Rosin derivative modified thermosetting bio-based polyurethane and preparation method thereof

Abstract

The invention discloses rosin derivative modified thermosetting bio-based polyurethane, which is prepared from the following ingredients in parts by weight: 5 to 50 parts of acrylpimaric acid (1-chloro-2 hydroxyl) propylene diester, 20 to 95 parts of dihydric alcohol, 0 to 25 parts of chain extenders, 5 to 55 parts of petroleum-based diisocyanate and 0.001 part of catalysts, and the amounts of the dihydric alcohol and the chain extenders are not 0. The polyurethane synthesized by the method has the characteristics of thermoplasticity and thermoset, the processing fluidity of a system can be improved, the process temperature can be reduced, the production cost can be reduced, and meanwhile, the mechanical property and the comprehensive property of the material system can be improved. And the compound can also be used as a plasticizing and reinforcing modified component to be blended with a polyurethane powder material to prepare a high-performance powder coating, so that the adhesive force, hardness, luster, hydrophobicity, corrosion resistance and other comprehensive properties of the powder coating are improved.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane materials, and in particular to a rosin derivative-modified thermosetting bio-based polyurethane and a preparation method thereof. Background Art

[0002] At present, the contradictions between population, resources and environment are becoming increasingly prominent. Vigorously developing low-carbon, green and environmentally friendly materials has become an important development direction for 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. 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 rosin acid, pimaric acid, and a small amount of fatty acids and neutral substances. Since the hydrogenated phenanthrene ring structure of rosin acid is similar to some petroleum-based aliphatic and aromatic compounds, it has great potential in replacing petroleum-based compounds to synthesize polyurethane.

[0003] Therefore, it is very meaningful to use rosin as a modified raw material to provide a method for preparing bio-based polyurethane with a simplified production process and low production cost. Summary of the invention

[0004] In view of this, the present invention provides a rosin derivative modified thermosetting bio-based polyurethane and a preparation method thereof, so as to improve the mechanical properties of the polyurethane.

[0005] In one aspect, the present invention provides a rosin derivative modified thermosetting bio-based polyurethane, comprising, by weight:

[0006] 5-50 parts of acrylpimaric acid (1-chloro-2-hydroxy)propylene glycol, 20-95 parts of diol, 0-25 parts of chain extender, 5-55 parts of petroleum-based diisocyanate, and 0.001 parts of catalyst, wherein the diol and chain extender are not zero.

[0007] Preferably, the sum of the bio-based component contents in propylene pimaric acid (1-chloro-2-hydroxy)propylene glycol, diol and chain extender is greater than or equal to 50 wt %, wherein the bio-based component content refers to the percentage of biologically derived components in the total mass of all components.

[0008] Preferably, the diol has a number average molecular weight of 800 to 6000 g / mol, and the diol includes bio-based polyester diol and petroleum-based polyester diol;

[0009] The diol has a hydroxyl value ranging from 18 to 140 mg KOH / g and a moisture content of less than or equal to 300 ppm.

[0010] Preferably, the chain extender comprises 50 to 100 wt % of a bio-based chain extender and 0 to 50 wt % of a petroleum-based chain extender based on the total weight of the chain extender component.

[0011] Preferably, the petroleum-based diisocyanate contains 10 to 60 wt% of bio-based diisocyanate and 40 to 90 wt% of petroleum-based diisocyanate based on the total weight of the diisocyanate component;

[0012] The bio-based polyester diol 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, a catalyst content less than or equal to 400 ppm, and a biobased content greater than or equal to 50 wt% based on the total weight of the bio-based polyester diol component.

[0013] Preferably, based on the total weight of the diisocyanate component, the diisocyanate comprises 10-60 wt% of bio-based diisocyanate and 40-90 wt% of petroleum-based diisocyanate; wherein the petroleum-based diisocyanate is a mixture of one or more of hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, 4,4-dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, meta-xylylene diisocyanate, and 1,5-naphthalene diisocyanate;

[0014] The bio-based diisocyanate is one of bio-based 1,4-butanediisocyanate and bio-based 1,5-pentanediisocyanate, or a mixture of the two.

[0015] Preferably, based on the total weight of the catalyst components, the catalyst comprises 50-100wt% of a non-tin environmentally friendly catalyst and 0-50wt% of a tin-containing catalyst; 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;

[0016] The organotin catalyst is one of stannous octoate, dibutyltin dilaurate, dibutyltin dioxalate, dibutyltin didodecylsulfide, or a mixture of several of them, preferably dibutyltin dilaurate.

[0017] Preferably, the preparation method of the acrylpimaric acid (1-chloro-2-hydroxy) propanediol is as follows: dissolving acrylpimaric acid in a non-aqueous solvent, then sequentially adding epichlorohydrin and an accelerator, and reacting at 40 to 110° C. for 0.5 to 48 hours; after the reaction is completed, adding deionized water, shaking thoroughly, standing to separate, removing the water layer, and subjecting the obtained oil-containing layer liquid to high vacuum rotary evaporation to obtain acrylpimaric acid (1-chloro-2-hydroxy) propanediol;

[0018] The amount of the non-water-soluble solvent is 3 to 200 wt% of the mass of acrylpimaric acid; the mass ratio of acrylpimaric acid to epichlorohydrin is 1:1.05 to 1.50;

[0019] The amount of the accelerator added is 0.5-3.5wt% of the total mass of acrylpimaric acid and epichlorohydrin;

[0020] The non-aqueous solvent is a mixture of one or more of toluene, xylene, ethyl acetate, butyl acetate, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, trichloroethylene, and dichloroethylene;

[0021] The accelerator is a mixture of one or more of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium fluoride and tetrabutylammonium hydroxide.

[0022] Preferably, the accelerator is added in multiple times, with the first addition being 1 / 2 of the total mass of the accelerator, and the remaining additions being 1 / 2 of the remaining mass of the accelerator, until all the accelerator is added.

[0023] In a second aspect, the present invention also provides a method for preparing a rosin derivative modified thermosetting bio-based polyurethane, comprising: blending three components of propylene pimaric acid (1-chloro-2-hydroxy) propanediol, diol, and chain extender, adding a solvent to mix the three components evenly, adding a diisocyanate and stirring evenly, then adding a catalyst and stirring evenly, reacting at 40 to 120° C., removing the solvent to obtain a modified thermoplastic polyurethane, and continuing to react at 120 to 200° C. to obtain a modified thermosetting polyurethane;

[0024] The solvent is one or more of xylene, ethyl acetate, butyl acetate, dichloromethane, tetrahydrofuran, and toluene, preferably xylene, ethyl acetate, butyl acetate, and dichloromethane;

[0025] or,

[0026] The method comprises: dividing the diol into two parts of equal mass, then adding one part of the diol, polyisocyanate, chain extender and catalyst into a first reaction kettle, reacting at 110-120° C., and then evacuating the first reaction kettle to obtain a first reactant;

[0027] Add another portion of diol and propylene glycol (1-chloro-2-hydroxy)pimaric acid into the second reaction kettle, heat and stir evenly at 110-120° C., and then evacuate the second reaction kettle to obtain a second reactant;

[0028] The oven is preheated to 110-120° C., the first reactant and the second reactant are poured into a preheated pouring mold by a pouring machine, and then placed in an oven for curing. The first period of the curing step is 1 hour, and the first curing temperature is maintained at 120° C. The second period of curing is at 140° C. for 48 hours. After the curing is completed, the mold is demolded to obtain acrylpimaric acid (1-chloro-2-hydroxy) propanediol modified bio-based thermosetting polyurethane.

[0029] The present invention provides a rosin derivative modified thermosetting bio-based polyurethane and a preparation method thereof. The polyurethane synthesized by the method has both thermoplastic and thermosetting characteristics, which can not only improve the processing fluidity of the system, reduce the process temperature, and reduce the production cost, but also improve the mechanical properties and comprehensive properties of the material system. It can also be used as a plasticizing and reinforcing modified component to be blended with polyurethane powder materials to prepare high-performance powder coatings, thereby improving the adhesion, hardness, gloss, and comprehensive properties of the powder coatings such as hydrophobicity and corrosion resistance.

[0030] Specifically, the thermosetting bio-based polyurethane obtained by this method can be used as a plasticizer to blend with other polyurethanes and polymer materials, which can improve the melt fluidity of the material, reduce the initial processing temperature, and improve the material's processing properties while increasing the material's mechanical strength; it can also be used as a polyurethane coating material, and the resulting coating film has the characteristics of high hardness, high gloss, and high adhesion; it can also be used as a reinforcing material, used in the reinforcing component of powder coatings, which can increase the coating's hardness, glossiness, and adhesion to the substrate.

[0031] The present invention has important scientific significance and practical application prospects for further promoting the greening and functionalization of high-performance polyurethane.

[0032] 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

[0033] 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.

[0034] 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.

[0035] Figure 1 The molecular structure diagram of acrylpimaric acid disclosed in the present invention;

[0036] Figure 2 The schematic diagram of the synthesis of propylene pimaric acid (1-chloro-2-hydroxy) propanediol disclosed in the present invention is shown;

[0037] Figure 3 The invention discloses a reaction process for preparing thermoplastic polyurethane from propylene pimaric acid (1-chloro-2-hydroxy) propanediol and diisocyanate;

[0038] Figure 4It is a schematic diagram of the thermoplastic polyurethane disclosed in the present invention being heated and dechlorinated to generate a compound containing a double bond;

[0039] Figure 5 It is a schematic diagram of double bond free radical crosslinking of the thermoplastic polyurethane disclosed in the present invention after heating and dechlorination. DETAILED DESCRIPTION

[0040] 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.

[0041] As one of the important derivatives of rosin, a renewable resource, the structure of propylene pimaric acid (such as Figure 1 ) contains a three-membered phenanthrene ring structure and two carboxyl structures, which have rigidity and good chemical stability, and can effectively improve the mechanical stability of polymer materials; in addition, the two carboxyl groups in its structure are chemically reactive and can react with epichlorohydrin under the action of a catalyst to open the ring of epichlorohydrin and combine with the carboxyl groups to generate acrylpimaric acid (1-chloro-2-hydroxy) propanediol (such as Figure 2 The acrylpimaric acid (1-chloro-2-hydroxy) propanediol has two hydroxyl groups in its structure and can be used as a polyol component to react with polyisocyanate to obtain a new type of polyurethane material, which has broad application prospects.

[0042] To this end, the present invention first provides a rosin derivative modified thermosetting bio-based polyurethane, which is polymerized by the following components: propylene pimaric acid (1-chloro-2-hydroxy) propanediol, diol, chain extender, diisocyanate curing agent, catalyst, and the like, in parts by weight:

[0043] a) propylene glycol pimaric acid (1-chloro-2-hydroxy) propylene glycol component is 5 to 100 parts, preferably 5 to 50 parts. The preparation method of propylene glycol pimaric acid (1-chloro-2-hydroxy) propylene glycol is as follows: dissolve propylene glycol pimaric acid in a non-water-soluble solvent, add epichlorohydrin, add a promoter, and react at 40 to 110° C. for 0.5 to 48 hours. After the reaction is completed, add deionized water, shake thoroughly, stand and separate, remove the water layer, and perform high vacuum rotary evaporation on the oil layer liquid to obtain propylene glycol pimaric acid (1-chloro-2-hydroxy) propylene glycol.

[0044] Specifically, the amount of the non-water-soluble solvent is 3 to 200 wt % of the mass of acrylpimaric acid, preferably 10 to 50 wt %;

[0045] Specifically, the mass ratio of acrylpimaric acid to epichlorohydrin is 1:1.05 to 1.50, preferably 1:1.10 to 1.20;

[0046] Specifically, the amount of the accelerator added is 0.5 to 3.5 wt % of the total mass of acrylpimaric acid and epichlorohydrin, preferably 0.8 to 1.5 wt %;

[0047] Specifically, in order to improve the reaction conversion rate, the promoter is preferably added in multiple times, and the best number of additions is 3-4 times. The first addition is 1 / 2 of the total amount of promoter, and the remaining additions are 1 / 2 of the remaining amount of promoter until all the promoter is added.

[0048] The non-aqueous solvent is preferably a mixture of one or more of toluene, xylene, ethyl acetate, butyl acetate, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, trichloroethylene, and dichloroethylene.

[0049] The accelerator is a mixture of one or more of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium fluoride, and tetrabutylammonium hydroxide, wherein tetrabutylammonium bromide and tetrabutylammonium chloride are preferred;

[0050] b) The diol component is 0 to 80 parts, preferably 25 to 60 parts.

[0051] The diol has a number average molecular weight of 800 to 6000 g / mol, preferably 1000 to 4000 g / mol, based on the total weight of the diol component, and the diol comprises 50 to 100 wt% of bio-based polyester diol and 0 to 50 wt% of petroleum-based diol, wherein 70 to 100 wt% of bio-based polyester diol and 0 to 30 wt% of petroleum-based diol are preferred;

[0052] Furthermore, the diol hydroxyl value ranges from 18 to 140 mg KOH / g; the water content is less than or equal to 300 ppm, preferably less than or equal to 200 ppm; the catalyst content is less than or equal to 400 ppm, preferably less than or equal to 200 ppm. The catalyst here refers to the catalyst used in the synthesis process of bio-based polyester diols, which may be residual;

[0053] The petroleum-based diol is 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 diol, among which petroleum-based polyester diol is preferred, specifically one or more of polybutylene adipate diol (PBA), polyethylene adipate diol (PEA), and polyhexamethylene adipate diol (PHA).

[0054] The bio-based polyester diol is 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, and neopentyl glycol.

[0055] The bio-based polyester diol 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 bio-based 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 diol component. The above catalyst is a catalyst used in the synthesis process of the bio-based polyester diol, and may be residual.

[0056] The bio-based polyester diol is preferably one or more of poly(1,3-propylene succinate) diol (PPSu), poly(butylene succinate) diol (PBSu), poly(1,3-propylene sebacate) diol (PPSe), and poly(butylene sebacate) diol (PBSe).

[0057] c) Chain extender component 0 to 30 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] 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. Petroleum-based 1,4-butanediol is preferred.

[0060] 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.

[0061] d) 5 to 55 parts of diisocyanate component, preferably 12 to 42 parts.

[0062] Based on the total weight of the diisocyanate component, the diisocyanate contains 10 to 60 wt% of bio-based diisocyanate and 40 to 90 wt% of petroleum-based diisocyanate, wherein 30 to 60 wt% of bio-based diisocyanate and 40 to 70% of petroleum-based diisocyanate are preferred;

[0063] The petroleum-based diisocyanate is a mixture of one or more of hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, 4,4-dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, meta-xylylene diisocyanate, and 1,5-naphthalene diisocyanate, preferably 4,4-diphenylmethane diisocyanate and hexamethylene diisocyanate.

[0064] The bio-based diisocyanate is one of bio-based 1,4-butanediisocyanate and bio-based 1,5-pentanediisocyanate, or a mixture of the two.

[0065] e) Catalyst component 0.001 to 0.3 parts, preferably 0.01 to 0.1 parts.

[0066] 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.

[0067] The organotin catalyst is one of stannous octoate, dibutyltin dilaurate, dibutyltin dioxalate, dibutyltin didodecylsulfide, or a mixture of several of them, preferably dibutyltin dilaurate.

[0068] 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.

[0069] In addition, the present invention also provides a method for preparing a rosin derivative modified thermosetting bio-based polyurethane, which specifically comprises the following steps: blending three components, namely a) propylene pimaric acid (1-chloro-2-hydroxy)propylene glycol, b) diol, and c) chain extender, adding solvent 2 to uniformly mix the three components a) to c), then adding d) diisocyanate and stirring evenly, then adding e) catalyst and stirring evenly, reacting at 40 to 120° C., removing the solvent to obtain a modified thermoplastic polyurethane, and continuing to react at 120 to 200° C. to obtain a modified thermosetting polyurethane.

[0070] 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.

[0071] The preparation method may further include the following steps: dividing the required b) diol into two equal parts, adding one part of b) diol polyol, d) polyisocyanate, c) chain extender, and e) catalyst into a first reaction kettle, reacting at 110-120° C., and then evacuating the first reaction kettle to obtain a first reactant;

[0072] Add the remaining portion b) of diol and a) of propylene glycol (1-chloro-2-hydroxy)pimaric acid to a second reaction kettle, heat and stir evenly at 110-120° C., and then evacuate the second reaction kettle to obtain a second reactant;

[0073] The oven is preheated to 110-120° C., the first reactant and the second reactant are poured into a preheated pouring mold by a pouring machine, and then placed in an oven 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. After the curing is completed, demolding is performed to obtain acrylpimaric acid (1-chloro-2-hydroxy) propanediol modified bio-based thermosetting polyurethane.

[0074] The invention adopts an important derivative of rosin from renewable resources, acrylpimaric acid, as a raw material to react with epichlorohydrin to prepare acrylpimaric acid (1-chloro-2-hydroxy) propanediol monomer. The acrylpimaric acid (1-chloro-2-hydroxy) propanediol monomer contains two hydroxyl groups as diol components in its structure, and reacts with a diisocyanate curing agent to generate a linear thermoplastic polyurethane structure (such as Figure 3 ), by further heating, the chlorine atoms in the polyurethane structure react with the hydrogen on the adjacent carbon to form double bonds (such as Figure 4 ), the double bonds can undergo free radical polymerization under the action of heat, further cross-linking the polyurethane macromolecular chains to form a network structure, and finally generate thermosetting polyurethane materials (such as Figure 5 ).

[0075] Compared with common thermosetting polyurethane materials, the thermosetting polyurethane material provided by the present invention not only applies bio-based materials to polyurethane modification to prepare bio-based polyurethane materials, which have excellent green and environmental protection properties, but also introduces the bulky ternary phenanthrene ring structure of rosin into the polymer main chain, and blends it with other polyurethane materials to further improve the hardness, heat resistance, hydrophobicity and other comprehensive properties of the polyurethane material.

[0076] In addition, the polyurethane in the technical solution of the present invention has the characteristic of being transformed from a thermoplastic material to a thermosetting material. Therefore, the material has two process temperatures during use. The fluidity of the thermoplastic polyurethane body heated at low temperature can be used for extrusion molding, or solvent dissolution can be used for solution molding. Later, it can be further reacted by heating to remove chlorine and cross-link, so as to obtain a thermosetting polyurethane resin with better chemical properties, higher heat resistance and excellent comprehensive performance. That is, the process operation temperature window of actual construction is wider, and the construction process has stronger operability, which is conducive to promoting the development of green bio-based polyurethane materials and improving the technical level.

[0077] 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.

[0078] The bio-based raw material information involved in the examples is as follows:

[0079] (1) Acrylopimaric acid: Acrylopimaric acid was prepared according to the literature (Wan Guoyun, Wang Zhenguo, Su Jianxiong. Preparation of acrylic rosin polyester fiberglass from rosin [J]. Plastic Industry, 1987, (01): 30-32+2.) Rosin and acrylic acid were added into a three-necked flask at a mass ratio of 4:25, and heated to 170°C for 2 h under nitrogen protection to isomerize the abietic acid in the rosin to generate L-pimaric acid. The temperature was then raised to 225°C for 2 h. Since the conjugated double bond of L-pimaric acid is S-cis, it has high reactivity, so it reacts with the dienophile acrylic acid to produce a light yellow transparent solid acrylopimaric acid by Diels-Alder reaction.

[0080] (2) Bio-based dicarboxylic acids: bio-based succinic acid, purchased from BioAmber; bio-based sebacic acid, purchased from Hebei Kaide Biomaterials Co., Ltd.;

[0081] (3) Bio-based polyester diol: Bio-based 1,3-propylene glycol, purchased from DuPont.

[0082] Preparation of bio-based poly(1,3-propylene succinate) diol: According to the literature (Liu Yiwu, Wang Qian, Tan Jinghua, et al. Synthesis and characterization of biodegradable poly(1,3-propylene succinate) diol / 1,3-propylene glycol ester [J]. Journal of Packaging, 2014, 6(01): 10-15), bio-based succinic acid and bio-based 1,3-propylene glycol were put into a three-necked flask equipped with a stirrer at a molar ratio of 1:1.2, and dibutyltin dilaurate was added at a mass fraction of 0.3% of the total amount of raw materials. The mixture was heated to 140°C under argon protection; after reacting for 1 hour, the mixture was switched to a reduced pressure reaction device and heated to 160°C; the vacuum degree of the flask was adjusted to -0.1 MPa and the reaction was carried out for 2 hours; the temperature was then raised to 190°C to continue the reaction; the reaction was stopped when the acid value was less than 1.5 mg KOH / g and the hydroxyl value reached a predetermined value. The hydroxyl value of 56 mg KOH / g corresponds to a number average molecular weight of 2000 g / mol, and the hydroxyl value of 112 KOH / g corresponds to a number average molecular weight of 1000 g / mol. The obtained product was purified and then dried under vacuum at 60° C. for 24 h.

[0083] Preparation of bio-based poly (1,3-propylene glycol sebacic acid) diol: According to the literature (Liu Quanyong, Tan Tianwei, Weng Jingyi, et al. Synthesis of poly (1,3-propylene glycol sebacic acid) ester under catalyst-free conditions and its molecular weight study [J]. Modern Chemical Industry, 2008, (S2): 169-173.), bio-based sebacic acid and bio-based 1,3-propylene glycol were mixed in a three-necked flask at a molar ratio of 1:1.1, and then heated and evacuated 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 a predetermined value, the reaction was stopped. The hydroxyl value of 38mg KOH / 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.

[0084] Preparation of bio-based poly 1,4-butylene sebacic acid diol: 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), bio-based sebacic acid and petroleum-based 1,4-butanediol were added to a three-necked flask at 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 mgKOH / 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.

[0085] Preparation of bio-based poly 1,4-butylene succinate diol: According to the literature (Wu Jianning, Meng Guihua, Liu Zhiyong, et al. Synthesis and process research of poly butylene succinate diol [J]. Synthetic Materials Aging and Application, 2012, 41(02): 6-9+60.), bio-based succinic acid and petroleum-based 1,4-butanediol were added to a four-necked flask at a molar ratio of 1:1.3, and a stannous chloride catalyst with a mass fraction of 1.2% of the total amount of raw materials was added; a stirring device and a distillation device were installed; the oil bath temperature was controlled to 140°C, and the reaction was carried out under stirring for 1 hour. The reaction device was changed to a vacuum distillation device, stirred, and heated to 180°C at 10°C / 10min. The internal pressure was reduced to 1kPa and the reaction was carried out at a constant temperature; when the acid value was less than 1mg KOH / g and the hydroxyl value reached 56mg KOH / g, the reaction was stopped, and the corresponding number average molecular weight was 2000g / mol.

[0086] Preparation of bio-based poly(1,3-propylene glycol adipate) diol, according to 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, 2012, 26 (S2): 64-68.)

[0087] 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.

[0088] (4) Bio-based chain extender: Bio-based 1,3-propylene glycol, purchased from DuPont.

[0089] (5) Bio-based diisocyanate: 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), bio-based succinic acid is hydrogenated to synthesize bio-based 1,4-butanediamine, and then the bio-based 1,4-butanediisocyanate is synthesized with phosgene via a gas phase phosgene method.

[0090] 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.

[0091] Example 1

[0092] 23.01wt% PPSu (bio-based poly(1,3-propylene glycol) succinate) with a molecular weight of 2000g / mol, a total amount of diisocyanate of 32.54% (of which petroleum-based diisocyanate accounts for 70wt% and bio-based diisocyanate accounts for 30wt%), namely 22.78wt% MDI (4,4-diphenylmethane diisocyanate), 9.76wt% BDI (bio-based 1,4-butylene diisocyanate), 12.4wt% 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.

[0093] 9.03wt% of 1-chloro-2-hydroxypropylenepimaric acid with a molecular weight of 558g / mol and the remaining 23.01wt% of PPSu (bio-based poly(1,3-propylene succinate diol) with a molecular weight of 2000g / mol) were added into the second reactor, heated and stirred to mix evenly, and then the second reactor was evacuated to a vacuum degree of -0.08 to 0.1Mpa, and the temperature in the second reactor was maintained between 110°C and 120°C, preferably at 120°C, and the reaction was completed to form a second reactant.

[0094] 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.

[0095] Example 2

[0096] The difference between this embodiment and embodiment 1 is that in this embodiment, the weight fraction of acrylpimaric acid (1-chloro-2-hydroxy) propanediol with a molecular weight of 558 g / mol is changed to 9.3 wt %, the weight fraction of bio-based polyol ester is changed to 24.72 wt %, and the bio-based polyol ester is replaced by PPSu (bio-based polysuccinate 1,3-propylene glycol ester) with a molecular weight of 1000 g / mol, and the total amount of diisocyanate is changed to 43.5% (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 26.1 wt %, the weight fraction of bio-based isocyanate BDI (bio-based 1,4-butylene diisocyanate) is changed to 17.4 wt %, and the weight fraction of chain extender PDO (bio-based 1,3-propylene glycol) is changed to 22.47 wt %.

[0097] Example 3

[0098] The difference between this embodiment and embodiment 1 is that in this embodiment, the weight fraction of acrylpimaric acid (1-chloro-2-hydroxy) propanediol with a molecular weight of 558 g / mol is changed to 9.4 wt %, the weight fraction of bio-based polyol ester is changed to 75.59 wt %, and the bio-based polyol ester is replaced by PPSe (bio-based poly 1,3-propylene glycol 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 %), and the petroleum-based isocyanate is replaced by HDI (hexamethylene diisocyanate), and the weight fraction is changed to 6.08%, the bio-based isocyanate is replaced by PDI (bio-based 1,5-pentane diisocyanate), and the weight fraction of bio-based isocyanate is changed to 6.08 wt %, and the weight fraction of chain extender PDO (bio-based 1,3-propylene glycol) is changed to 2.84 wt %.

[0099] Example 4

[0100] The difference between this embodiment and embodiment 1 is that in this embodiment, the weight fraction of acrylpimaric acid (1-chloro-2-hydroxy) propanediol with a molecular weight of 558 g / mol is changed to 6.8 wt %, the weight fraction of bio-based polyol ester is changed to 73.2 wt %, and the bio-based polyol ester 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 40 wt % and bio-based diisocyanate accounts for 60 wt %), the petroleum-based isocyanate is replaced by HMDI (4,4-dicyclohexylmethane diisocyanate), and the weight fraction is changed to 6.33%, the bio-based isocyanate is replaced by PDI (bio-based 1,5-pentane diisocyanate), and the weight fraction is changed to 9.49 wt %, and the weight fraction of the chain extender PDO (bio-based 1,3-propylene glycol) is changed to 4.17 wt %.

[0101] Example 5

[0102] The difference between this embodiment and embodiment 1 is that in this embodiment, the weight fraction of acrylpimaric acid (1-chloro-2-hydroxy) propanediol with a molecular weight of 558 g / mol is changed to 49.15%, and the total amount of diisocyanate is 50.84% ​​(of which petroleum-based diisocyanate accounts for 70wt% and bio-based diisocyanate accounts for 30wt%), that is, 35.56wt% MDI (4,4-diphenylmethane diisocyanate) and 15.24wt% BDI (bio-based 1,4-butanediisocyanate), and no polyester polyol and chain extender are added.

[0103] Comparative Example 1

[0104] 33.5wt% PPSu (bio-based poly(1,3-propylene glycol) succinate) with a molecular weight of 2000g / mol, a total amount of diisocyanate of 32.54% (of which petroleum-based diisocyanate accounts for 70wt% and bio-based diisocyanate accounts for 30wt%), namely 16.7wt% MDI (4,4-diphenylmethane diisocyanate), 7wt% BDI (bio-based 1,4-butylene diisocyanate), 9.29wt% 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.

[0105] 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.

[0106] 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.

[0107] Comparative Example 2

[0108] The difference between this comparative example and comparative example 1 is that in this comparative example, the weight fraction of the bio-based polyol ester is changed to 41.5wt%, and the bio-based polyol ester 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 35.49% (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 21.29wt%, the weight fraction of bio-based isocyanate BDI (bio-based 1,4-butylene diisocyanate) is changed to 14.2wt%, and the weight fraction of chain extender PDO (bio-based 1,3-propylene glycol) is changed to 19wt%.

[0109] Comparative Example 3

[0110] The difference between this comparative example and comparative example 1 is that in this comparative example, the weight fraction of the bio-based polyol ester is changed to 91wt%, and the bio-based polyol ester is replaced by PPSe (bio-based poly 1,3-propylene sebacate) with a molecular weight of 3000g / mol, the total amount of diisocyanate is 7.29%, (of which petroleum-based diisocyanate accounts for 50wt% and bio-based diisocyanate accounts for 50wt%), that is, the weight fraction of petroleum-based isocyanate is changed to 3.645wt%, and petroleum-based isocyanate is replaced by HDI (hexamethylene diisocyanate), the weight fraction of bio-based isocyanate is changed to 3.645wt%, and 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 1.7wt%.

[0111] Comparative Example 4

[0112] The difference between this comparative example and comparative example 1 is that in this comparative example, the weight fraction of the bio-based polyol ester is changed to 88wt%, and the bio-based polyol ester is replaced by PBSe (bio-based poly 1,4-butylene sebacate) with a molecular weight of 4000g / mol, the total amount of diisocyanate is 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 3.792%, the bio-based isocyanate is replaced by PDI (bio-based 1,5-pentane diisocyanate), and the weight fraction is changed to 5.688wt%, and the weight fraction of the chain extender PDO (bio-based 1,3-propylene glycol) is changed to 2.51wt%.

[0113] Comparative Example 5

[0114] The difference between this comparative example and comparative example 1 is that in this comparative example, the weight fraction of the bio-based polyol ester is changed to 73wt%, and the bio-based polyol ester 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%.

[0115] Comparative Example 6

[0116] The difference between this comparative example and comparative example 1 is that this comparative example does not use bio-based polyester diol, only uses petroleum-based polyester diol, the weight fraction of polyester diol is changed to 47.82wt%, and the polyester diol is replaced by PPA (polypropylene 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 35.42wt%, and the chain extender is replaced by petroleum-based HDO (1,6-hexanediol), and the weight fraction is changed to 16.75wt%.

[0117]

[0118]

[0119]

[0120] It can be seen from the above two tables that compared with the comparative example and the prior art, 1) the raw materials used in the present invention 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 example are even less environmentally friendly; (2) the polyurethane synthesized by the present invention has both thermoplastic and thermosetting characteristics, which can not only improve the processing fluidity of the system, reduce the process temperature, and reduce the production cost, but also improve the mechanical properties and comprehensive properties of the material system. (3) By introducing a rigid rosin structure, the present invention significantly increases the mechanical properties of the polyurethane compared with the comparative example, especially the hardness reaches 98A, which can be used as a rigid modified polyurethane material and mixed with other polyurethane materials for modification, further expanding its application field; (4) The product obtained by the present invention can also be used as a plasticizing and reinforcing modified component and mixed with polyurethane powder materials to prepare high-performance powder coatings, thereby improving the adhesion, hardness, gloss, and comprehensive properties of the powder coatings such as hydrophobicity and corrosion resistance.

[0121] 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.

[0122] 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 rosin derivative modified thermosetting bio-based polyurethane, characterized in that: In parts by weight, it includes: 5-50 parts of acrylpimaric acid (1-chloro-2-hydroxy)propylene glycol, 20-95 parts of diol, 0-25 parts of chain extender, 5-55 parts of petroleum-based diisocyanate, and 0.001 parts of catalyst, wherein the diol and chain extender are not zero.

2. The rosin derivative modified thermosetting bio-based polyurethane according to claim 1, characterized in that: The total content of bio-based components in propylene pimaric acid (1-chloro-2-hydroxy) propanediol, diol and chain extender is greater than or equal to 50wt%, wherein the bio-based component content refers to the percentage of biologically derived components in the total mass of all components.

3. The rosin derivative modified thermosetting bio-based polyurethane according to claim 1, characterized in that: The diol has a number average molecular weight of 800 to 6000 g / mol, and the diol includes bio-based polyester diol and petroleum-based polyester diol; The diol has a hydroxyl value ranging from 18 to 140 mg KOH / g and a moisture content of less than or equal to 300 ppm.

4. The rosin derivative modified thermosetting bio-based polyurethane according to claim 1, characterized in that: The chain extender comprises 50 to 100 wt % of a bio-based chain extender and 0 to 50 wt % of a petroleum-based chain extender, based on the total weight of the chain extender component.

5. The rosin derivative modified thermosetting bio-based polyurethane according to claim 1, characterized in that: Based on the total weight of the diisocyanate component, the petroleum-based diisocyanate contains 10 to 60 wt% of bio-based diisocyanate and 40 to 90 wt% of petroleum-based diisocyanate; The bio-based polyester diol 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, a catalyst content less than or equal to 400 ppm, and a biobased content greater than or equal to 50 wt% based on the total weight of the bio-based polyester diol component.

6. The rosin derivative modified thermosetting bio-based polyurethane according to claim 1, characterized in that: Based on the total weight of the diisocyanate component, the diisocyanate includes 10 to 60 wt% of bio-based diisocyanate and 40 to 90 wt% of petroleum-based diisocyanate; wherein the petroleum-based diisocyanate is a mixture of one or more of hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, 4,4-dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, meta-xylylene diisocyanate, and 1,5-naphthalene diisocyanate; The bio-based diisocyanate is one of bio-based 1,4-butanediisocyanate and bio-based 1,5-pentanediisocyanate, or a mixture of the two.

7. The rosin derivative modified thermosetting bio-based polyurethane according to claim 1, characterized in that: Based on the total weight of the catalyst components, the catalyst comprises 50-100wt% of a non-tin environmentally friendly catalyst and 0-50wt% of a tin-containing catalyst; 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; The organotin catalyst is one of stannous octoate, dibutyltin dilaurate, dibutyltin dioxalate, dibutyltin didodecylsulfide, or a mixture of several of them, preferably dibutyltin dilaurate.

8. The rosin derivative modified thermosetting bio-based polyurethane according to claim 1, characterized in that: The preparation method of the propylene pimaric acid (1-chloro-2-hydroxy) propanediol is as follows: dissolving propylene pimaric acid in a non-water-soluble solvent, then sequentially adding epichlorohydrin and an accelerator, and reacting at 40 to 110° C. for 0.5 to 48 hours; after the reaction, adding deionized water, shaking thoroughly, standing to separate, removing the water layer, and subjecting the obtained oil-containing layer liquid to high-vacuum rotary evaporation to obtain propylene pimaric acid (1-chloro-2-hydroxy) propanediol; The amount of the non-water-soluble solvent is 3 to 200 wt% of the mass of acrylpimaric acid; the mass ratio of acrylpimaric acid to epichlorohydrin is 1:1.05 to 1.50; The amount of the accelerator added is 0.5-3.5wt% of the total mass of acrylpimaric acid and epichlorohydrin; The non-aqueous solvent is a mixture of one or more of toluene, xylene, ethyl acetate, butyl acetate, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, trichloroethylene, and dichloroethylene; The accelerator is a mixture of one or more of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium fluoride and tetrabutylammonium hydroxide.

9. The rosin derivative modified thermosetting bio-based polyurethane according to claim 8, characterized in that: The accelerator is added in multiple times, with the first addition being 1 / 2 of the total mass of the accelerator, and the remaining additions being 1 / 2 of the remaining mass of the accelerator, until all the accelerator is added.

10. The method for preparing a rosin derivative modified thermosetting bio-based polyurethane according to any one of claims 1 to 9, characterized in that: include: The three components of propylene pimaric acid (1-chloro-2-hydroxy) propanediol, diol and chain extender are mixed, a solvent is added to mix the three components evenly, a diisocyanate is added and stirred evenly, a catalyst is added and stirred evenly, the mixture is reacted at 40 to 120° C., the solvent is removed to obtain a modified thermoplastic polyurethane, and the mixture is reacted at 120 to 200° C. to obtain a modified thermosetting polyurethane; The solvent is one or more of xylene, ethyl acetate, butyl acetate, dichloromethane, tetrahydrofuran, and toluene, preferably xylene, ethyl acetate, butyl acetate, and dichloromethane; or, The method comprises: dividing the diol into two parts of equal mass, then adding one part of the diol, polyisocyanate, chain extender and catalyst into a first reaction kettle, reacting at 110-120° C., and then evacuating the first reaction kettle to obtain a first reactant; Add another portion of diol and propylene glycol (1-chloro-2-hydroxy)pimaric acid into the second reaction kettle, heat and stir evenly at 110-120° C., and then evacuate the second reaction kettle to obtain a second reactant; The oven is preheated to 110-120° C., the first reactant and the second reactant are poured into a preheated pouring mold by a pouring machine, and then placed in an oven for curing. The first period of the curing step is 1 hour, and the first curing temperature is maintained at 120° C. The second period of curing is at 140° C. for 48 hours. After the curing is completed, the mold is demolded to obtain acrylpimaric acid (1-chloro-2-hydroxy) propanediol modified bio-based thermosetting polyurethane.

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