Maleopimarinol modified thermosetting polyurethane and preparation method thereof

Abstract

The invention discloses maleopimaric alcohol modified thermosetting polyurethane which is characterized by being prepared from the following components in parts by weight: 5 to 10 parts of maleopimaric alcohol, 20 to 95 parts of polyester polyol, 1 to 25 parts of chain extender, 10 to 45 parts of polyisocyanate and 0.001 part of catalyst, wherein the chain extender is not 0; the total content of the bio-based components in the maleopimaric alcohol, the polyhydric alcohol and the chain extender is greater than or equal to 50wt%. According to the maleopimaric alcohol modified thermosetting polyurethane provided by the invention, trihydric alcohol of maleopimaric alcohol reacts with isocyanate, so that a rosin ternary phenanthrene ring structure is introduced into a main chain structure of the thermosetting polyurethane; compared with a traditional carbon chain structure, the rigid structure characteristic of rosin is reserved, and good flexibility of a fat six-membered ring non-planar structure is reserved; the method takes the bio-based material rosin as the raw material to replace the traditional petroleum-based raw material, and has the characteristics of being green and environment-friendly.

Description

Technical Field

[0001] The invention discloses a polyurethane material technology field, and in particular relates to a maleopimarol-modified thermosetting polyurethane and a preparation method thereof. Background Art

[0002] At this stage, the contradiction between population, resources and environment is becoming increasingly prominent. Vigorously developing low-carbon, green and environmentally friendly materials has become an important development direction of the chemical industry. Among them, replacing petroleum-based materials with biomass raw materials is one of the important ways to develop new green high-performance materials.

[0003] Rosin has been used as a bio-based material for a long time. It is a mixture of tricyclic diterpene resin acids with hydrogenated phenanthrene structures, mainly including abietic acid, pimaric acid, and a small amount of fatty acids and neutral substances. Since the hydrogenated phenanthrene ring structure of abietic acid is similar to some petroleum-based aliphatic and aromatic compounds, it has great potential in replacing petroleum-based compounds to synthesize polyurethane.

[0004] Therefore, it is very meaningful to use rosin as a modified material to prepare high-performance bio-based thermosetting polyurethane materials. Summary of the invention

[0005] In view of this, the present invention provides a maleopimarol-modified thermosetting polyurethane and a preparation method thereof, so as to improve the mechanical strength, heat resistance and hydrophobicity of the thermosetting polyurethane resin through a green method, so that the comprehensive performance of the polyurethane system can be improved;

[0006] The present invention includes the following technical solutions: On the one hand, the present invention provides a maleopimarol-modified thermosetting polyurethane, which comprises, by weight:

[0007] 5-10 parts of maleopimarol, 20-95 parts of polyester polyol, 1-25 parts of chain extender, 10-45 parts of polyisocyanate, and 0.001 parts of catalyst; wherein the amount of chain extender is not 0;

[0008] The total content of bio-based components in maleopimarol, polyester polyol and chain extender is greater than or equal to 50wt%.

[0009] Preferably, the number average molecular weight of the polyol is 800 to 6000 g / mol, the hydroxyl value of the polyol is in the range of 18 to 140 mg KOH / g; the water content is less than or equal to 300 ppm;

[0010] Preferably, the polyol comprises 50 to 100 wt% of bio-based polyol and / or bio-based polyester polyol, and 0 to 50 wt% of petroleum-based polyol, based on the total weight of the polyol component;

[0011] The bio-based polyol is one or more of lignin, polysaccharide, cellulose, and dextrin;

[0012] The petroleum-based polyol includes one or more of petroleum-based diol, petroleum-based triol, petroleum-based tetraol and petroleum-based polyester polyol;

[0013] The hydroxyl value of the bio-based polyester polyol ranges from 18 to 140 mg KOH / g; the acid value is less than or equal to 2 mg KOH / g; the moisture content is less than or equal to 300 ppm, and the biobased content is greater than or equal to 50 wt% based on the total weight of the bio-based polyester polyol component; the bio-based polyester polyol is a polyol extracted from natural products, or obtained by reacting a bio-based acid with one or more small molecule alcohols, and the small molecule alcohol is a bio-based small molecule alcohol or a petroleum-based small molecule alcohol or both.

[0014] Preferably, the petroleum-based triol is one or more of polycaprolactone triol, propylene glycol, and polyether triol;

[0015] The petroleum-based tetraol is pentaerythritol;

[0016] The petroleum-based polyester polyol is one or more of polybutylene adipate diol (PBA), polyethylene adipate diol (PEA), and polyhexamethylene adipate diol (PHA);

[0017] The bio-based acid is one or more of bio-based succinic acid, sebacic acid, and polylactic acid;

[0018] The bio-based small molecule alcohol is one or more of bio-based 1,3-propylene glycol, bio-based 1,2-propylene glycol, bio-based ethylene glycol, and bio-based 1,4-butanediol;

[0019] The petroleum-based small molecule alcohol is one or more of petroleum-based 1,3-propylene glycol, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, dipropylene glycol, hexylene glycol, diethylene glycol, methyl propanediol, neopentyl glycol, polycaprolactone triol, glycerol, polyether triol, and pentaerythritol.

[0020] The bio-based polyester polyol is a polyol extracted from natural products, including one or more of poly(propylene succinate) diol (PPSu), poly(butylene succinate) diol (PBSu), poly(propylene sebacate) diol (PPSe), and poly(butylene sebacate) diol (PBSe).

[0021] Preferably, based on the total weight of the chain extender component, the chain extender contains 50-100wt% of a bio-based chain extender and 0-50wt% of a petroleum-based chain extender, wherein the petroleum-based chain extender is one or a mixture of petroleum-type ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, dipropylene glycol, hexanediol, diethylene glycol, methyl propylene glycol, and neopentyl glycol;

[0022] The polyisocyanate is preferably diisocyanate, triisocyanate or tetraisocyanate;

[0023] Based on the total weight of the polyisocyanate component, the polyisocyanate contains 10 to 60 wt% of bio-based isocyanate and 40 to 90 wt% of petroleum-based isocyanate;

[0024] The bio-based polyisocyanate is one or a mixture of bio-based 1,4-butanediisocyanate or bio-based 1,5-pentanediisocyanate;

[0025] The petroleum-based polyisocyanate is a mixture of one or more of hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, 4,4-dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, meta-xylyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4',4"-triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, dimethylisoxazole tetraisocyanate and tetraisocyanatosilane.

[0026] Preferably, the catalyst comprises 50 to 100 wt% of a non-tin environmentally friendly catalyst and 0 to 50 wt% of a tin-containing catalyst based on the total weight of the catalyst components;

[0027] The organotin catalyst is one or a mixture of stannous octoate, dibutyltin dilaurate, dibutyltin dioxalate, and dibutyltin didodecylsulfide;

[0028] The non-tin environmentally friendly catalyst is a mixture of one or more of triethylamine, triethylenediamine, dimethylcyclohexylamine, dimethylcyclohexylamine of tertiary amines and potassium isooctanoate, potassium oleate, bismuth isooctanoate and zinc isooctanoate of organic metals.

[0029] Preferably, the preparation method of maleopimaric acid is as follows: maleopimaric acid is dissolved in a solvent, and a reducing agent is slowly added under low temperature conditions and under the protection of an inert gas, and the reaction is carried out for 0.5 to 10 hours after the reducing agent is added, and then the temperature is raised to 40 to 80° C. and the reaction is carried out for 6 to 48 hours; after the reaction is completed, the excess reducing agent is quenched with a quenching agent, and then deionized water is added and fully shaken, and after filtering, vacuum filtration is carried out at 40 to 60° C. to constant weight; a non-aqueous solvent is added to the constant weight filtrate, and after sufficient shaking, the filtrate is allowed to stand for stratification, the water layer is removed, and the oil-containing layer liquid is subjected to high vacuum rotary evaporation to obtain a product having a triol structure - maleopimaric acid;

[0030] The solvent is one or more mixed solvents selected from anhydrous tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethyl ether, ethyl butyl ether, dihexyl ether, dipentyl ether, and 3-methylfuran;

[0031] The low temperature condition is a temperature condition of -10°C to 15°C;

[0032] The inert gas is one of nitrogen or argon or a mixture of the two;

[0033] The reducing agent is one or more mixtures of lithium aluminum hydride, sodium borohydride, potassium borohydride or dibutylaluminum hydride;

[0034] The quenching agent is one or more of water, sodium hydroxide aqueous solution, sodium carbonate aqueous solution, sodium bicarbonate aqueous solution, hydrochloric acid solution or disulfuric acid solution;

[0035] The non-aqueous solvent is a mixture of one or more of toluene, xylene, ethyl acetate and butyl acetate.

[0036] The present invention also provides a preparation method of the maleopimarol-modified thermosetting polyurethane, comprising: dividing the required polyester polyol into two parts, adding one part of the polyester polyol, isocyanate, chain extender and catalyst into a first reaction kettle, heating to form a first reactant, and evacuating and keeping the reaction kettle warm for later use; adding the other part of the polyester polyol and maleopimarol into a second reaction kettle to form a second reactant, and evacuating and keeping the reaction kettle warm for later use; preheating an oven, pouring the first and second reactants into a mold by a pouring machine, and then putting the reactants into an oven for curing, and finally demolding to obtain the maleopimarol-modified thermosetting polyurethane.

[0037] Preferably, the method comprises: mixing maleopimarol, polyester polyol, chain extender, diisocyanate and catalyst, and reacting them at a temperature of 70 to 200° C. to obtain maleopimarol-modified thermosetting polyurethane.

[0038] The present invention provides a maleopimitol modified thermosetting polyurethane and a preparation method thereof. The method uses bio-based material rosin as a raw material to replace traditional petroleum-based raw materials, and has the characteristics of being green and environmentally friendly. In addition, the maleopimitol modified thermosetting polyurethane provided by the present invention introduces the rosin ternary phenanthrene ring structure into the main chain structure of the thermosetting polyurethane through the reaction of the maleopimitol triol with isocyanate (see the attached Figure 1 ), compared with the traditional carbon chain structure, it retains both the rigid structural characteristics of rosin and the good flexibility of the non-planar structure of the aliphatic six-membered ring. Therefore, when used as a modifier in the preparation of powder coatings, the hardness, adhesion, and glossiness of the powder coatings can be improved, and the hydrophobic and anti-corrosion properties of the coatings can be improved; when used in the preparation of other thermosetting polyurethanes, the mechanical strength, heat resistance and hydrophobic properties of thermosetting polyurethane resins can be further improved, thereby improving the comprehensive performance of the polyurethane system.

[0039] The present invention has important scientific significance and practical application prospects for further promoting the greening of high-performance polyurethane.

[0040] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0042] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0043] Figure 1 The present invention discloses a schematic diagram of the reaction process of thermoplastic polyurethane prepared by reacting maleopimarol with diisocyanate. DETAILED DESCRIPTION

[0044] Exemplary embodiments will be described in detail herein, examples of which are shown in the accompanying drawings. When the following description refers to the drawings, unless otherwise indicated, the same numbers in different drawings represent the same or similar elements. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Instead, they are merely examples of methods consistent with some aspects of the present invention as detailed in the appended claims.

[0045] Maleopimaric acid is one of the important derivatives of rosin, a renewable resource. Its structure contains a ternary phenanthrene ring structure and three carboxyl structures. This structure has rigidity and good chemical stability, and can effectively improve the mechanical stability of polymer materials. Maleopimaric acid can be hydrogenated to obtain maleopimaric alcohol, in which the original three carboxylic acid structures are converted into three alcohol hydroxyl structures, and it is a polyol. Maleopimaric alcohol is used as a polyol component to react with a polyisocyanate curing agent, and the large-volume ternary phenanthrene ring structure of rosin can be introduced into the polymer main chain to prepare high-performance bio-based thermosetting polyurethane materials. Blending it with other polyurethane materials can further improve the hardness, heat resistance, hydrophobicity and other comprehensive properties of polyurethane materials, and promote the development of green bio-based polyurethane materials and the improvement of technical level.

[0046] Specifically, a maleopimarol-modified thermosetting polyurethane is prepared by polymerizing the following components: maleopimarol, polyol, chain extender, polyisocyanate curing agent, and catalyst, calculated by mass:

[0047] a) The maleopimarol component is 5 to 10 parts, preferably 6 to 10 parts.

[0048] The preparation method of maleopimaric acid is as follows: maleopimaric acid is dissolved in solvent 1, and a reducing agent is slowly added under low temperature conditions under the protection of an inert gas, and the reaction is carried out for 0.5 to 10 hours after the reducing agent is added, and then the temperature is raised to 40 to 80° C. and the reaction is carried out for 6 to 48 hours. After the reaction is completed, the excess reducing agent is quenched with a quenching agent, and then deionized water is added and fully shaken, and after filtering, vacuum filtration is performed at 40 to 60° C. to constant weight. A non-aqueous solvent is added to the constant weight filtrate, and after sufficient shaking, the mixture is allowed to stand for stratification, the water layer is removed, and the oil-containing layer liquid is subjected to high vacuum rotary evaporation to obtain a product having a triol structure-maleopimaric acid.

[0049] The solvent 1 is preferably a mixed solvent of one or more of anhydrous tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl ether, ethyl butyl ether, dihexyl ether, dipentyl ether, and 3-methylfuran.

[0050] The low temperature condition can be achieved by a liquid nitrogen quick freezing method, or by maintaining a temperature condition of -10°C to 15°C through a temperature control device.

[0051] The inert gas is preferably nitrogen or argon, or a mixture of the two.

[0052] The reducing agent is preferably one or more of lithium aluminum hydride, sodium borohydride, potassium borohydride or dibutylaluminum hydride.

[0053] The quenching agent is one or more of water, sodium hydroxide aqueous solution, sodium carbonate aqueous solution, sodium bicarbonate aqueous solution, hydrochloric acid solution or diethyl sulfuric acid solution.

[0054] The non-aqueous solvent is preferably a mixture of one or more of toluene, xylene, ethyl acetate and butyl acetate.

[0055] b) The polyester polyol component is 20 to 95 parts, preferably 24 to 91 parts.

[0056] The number average molecular weight of the polyol is 800-6000 g / mol, preferably 1000-4000 g / mol, and based on the total weight of the polyol component, the polyol comprises 50-100 wt% of bio-based polyester polyol and 0-50 wt% of petroleum-based polyol, wherein 70-100 wt% of bio-based polyester polyol and 0-30 wt% of petroleum-based polyol are preferred;

[0057] c) Chain extender component 0 to 25 parts, preferably 1.5 to 23 parts.

[0058] Based on the total weight of the chain extender component, the chain extender contains 50-100 wt% of a bio-based chain extender and 0-50 wt% of a petroleum-based chain extender, preferably 70-100 wt% of a bio-based chain extender and 0-30 wt% of a petroleum-based chain extender;

[0059] d) 10 to 45 parts of polyisocyanate component, preferably 12 to 44 parts.

[0060] The polyisocyanate is preferably diisocyanate, triisocyanate or tetraisocyanate;

[0061] Based on the total weight of the polyisocyanate component, the polyisocyanate contains 10 to 60 wt% of bio-based isocyanate and 40 to 90 wt% of petroleum-based isocyanate, wherein 30 to 60 wt% of bio-based isocyanate and 40 to 70% of petroleum-based isocyanate are preferred;

[0062] e) Catalyst component 0.001 parts.

[0063] The catalyst is preferably 50 to 100 wt% of a non-tin environmentally friendly catalyst and 0 to 50 wt% of a tin-containing catalyst, based on the total weight of the catalyst components.

[0064] Preferably, in components a) to c), the total content of bio-based components is greater than or equal to 50wt%, preferably greater than or equal to 60wt%. The bio-based described herein refers to biological origin, and the petroleum-based described herein refers to petroleum origin. The content of bio-based components described here refers to the percentage of biological origin components in the total mass of components a) to e).

[0065] Furthermore, the polyol has a hydroxyl value ranging from 18 to 140 mg KOH / g; a water content less than or equal to 300 ppm, preferably less than or equal to 200 ppm; and a catalyst content less than or equal to 400 ppm, preferably less than or equal to 200 ppm.

[0066] The petroleum-based polyol includes one or more of petroleum-based diols, petroleum-based triols, petroleum-based tetraols and petroleum-based polyester polyols; wherein the petroleum-based diols are preferably one or more of 1,3-propylene glycol, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, dipropylene glycol, hexanediol, diethylene glycol, methyl propanediol, neopentyl glycol and polycarbonate diols; the petroleum-based triols are preferably one or more of polycaprolactone triols, propylene glycol and polyether triols; and the petroleum-based tetraols are preferably pentaerythritol.

[0067] Among them, petroleum-based polyester polyols are preferred, specifically one or more of polybutylene adipate diol (PBA), polyethylene adipate diol (PEA), and polyhexamethylene adipate diol (PHA).

[0068] The bio-based polyester polyol is a polyol extracted from natural products, or obtained by reacting a bio-based acid with one or more small molecule alcohols, and the small molecule alcohol can be bio-based or petroleum-based or both. The bio-based acid is mainly one or more of bio-based succinic acid, sebacic acid, and polylactic acid. The bio-based small molecule alcohol is mainly one or more of bio-based 1,3-propylene glycol, bio-based 1,2-propylene glycol, bio-based ethylene glycol, and bio-based 1,4-butanediol. The petroleum-based small molecule alcohol is one or more of petroleum-based 1,3-propylene glycol, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, dipropylene glycol, hexanediol, diethylene glycol, methyl propanediol, neopentyl glycol, polycaprolactone triol, glycerol, polyether triol, pentaerythritol, lignin, polysaccharide, cellulose, and dextrin.

[0069] The bio-based polyester polyol has a hydroxyl value ranging from 18 to 140 mg KOH / g, preferably 28 to 115 mg KOH / g; an acid value less than or equal to 2 mg KOH / g, preferably less than or equal to 1 mg KOH / g; a moisture content less than or equal to 300 ppm, preferably less than or equal to 200 ppm; a catalyst content less than or equal to 400 ppm, preferably less than or equal to 200 ppm; and a biobased content greater than or equal to 50 wt%, preferably greater than or equal to 60 wt%, based on the total weight of the bio-based polyester polyol component.

[0070] The bio-based polyester polyol is preferably one or more of poly(propylene succinate) diol (PPSu), poly(butylene succinate) diol (PBSu), poly(propylene sebacate) diol (PPSe), and poly(butylene sebacate) diol (PBSe).

[0071] Furthermore, the petroleum-based chain extender is one or a mixture of petroleum-based ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, dipropylene glycol, hexanediol, diethylene glycol, methyl propylene glycol, and neopentyl glycol, preferably petroleum-based 1,4-butanediol.

[0072] The bio-based chain extender is one or a mixture of bio-based 1,3-propylene glycol, bio-based 1,2-propylene glycol, bio-based ethylene glycol, and bio-based 1,4-butanediol, preferably bio-based 1,3-propylene glycol.

[0073] Further, the petroleum-based polyisocyanate is a mixture of one or more of hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, 4,4-dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, m-xylyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4',4"-triphenylmethane triisocyanate, dimethyl triphenylmethane tetraisocyanate, dimethyl isoxazole tetraisocyanate, and tetraisocyanatosilane. Preferably, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4',4"-triphenylmethane triisocyanate, dimethyl triphenylmethane tetraisocyanate, and tetraisocyanatosilane are used.

[0074] The bio-based polyisocyanate is one of bio-based 1,4-butanediisocyanate and bio-based 1,5-pentanediisocyanate, or a mixture of the two.

[0075] Furthermore, the organotin catalyst is one of stannous octoate, dibutyltin dilaurate, dibutyltin dioxalate, dibutyltin didodecylsulfide, or a mixture of several of them, preferably dibutyltin dilaurate.

[0076] The non-tin environmentally friendly catalyst is a mixture of one or more of triethylamine, triethylenediamine, dimethylcyclohexylamine, dimethylcyclohexylamine of tertiary amines, potassium isooctanoate, potassium oleate, bismuth isooctanoate and zinc isooctanoate of organic metals, preferably bismuth isooctanoate.

[0077] The first method for preparing a maleopimarol-modified thermosetting polyurethane disclosed by the present invention comprises the following specific steps: blending three components, namely a) maleopimarol, b) polyol and c) chain extender; adding solvent 2 to uniformly mix the three components, then adding d) polyisocyanate and stirring evenly; then adding e) catalyst and stirring evenly; reacting at 40-200° C.; and removing the solvent to obtain maleopimarol-modified thermosetting polyurethane.

[0078] The solvent 2 is one or more of xylene, ethyl acetate, butyl acetate, dichloromethane, tetrahydrofuran, and toluene, preferably xylene, ethyl acetate, butyl acetate, and dichloromethane.

[0079] The second method for preparing a maleopimarol-modified thermosetting polyurethane according to the present invention comprises the following specific steps: a) maleopimarol, b) polyol, c) chain extender, d) diisocyanate, and e) catalyst are mixed and reacted at a temperature of 70 to 200° C. to obtain maleopimarol-modified thermosetting polyurethane.

[0080] In addition, the present invention also provides a method for preparing maleopimarol-modified thermosetting polyurethane, which specifically comprises the following steps: dividing the required bio-based polyester polyol into two parts, adding one part b) polyester polyol, d) isocyanate, c) chain extender and e) catalyst into a first reaction kettle, heating to form a first reactant, and evacuating and keeping warm for later use; adding the other part b) polyester polyol and a) maleopimarol into a second reaction kettle to form a second reactant, and evacuating and keeping warm for later use; preheating an oven, pouring the first and second reactants into a mold by a pouring machine, and then putting them into an oven for curing, and finally demolding to obtain maleopimarol-modified thermosetting polyurethane.

[0081] The present invention utilizes the alcohol hydroxyl group of the triol compound maleopimarol to react with the isocyanate group of the polyisocyanate to form an urethane chemical bond, and the system with a functionality greater than 2 undergoes polymerization to form a cross-linked network polymer with thermosetting properties. In the system, maleopimarol reacts with the polyisocyanate (taking diisocyanate as an example) to form a rigid urethane chain component, and the polyol and the chain extender are mainly long carbon chain diols, which react with the polyisocyanate to form a flexible chain component, and a product with better performance is obtained by matching the rigid chain with the flexible chain. Due to the room temperature reaction, a catalyst needs to be added to adjust the polymerization reaction time, so a portion of the catalyst is added. The reaction mechanism is shown in the attached Figure 1 .

[0082] The bio-based raw material information involved in the embodiments of the present invention is as follows:

[0083] (1) Maleopimaric acid is prepared by Diels-Alder reaction of rosin and maleic acid or maleic anhydride. According to the literature (Yin Hongmei, Guo Hong, Xu Feng, et al. Synthesis and application of maleopimaric acid [J]. Journal of Shenyang Institute of Chemical Technology, 1998, (02): 15-21.)

[0084] Add a certain amount of rosin and maleic anhydride into a three-necked flask, heat to 180℃ and react for 4-5 hours, and cool to a light yellow solid. Treat the powder with carbon tetrachloride for 2-3 times to remove the unreacted rosin, and then treat it with water for several times to remove the unreacted maleic anhydride to obtain a white powder product. The rosin and maleopimaric acid in the carbon tetrachloride treatment solution can be recovered.

[0085] (2) Bio-based polycarboxylic acids:

[0086] Bio-based succinic acid was purchased from BioAmber;

[0087] Bio-based sebacic acid was purchased from Hebei Kaide Biomaterials Co., Ltd.;

[0088] (3) Bio-based polyester polyols:

[0089] Bio-based 1,3-propanediol was purchased from DuPont.

[0090] Preparation of bio-based poly(1,3-propylene glycol succinate) diol was prepared according to the literature (Liu Yiwu, Wang Qian, Tan Jinghua, et al. Synthesis and characterization of biodegradable poly(1,3-propylene glycol succinate) diol [J]. Journal of Packaging, 2014, 6(01): 10-15.)

[0091] Bio-based succinic acid and bio-based 1,3-propylene glycol were put into a three-necked flask equipped with a stirrer in a molar ratio of 1:1.2, and dibutyltin dilaurate was added with a mass fraction of 0.3% of the total amount of raw materials, and heated to 140°C under argon protection; after reacting for 1h, switch to a reduced pressure reaction device and heat to 160°C; adjust the vacuum degree of the flask to -0.1MPa and react for 2h; then heat to 190°C and continue the reaction; when the acid value is less than 1.5mg KOH / g and the hydroxyl value reaches a predetermined value, stop the reaction. The hydroxyl value of 56mg KOH / g corresponds to a number average molecular weight of 2000g / mol, and the hydroxyl value of 112KOH / g corresponds to a number average molecular weight of 1000g / mol. The obtained product was purified and then vacuum dried at 60°C for 24h.

[0092] Preparation of bio-based poly (1,3-propylene glycol sebacate) diol, according to the literature (Liu Quanyong, Tan Tianwei, Weng Jingyi, et al. Synthesis of poly (1,3-propylene glycol sebacate) ester under catalyst-free conditions and study of its molecular weight [J]. Modernization

[0093] Engineering, 2008, (S2): 169-173.)

[0094] Bio-based sebacic acid and bio-based 1,3-propylene glycol were mixed in a three-necked flask in a molar ratio of 1:1.1, and then heated and vacuumed to melt them at 120°C and 2kPa. When the reaction monomers were completely melted, the magnetic stirrer was started to start the reaction; when the acid value was less than 1mg KOH / g and the hydroxyl value reached the predetermined value, the reaction was stopped. The hydroxyl value of 38mgKOH / g corresponds to a number average molecular weight of 3000g / mol, and the hydroxyl value of 112mg KOH / g corresponds to a number average molecular weight of 1000g / mol.

[0095] Preparation of bio-based poly 1,4-butylene sebacic acid diol was prepared according to the literature (Cai Guoxing, Wu Manjiang, Ai Li, Zhang Lijing. Study on the polymerization reaction of 1,4-butanediol and sebacic acid [J]. Chemistry and Bioengineering, 2008, (07): 17-19.)

[0096] Bio-based sebacic acid and petroleum-based 1,4-butanediol were added to a three-necked flask in a molar ratio of 1:1.2, and the temperature was raised to 140°C. After reacting for 1 hour, a solid-supported butyl titanate catalyst with a mass fraction of 1.2% of the total amount of raw materials was added, and then the temperature was raised to 160°C. When the acid value was less than 1 mg KOH / g and the hydroxyl value reached 28 mg KOH / g, the reaction was stopped, and the corresponding number average molecular weight was 4000 g / mol.

[0097] Preparation of bio-based poly(1,4-butylene succinate diol) was prepared according to the literature (Wu Jianning, Meng Guihua, Liu Zhiyong, et al. Synthesis and process research of poly(1,4-butylene succinate diol) [J]. Synthetic Materials Aging and Application, 2012, 41(02): 6-9+60.)

[0098] Add bio-based succinic acid and petroleum-based 1,4-butanediol in a molar ratio of 1:1.3 into a four-necked flask, add stannous chloride catalyst with a mass fraction of 1.2% of the total raw material; install a stirring device and a distillation device; control the oil bath temperature to 140℃, and react for 1h under stirring. Change the reaction device to a vacuum distillation device, stir, and heat to 180℃ at 10℃ / 10min. Reduce the internal pressure to 1kPa and react at a constant temperature; stop the reaction when the acid value is less than 1mg KOH / g and the hydroxyl value reaches 56mg KOH / g, and the corresponding number average molecular weight is 2000g / mol.

[0099] The preparation of bio-based poly(1,3-propylene glycol adipate) diol was based on the literature (Chen Si. Functionalization of carbon nanotubes and preparation and performance study of poly(1,3-propylene glycol adipate) diol-hydroxy carbon nanotube copolymer [J]. Materials Guide

[0100] Journal of Chinese Academy of Sciences, 2012, 26(S2): 64-68.)

[0101] Petroleum-based adipic acid and bio-based 1,3-propylene glycol are added to a three-necked flask in a molar ratio of 1:1.4, and stirred and heated in an oil bath at 200-300°C until almost no fraction is generated, and 0.3% of the mass of 1,3-propylene glycol is added as a butyl titanate catalyst; when the acid value is less than 1 mg KOH / g and the hydroxyl value reaches 56 mg KOH / g, the reaction is stopped, and the corresponding number average molecular weight is 2000 g / mol.

[0102] (4) Bio-based chain extender: Bio-based 1,3-propylene glycol, purchased from DuPont.

[0103] (5) Bio-based diisocyanates:

[0104] Bio-based 1,4-butanediisocyanate, according to the method reported in the literature (Zhang Yongzhen, Shi Sen, Li Yuan, et al. Preparation of biomass-based 1,4-butanediisocyanate and its application in medical polyurethane materials [J]. Polyurethane Industry, 2013, 28(6): 1-4), is prepared by hydrogenating bio-based succinic acid to synthesize bio-based 1,4-butanediamine, and then reacting it with phosgene to obtain bio-based 1,4-butanediisocyanate through a gas phase phosgene method.

[0105] Bio-based 1,5-pentane diisocyanate is prepared by thermally decomposing bio-based 1,5-pentanediamine through a phosgenation reaction according to the method disclosed in patent CN102782146.

[0106] The present invention is further explained below in conjunction with specific embodiments, but is not intended to limit the protection scope of the present invention.

[0107] Embodiment 1:

[0108] 23wt% PPSu (bio-based poly(1,3-propylene glycol) succinate) with a molecular weight of 2000g / mol, a total amount of diisocyanate of 32.56% (of which petroleum-based diisocyanate accounts for 70wt% and bio-based diisocyanate accounts for 30wt%), namely 22.92wt% MDI (4,4-diphenylmethane diisocyanate), 9.64wt% BDI (bio-based 1,4-butylene diisocyanate), 12.43wt% PDO (bio-based 1,3-propylene glycol), and 0.01wt% bismuth isooctanoate are added to the first reactor to react and form a first reactant, and the temperature of the first reactor is maintained between 110°C and 120°C, preferably at 120°C, and then the first reactor is evacuated so that the vacuum degree in the first reactor is -0.08 to 0.1Mpa. In this step, since the mixing reaction will release a large amount of heat, the temperature in the first reactor will exceed 120°C. Therefore, after the reaction is completed to form the first reactant, the temperature in the first reactor is cooled to 120°C before continuing with the subsequent steps.

[0109] 9wt% of maleic pinol with a molecular weight of 377g / mol and the remaining 23wt% of PPSu (bio-based poly(1,3-propylene glycol) succinate diol) with a molecular weight of 2000g / mol are added into the second reactor, heated and stirred to mix evenly, and then the second reactor is evacuated to a vacuum degree of -0.08 to 0.1Mpa, and the temperature in the second reactor is maintained between 110°C and 120°C, preferably at 120°C, and the reaction is completed to form a second reactant.

[0110] The oven is preheated, wherein the preheating temperature of the oven is 110°C to 120°C, and the preferred preheating temperature is 120°C, so that the temperature of the preheated oven is the same as the temperature in the first reactor and the second reactor. After the oven reaches the preheating temperature, the first reactant and the second reactant in the first reactor are poured into the pouring mold by a pouring machine, so that the first and second reactants will begin to produce a polymerization reaction, and then the pouring mold is placed in a preheated oven with a preheating temperature of 120°C for curing. The first period of the curing step is 1 hour, the first curing temperature is maintained at 120°C and the second curing temperature is maintained at 140°C for 48 hours, and demoulding is performed after the curing is completed to obtain bio-based thermosetting polyurethane.

[0111] Example 2

[0112] The difference between this embodiment and embodiment 1 is that in this embodiment, the weight fraction of maleopinol with a molecular weight of 377 g / mol is changed to 9.2 wt %, the weight fraction of bio-based polyester polyol is changed to 24.75 wt %, and the bio-based polyester polyol is replaced by PPSu (bio-based poly(1,3-propylene succinate)) with a molecular weight of 1000 g / mol, and the total amount of diisocyanate is changed to 43.27% (of which petroleum-based diisocyanate accounts for 60 wt % and bio-based diisocyanate accounts for 40 wt %), that is, the weight fraction of petroleum-based isocyanate MDI (4,4-diphenylmethane diisocyanate) is changed to 26.84 wt %, the weight fraction of bio-based isocyanate BDI (bio-based 1,4-butylene diisocyanate) is changed to 16.73 wt %, and the weight fraction of chain extender PDO (bio-based 1,3-propylene glycol) is changed to 22.47 wt %.

[0113] Example 3

[0114] The difference between this embodiment and embodiment 1 is that in this embodiment, the weight fraction of maleopinol with a molecular weight of 377 g / mol is changed to 9.4 wt %, the weight fraction of bio-based polyester polyol is changed to 75.6 wt %, and the bio-based polyester polyol is replaced by PPSe (bio-based poly 1,3-propylene sebacate) with a molecular weight of 3000 g / mol, the total amount of diisocyanate is changed to 12.16% (of which petroleum-based diisocyanate accounts for 50 wt % and bio-based diisocyanate accounts for 50 wt %), that is, the weight fraction of petroleum-based isocyanate is changed to 6.08 wt %, and petroleum-based isocyanate is replaced by HDI (hexamethylene diisocyanate), the weight fraction of bio-based isocyanate is changed to 6.08 wt %, and bio-based isocyanate is replaced by PDI (bio-based 1,5-pentanediisocyanate), and the weight fraction of chain extender PDO (bio-based 1,3-propylene glycol) is changed to 2.83 wt %.

[0115] Example 4

[0116] The difference between this embodiment and embodiment 1 is that in this embodiment, the weight fraction of maleopimarol with a molecular weight of 377 g / mol is changed to 6.8wt%, the weight fraction of bio-based polyester polyol is changed to 73.2wt%, and the bio-based polyester polyol is replaced by PBSe (bio-based poly 1,4-butylene sebacate) with a molecular weight of 4000 g / mol, the total amount of diisocyanate is changed to 15.82%, (of which petroleum-based diisocyanate accounts for 40wt% and bio-based diisocyanate accounts for 60wt%), that is, petroleum-based isocyanate is replaced by HMDI (4,4-dicyclohexylmethane diisocyanate), and the weight fraction is changed to 6.33%, bio-based isocyanate is replaced by PDI (bio-based 1,5-pentane diisocyanate), and the weight fraction is changed to 9.49wt%, and the weight fraction of chain extender PDO (bio-based 1,3-propylene glycol) is changed to 4.17wt%.

[0117] Comparative Example 1

[0118] 33.5wt% PPSu (bio-based polysuccinic acid 1,3-propylene glycol) with a molecular weight of 2000g / mol, 16.7wt% MDI (4,4-diphenylmethane diisocyanate), 7wt% BDI (bio-based 1,4-butylene diisocyanate), 9.29wt% PDO (bio-based 1,3-propylene glycol), 0.01wt% bismuth isooctanoate are added to the first reactor to react and form the first reactant, and the temperature of the first reactor is maintained between 110°C and 120°C, preferably at 120°C, and then the first reactor is evacuated to a vacuum degree of -0.08 to 0.1Mpa. In this step, since the mixing reaction releases a large amount of heat, the temperature in the first reactor will exceed 120°C, so after the reaction is completed to form the first reactant, the temperature in the first reactor is cooled to 120°C before continuing to use in subsequent steps.

[0119] The remaining 33.5wt% of PPSu (bio-based poly(1,3-propylene succinate diol) with a molecular weight of 2000g / mol) was added into the second reactor, heated and stirred, and then the second reactor was evacuated to a vacuum degree of -0.08 to 0.1Mpa. The temperature in the second reactor was maintained between 110°C and 120°C, with a preferred temperature of 120°C. The reaction was completed to form a second reactant.

[0120] The oven is preheated, wherein the preheating temperature of the oven is 110°C to 120°C, and the preferred preheating temperature is 120°C, so that the temperature of the preheated oven is the same as the temperature in the first reactor and the second reactor. After the oven reaches the preheating temperature, the first reactant and the second reactant in the first reactor are poured into the pouring mold by a pouring machine, so that the first and second reactants will begin to produce a polymerization reaction, and then the pouring mold is placed in a preheated oven with a preheating temperature of 120°C for curing. The first period of the curing step is 1 hour, the first curing temperature is maintained at 120°C and the second curing temperature is maintained at 140°C for 48 hours, and after the curing is completed, the mold is demoulded to obtain thermosetting polyurethane.

[0121] Comparative Example 2

[0122] The difference between this comparative example and comparative example 1 is that in this comparative example, the weight fraction of the bio-based polyester polyol is changed to 41.5wt%, and the bio-based polyester polyol is replaced by PPSu (bio-based poly 1,3-propylene succinate) with a molecular weight of 1000g / mol, and the total amount of diisocyanate is changed to 39.49% (of which petroleum-based diisocyanate accounts for 60wt% and bio-based diisocyanate accounts for 40wt%), that is, the weight fraction of petroleum-based isocyanate MDI (4,4-diphenylmethane diisocyanate) is changed to 23.69wt%, the weight fraction of bio-based isocyanate BDI (bio-based 1,4-butylene diisocyanate) is changed to 15.8wt%, and the weight fraction of chain extender PDO (bio-based 1,3-propylene glycol) is changed to 19wt%.

[0123] Comparative Example 3

[0124] The difference between this comparative example and comparative example 1 is that in this comparative example, the weight fraction of the bio-based polyester polyol is changed to 91wt%, and the bio-based polyester polyol is replaced by PPSe (bio-based poly 1,3-propylene sebacate) with a molecular weight of 3000g / mol, the weight fraction of the petroleum-based isocyanate is changed to 5wt%, and the total amount of diisocyanate is changed to 7.29% (of which the petroleum-based diisocyanate accounts for 50wt% and the bio-based diisocyanate accounts for 50wt%), that is, the petroleum-based isocyanate is replaced by HDI (hexamethylene diisocyanate), the weight fraction of the bio-based isocyanate is changed to 3.645wt%, and the bio-based isocyanate is replaced by PDI (bio-based 1,5-pentane diisocyanate), and the weight fraction of the chain extender PDO (bio-based 1,3-propylene glycol) is changed to 3.645wt%.

[0125] Comparative Example 4

[0126] The difference between this comparative example and comparative example 1 is that in this comparative example, the weight fraction of the bio-based polyester polyol is changed to 88wt%, and the bio-based polyester polyol is replaced by PBSe (bio-based poly 1,4-butylene sebacate) with a molecular weight of 4000g / mol, the total amount of diisocyanate is changed to 9.48%, (of which petroleum-based diisocyanate accounts for 40wt% and bio-based diisocyanate accounts for 60wt%), that is, the petroleum-based isocyanate is replaced by HMDI (4,4-dicyclohexylmethane diisocyanate), and the weight fraction is changed to 3.79%, the bio-based isocyanate is replaced by PDI (bio-based 1,5-pentane diisocyanate), and the weight fraction is changed to 5.69wt%, and the weight fraction of the chain extender PDO (bio-based 1,3-propylene glycol) is changed to 2.51wt%.

[0127] Comparative Example 5

[0128] The difference between this comparative example and comparative example 1 is that in this comparative example, the weight fraction of the bio-based polyester polyol is changed to 73wt%, and the bio-based polyester polyol is replaced by PBSu (bio-based polybutylene succinate) with a molecular weight of 2000g / mol, the petroleum-based isocyanate only uses MDI (4,4-diphenylmethane diisocyanate), and the weight fraction is changed to 19.93wt%, and the chain extender is replaced by petroleum-based BDO (1,4-butanediol), and the weight fraction is changed to 7.06wt%.

[0129] Comparative Example 6

[0130] The difference between this comparative example and comparative example 1 is that in this comparative example, the weight fraction of the bio-based polyester polyol is changed to 44.21wt%, and the bio-based polyester polyol is replaced by 2000g / mol PPA (bio-based poly 1,3-propylene adipate) with a molecular weight of 2000g / mol, the petroleum-based isocyanate only uses HDI (4,4-hexamethylene diisocyanate), and the weight fraction is changed to 33.91wt%, and the chain extender is replaced by petroleum-based HDO (1,6-hexanediol), and the weight fraction is changed to 13.65wt%.

[0131] The differences in the composition of the above examples and the comparative examples are summarized in the following table:

[0132]

[0133] The comparison of product parameters obtained in the above embodiment and the comparative example is shown in the following table:

[0134]

[0135]

[0136] Compared with the comparative examples 1-6, the raw materials used in the above-mentioned embodiments 1-4 are mostly natural rosin derivatives and other bio-based materials, and organic bismuth is used to replace organic tin as a catalyst, which is green and environmentally friendly; the petroleum-based solvents or plasticizers and organic tin curing agents used in the comparative examples are more environmentally friendly; the polyurethane synthesized in the embodiments 1-4 has the advantage of high solid content, which reduces the impact of the volatilization of organic solvents on the environment. At the same time, the reaction temperature is reduced, so that the possible energy consumption in actual production is reduced, the manufacturing cost in actual production is reduced, and the product is more competitive in the market. Finally, by introducing a rigid rosin structure in the embodiment of the present invention, the mechanical properties of the polyurethane are significantly increased compared with the comparative example, especially the hardness reaches 97A, so it can be used as a rigid modified polyurethane material and mixed with other polyurethane materials for modification, further expanding its application field; the present invention can be used as a reinforcing modified component and mixed with polyurethane materials to prepare high-performance thermosetting polyurethane, and improve the material's pressure resistance, tensile strength, hardness, and comprehensive properties such as hydrophobicity and corrosion resistance.

[0137] Those skilled in the art will readily appreciate other embodiments of the present invention after considering the specification and practicing the invention disclosed herein. This application is intended to cover any variations, uses or adaptations of the present invention that follow the general principles of the present invention and include common knowledge or customary techniques in the art that are not disclosed by the present invention. The specification and examples are to be considered exemplary only, and the true scope and spirit of the present invention are indicated by the following claims.

[0138] It should be understood that the present invention is not limited to what has been described above and that various modifications and changes may be made without departing from its scope. The scope of the present invention is limited only by the appended claims.

Claims

1. A maleopimarol-modified thermosetting polyurethane, characterized in that: In parts by weight, it includes: 5-10 parts of maleopimarol, 20-95 parts of polyester polyol, 1-25 parts of chain extender, 10-45 parts of polyisocyanate, and 0.001 parts of catalyst; wherein the amount of chain extender is not 0; The total content of bio-based components in maleopimarol, polyester polyol and chain extender is greater than or equal to 50wt%.

2. The maleopimarol-modified thermosetting polyurethane according to claim 1, characterized in that: The number average molecular weight of the polyol is 800 to 6000 g / mol, the hydroxyl value of the polyol is in the range of 18 to 140 mg KOH / g; the water content is less than or equal to 300 ppm; Based on the total weight of the polyol component, the polyol includes 50 to 100 wt% of bio-based polyol and / or bio-based polyester polyol, and 0 to 50 wt% of petroleum-based polyol; The bio-based polyol is one or more of lignin, polysaccharide, cellulose, and dextrin; The petroleum-based polyol includes one or more of petroleum-based diol, petroleum-based triol, petroleum-based tetraol and petroleum-based polyester polyol; The bio-based polyester polyol has a hydroxyl value ranging from 18 to 140 mg KOH / g; an acid value less than or equal to 2 mg KOH / g; a moisture content less than or equal to 300 ppm, and a bio-based content greater than or equal to 50 wt% based on the total weight of the bio-based polyester polyol component; The bio-based polyester polyol is a polyol extracted from natural products, or obtained by reacting a bio-based acid with one or more small molecule alcohols, wherein the small molecule alcohol is a bio-based small molecule alcohol or a petroleum-based small molecule alcohol or both.

3. The maleopimarol-modified thermosetting polyurethane according to claim 2, characterized in that: The petroleum-based triol is one or more of polycaprolactone triol, propylene glycol, and polyether triol; The petroleum-based tetraol is pentaerythritol; The petroleum-based polyester polyol is one or more of polybutylene adipate diol (PBA), polyethylene adipate diol (PEA), and polyhexamethylene adipate diol (PHA); The bio-based acid is one or more of bio-based succinic acid, sebacic acid, and polylactic acid; The bio-based small molecule alcohol is one or more of bio-based 1,3-propylene glycol, bio-based 1,2-propylene glycol, bio-based ethylene glycol, and bio-based 1,4-butanediol; The petroleum-based small molecule alcohol is one or more of petroleum-based 1,3-propylene glycol, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, dipropylene glycol, hexylene glycol, diethylene glycol, methyl propanediol, neopentyl glycol, polycaprolactone triol, glycerol, polyether triol, and pentaerythritol; The bio-based polyester polyol is a polyol extracted from natural products, including one or more of poly(propylene succinate) diol (PPSu), poly(butylene succinate) diol (PBSu), poly(propylene sebacate) diol (PPSe), and poly(butylene sebacate) diol (PBSe).

4. The maleopimarol-modified thermosetting polyurethane according to claim 1, characterized in that: Based on the total weight of the chain extender component, the chain extender contains 50 to 100 wt% of a bio-based chain extender and 0 to 50 wt% of a petroleum-based chain extender; The petroleum-based chain extender is one or a mixture of petroleum-type ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, dipropylene glycol, hexanediol, diethylene glycol, methyl propylene glycol, and neopentyl glycol.

5. The maleopimarol-modified thermosetting polyurethane according to claim 1, characterized in that: The polyisocyanate is preferably diisocyanate, triisocyanate or tetraisocyanate; Based on the total weight of the polyisocyanate component, the polyisocyanate contains 10 to 60 wt% of bio-based isocyanate and 40 to 90 wt% of petroleum-based isocyanate; The bio-based polyisocyanate is one or a mixture of bio-based 1,4-butanediisocyanate or bio-based 1,5-pentanediisocyanate; The petroleum-based polyisocyanate is a mixture of one or more of hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, 4,4-dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, meta-xylyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4',4"-triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, dimethylisoxazole tetraisocyanate and tetraisocyanatosilane.

6. The maleopimarol-modified thermosetting polyurethane according to claim 1, characterized in that: Based on the total weight of the catalyst components, the catalyst includes 50 to 100 wt% of a non-tin environmentally friendly catalyst and 0 to 50 wt% of a tin-containing catalyst; The organotin catalyst is one or a mixture of stannous octoate, dibutyltin dilaurate, dibutyltin dioxalate, and dibutyltin didodecylsulfide; The non-tin environmentally friendly catalyst is a mixture of one or more of triethylamine, triethylenediamine, dimethylcyclohexylamine, dimethylcyclohexylamine of tertiary amines and potassium isooctanoate, potassium oleate, bismuth isooctanoate and zinc isooctanoate of organic metals.

7. The maleopimarol-modified thermosetting polyurethane according to claim 1, characterized in that: The preparation method of maleopimaric acid is as follows: maleopimaric acid is dissolved in a solvent, and a reducing agent is slowly added under low temperature conditions and inert gas protection, and the reaction is carried out for 0.5 to 10 hours after the reducing agent is added, and then the temperature is raised to 40 to 80° C. and the reaction is carried out for 6 to 48 hours; after the reaction is completed, the excess reducing agent is quenched with a quenching agent, and then deionized water is added and fully shaken, and after filtering, vacuum filtration is carried out at 40 to 60° C. to constant weight; a non-aqueous solvent is added to the constant weight filtrate, and after fully shaking, the filtrate is allowed to stand for stratification, the water layer is removed, and the oil-containing layer liquid is subjected to high vacuum rotary evaporation to obtain a product having a triol structure-maleopimaric acid; The solvent is one or more mixed solvents selected from anhydrous tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethyl ether, ethyl butyl ether, dihexyl ether, dipentyl ether, and 3-methylfuran; The low temperature condition is a temperature condition of -10°C to 15°C; The inert gas is one of nitrogen or argon or a mixture of the two; The reducing agent is one or more mixtures of lithium aluminum hydride, sodium borohydride, potassium borohydride or dibutylaluminum hydride; The quenching agent is one or more of water, sodium hydroxide aqueous solution, sodium carbonate aqueous solution, sodium bicarbonate aqueous solution, hydrochloric acid solution or disulfuric acid solution; The non-aqueous solvent is a mixture of one or more of toluene, xylene, ethyl acetate and butyl acetate.

8. The method for preparing maleopimarol-modified thermosetting polyurethane according to any one of claims 1 to 6, characterized in that: include: The required polyester polyol is equally divided into two parts, one part of the polyester polyol, isocyanate, chain extender and catalyst is added into the first reaction kettle, heated to form the first reactant, and vacuumed and kept warm for later use; Another portion of polyester polyol and maleopimarol are added into the second reaction kettle to form a second reactant, which is then evacuated and kept warm for later use; the oven is preheated, the first and second reactants are poured into a mold using a pouring machine, and then put into the oven for curing, and finally demolded to obtain maleopimarol-modified thermosetting polyurethane.

9. The method for preparing maleopimarol-modified thermosetting polyurethane according to any one of claims 1 to 6, characterized in that: include: Maleopimarol, polyester polyol, chain extender, diisocyanate and catalyst are mixed and reacted at a temperature of 70-200 DEG C to obtain maleopimarol-modified thermosetting polyurethane.

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