyurethane intermediate product (the molar ratio of the rubber seed oil-based polyurethane intermediate product to the pyrazole methacrylate monomer is 1:3) to obtain rubber seed oil-based polyurethane resin PPU 11;

(4) and carrying out hot pressing (the hot pressing temperature is 150 ℃, the applied pressure is 10MPa, and the hot pressing time is 1h) treatment on the obtained product to obtain the rubber seed oil-based polyurethane material.

Example 12

(1) Adding 1H-pyrazole-4-formic acid, hydroxyethyl methacrylate (the molar ratio of the hydroxyethyl methacrylate to the 1H-pyrazole-4-formic acid is 1:1) and a catalyst p-toluenesulfonic acid (the addition of the catalyst is 0.5 percent of the total weight of reaction materials) into a reactor, uniformly stirring, heating to 30 ℃ and reacting for 20 hours to obtain a pyrazole methacrylate monomer PCM;

(2) adding the smooth bark tree seed oil, isophorone diisocyanate (the molar ratio of isophorone diisocyanate to smooth bark tree seed oil is 3:1) and a catalyst dibutyltin dilaurate (the adding amount of the catalyst is 0.5 percent of the total weight of reaction materials) into another reactor, uniformly stirring, heating to 50 ℃ and reacting for 2 hours to obtain a smooth bark tree seed oil-based polyurethane intermediate product GTI;

(3) uniformly mixing the synthesized vinylpyrazole ester monomer and a cornus wilsoniana seed oil-based polyurethane intermediate product (the molar ratio of the cornus wilsoniana seed oil-based polyurethane intermediate product to the vinylpyrazole ester monomer is 1:3) to obtain cornus wilsoniana seed oil-based polyurethane resin PPU 12;

(4) and carrying out hot pressing (the hot pressing temperature is 150 ℃, the applied pressure is 10MPa, and the hot pressing time is 1h) treatment on the obtained product to obtain the cornus wilsoniana seed oil-based polyurethane material.

Example 13

Tensile property: the mechanical properties of the polyurethane material were measured according to ASTM D638-2008 using a universal tester model SANS7 CMT-4304 (Shenzhen New Miss Instrument Co., Ltd.), with a gauge length of 50mm and a tensile rate of 5.0 mm/min. The sample size was 80X 10X 1mm³. Glass transition temperature: the dynamic thermomechanical properties were determined using a Q800 solid analyser (TA, USA). Thermogravimetric analysis: the thermodynamically stable properties of the polyurethane materials were determined using a STA409PC thermogravimetric analyzer (Netzsch, Germany). The heating interval is 40-600 ℃, and the heating rate is 15 ℃/min. Self-repairing efficiency: and the scratch repair efficiency is calculated by observing the reduction ratio of the scratch width before and after repair by using an ICC50W Leica optical microscope. The test results of each example are shown in Table 1.

Table 1 examples 1-12 main performance indicators of vegetable oil based polyurethane materials

As can be seen from the data in the table, the vegetable oil-based polyurethane material prepared by the invention has excellent tensile property and thermal property and high self-repairing efficiency, and can be used in the field of recyclable polyurethane materials.

The above examples are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.