Bio-based polyol, preparation method thereof and application of bio-based polyol in bio-based polyurethane

Abstract

The invention belongs to the field of bio-based polyol, and relates to bio-based polyol, a preparation method thereof and application of the bio-based polyol in bio-based polyurethane. Mixing the epoxidized vegetable oil with an acid catalyst to obtain a first mixed solution; mixing a carboxylic acid ring-opening reagent with an organic solvent to obtain a second mixed solution; mixing an alcohol ring-opening reagent with an organic solvent to obtain a third mixed solution; respectively and simultaneously pumping the first mixed solution and the second mixed solution into a first micro-mixer for mixing, and then continuously pumping the mixed solution into a first micro-reactor of the micro-reaction device for a first ring-opening reaction to obtain a reaction effluent; curing the reaction effluent liquid, simultaneously pumping the cured reaction effluent liquid and the third mixed liquid into a second micro-mixer to be mixed with the cured reaction liquid, then continuously pumping the mixture into a second micro-reactor of the micro-reaction device to carry out a second ring-opening reaction, and after the reaction is finished, carrying out post-treatment to obtain the bio-based polyol. The bio-based polyol provided by the invention can be used for preparing a high-performance polyurethane coating and / or a polyurethane structural adhesive.

Description

Technical Field

[0001] The present invention belongs to the field of bio-based polyols and relates to a bio-based polyol and a preparation method thereof and application thereof in bio-based polyurethane. Background Art

[0002] The development of vegetable oil polyols is considered an effective path forward for bio-based materials. As a key monomer in bio-based polyurethane materials, vegetable oil-based polyols are derived from chemically modified molecular structures and are a significant renewable resource. They react with isocyanate compounds to form polyurethanes, making them a promising alternative to petroleum-based polyols and a breakthrough in the development of bio-based polyurethane coatings. Oxidizing vegetable oils to epoxidized vegetable oils, followed by ring-opening reactions to generate polyols, offers high atom economy, flexibility, structural controllability, and molecular diversity, making it the primary approach for developing bio-based polyols.

[0003] The liquid-liquid two-phase reaction between vegetable oil macromolecules and reaction reagents often severely limits the reaction mass transfer process, resulting in low reaction efficiency, high material consumption, heavy emissions and other problems. The existing technology generally uses continuous flow reaction means and has made certain progress, but there are still some technical defects, making product quality difficult to control and high costs. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to address the deficiencies of the prior art and provide a bio-based polyol, a preparation method thereof and an application thereof in bio-based polyurethane.

[0005] Existing technologies for ring-opening epoxidized vegetable oils use relatively simple methods, such as simple acid ring-opening to introduce ester groups or simple alcohol ring-opening to introduce ether groups. These methods lack structural diversity, resulting in limited flexibility in subsequent polymerization formulations. Fully opening the epoxy groups in the structure maximizes the effective functionality of the epoxidized vegetable oil. However, the inventors' previous research has shown that when the epoxy groups are ring-opened, the viscosity of the resulting polyol product varies. Residual epoxy groups contribute to a lower viscosity (generally speaking, the viscosity of vegetable oil polyols is greater than that of similar petrochemical polyols, complicating system compatibility and operability during subsequent formulation adjustments). Furthermore, residual epoxy groups contribute to the material's antioxidant capacity and the coating's salt spray resistance. This application primarily utilizes microreaction technology to achieve controlled introduction of ester and ether groups, enabling precise polyol development and providing guidance for summarizing the structure-activity relationship of vegetable oil polyols.

[0006] In order to solve the above technical problems, the technical solutions adopted by the present invention are as follows: The present invention discloses a method for preparing a bio-based polyol, comprising the following steps: (1) mixing epoxidized vegetable oil and an acidic catalyst to obtain a first mixed solution; mixing a carboxylic acid ring-opening reagent and an organic solvent to obtain a second mixed solution; and mixing an alcohol ring-opening reagent and an organic solvent to obtain a third mixed solution; The first mixed liquid and the second mixed liquid are simultaneously pumped into a first micromixer for mixing, and then continuously pumped into a first microreactor of a microreactor device for a first ring-opening reaction to obtain a reaction effluent; (2) Open the valve in front of the first collector, and let the reaction effluent of the first microreactor flow continuously into the first collector. After the collection is completed, close the valve in front of the first collector; then open the valve in front of the second collector, and let the reaction effluent of the first microreactor flow into the second collector. After the collection is completed, close the valve in front of the second collector; then open the valve in front of the third collector, and let the reaction effluent of the first microreactor flow into the third collector. After the collection is completed, close the valve in front of the third collector; while the reaction effluent of the first microreactor is collected into each collector in turn, when the reaction effluent in each collector is matured, the matured reaction liquid in the first collector, the second collector, and the third collector is pumped into the second micromixer in turn, and the third mixed liquid is pumped into the second micromixer to mix with the matured reaction liquid, and then continues to be pumped into the second microreactor of the microreactor device for a second ring-opening reaction. After the reaction is completed, post-processing is performed to obtain bio-based polyol.

[0007] In some embodiments, in step (1), the epoxidized vegetable oil is any one or a combination of epoxidized vegetable oil, epoxidized cottonseed oil, epoxidized rapeseed oil, epoxidized sesame oil, epoxidized soybean oil, epoxidized rice bran oil, epoxidized olive oil, epoxidized peanut oil, epoxidized coconut oil, epoxidized palm oil, epoxidized corn oil and epoxidized sunflower oil; and / or, the acidic catalyst is any one or a combination of fluoroboric acid, concentrated sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid; and / or, the mass of the acidic catalyst accounts for 0.02% to 1.0% of the mass of the epoxidized vegetable oil.

[0008] In some embodiments, preferably, in step (1), the epoxidized vegetable oil is any one or a combination of epoxidized vegetable oil, epoxidized cottonseed oil, epoxidized rapeseed oil, epoxidized sesame oil, epoxidized soybean oil and epoxidized rice bran oil.

[0009] In some embodiments, preferably, in step (1), the acidic catalyst is fluoroboric acid; the fluoroboric acid is in the form of an aqueous solution with a concentration of 40 wt% to 50 wt%.

[0010] In some embodiments, preferably, in step (1), the mass of the acidic catalyst accounts for 0.02% to 0.8% of the mass of the epoxidized vegetable oil, more preferably 0.2% to 0.8%, and even more preferably 0.4%.

[0011] In some embodiments, in step (1), the carboxylic acid ring-opening reagent is any one or a combination of benzoic acid, 2-furancarboxylic acid, 3-thiophenecarboxylic acid, cyclohexanecarboxylic acid, cyclopentanecarboxylic acid, 2-tetrahydrofurancarboxylic acid, formic acid, propionic acid, n-pentanoic acid and n-hexanoic acid; and / or, the alcohol ring-opening reagent is any one or a combination of methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, cyclopentylmethanol, cyclohexylmethanol and furfuryl alcohol; and / or, the organic solvent is any one or a combination of ethyl acetate, dichloromethane, dichloroethane, chloroform, n-hexane, tetrahydrofuran, 1,4-dioxane, carbon tetrachloride, toluene and xylene.

[0012] In some embodiments, preferably, in step (1), the organic solvent is ethyl acetate or toluene.

[0013] In some embodiments, in step (1), the concentration of the carboxylic acid ring-opening reagent in the second mixed solution is 0.001~0.010 mol / mL; and / or the concentration of the alcohol ring-opening reagent in the third mixed solution is 0.001~0.010 mol / mL.

[0014] In some embodiments, preferably, in step (1), the concentration of the carboxylic acid ring-opening reagent in the second mixed solution is 0.001-0.005 mol / mL, more preferably 0.001-0.004 mol / mL.

[0015] In some embodiments, preferably, in step (1), the concentration of the alcohol ring-opening reagent in the third mixed solution is 0.001-0.005 mol / mL, more preferably 0.002-0.005 mol / mL.

[0016] In some embodiments, in step (1), the flow rate of the first mixed liquid pumped into the first microreactor of the microreactor is 1.0~10.0 mL / min; and / or, the flow rate of the second mixed liquid pumped into the first microreactor of the microreactor is 1.0~10.0 mL / min; and / or, in the first ring-opening reaction, the reaction molar ratio of the epoxy group in the epoxidized vegetable oil to the carboxylic acid group in the carboxylic acid ring-opening reagent is controlled to be 1.0:(0.2~0.4) during the reaction process.

[0017] In some embodiments, preferably, in step (1), the flow rate of the first mixed solution pumped into the first microreactor of the microreactor device is 1.0-5.0 mL / min, more preferably 1.5-4.0 mL / min.

[0018] In some embodiments, preferably, in step (1), the flow rate of the second mixed liquid pumped into the first microreactor of the microreactor is 2.0-6.0 mL / min, more preferably 3.0-5.0 mL / min.

[0019] In some embodiments, in step (1), the reaction temperature of the first ring-opening reaction is 70°C to 90°C; and / or the reaction time of the first ring-opening reaction is 2.0 min to 10.0 min.

[0020] In some embodiments, preferably, in step (1), the reaction temperature of the first ring-opening reaction is 75-85°C, more preferably 80°C; and / or the reaction time of the first ring-opening reaction is 2.0 min-8.0 min, more preferably 3.0 min-6.0 min.

[0021] In some embodiments, in step (2), the aging temperature is 60°C to 80°C; and / or the aging time is 20 to 40 min; and / or the flow rate at which the aging reaction liquid in the first collector is pumped into the second microreactor of the microreactor is 5.0 to 20.0 mL / min; and / or the flow rate at which the aging reaction liquid in the second collector is pumped into the second microreactor of the microreactor is 5.0 to 20.0 mL / min; and / or the flow rate at which the aging reaction liquid in the third collector is pumped into the second microreactor of the microreactor is 5.0 to 20.0 mL / min; and / or the flow rate at which the third mixed liquid is pumped into the second microreactor of the microreactor is 1.0 to 10.0 mL / min.

[0022] In some embodiments, preferably, in step (2), the aging temperature is 65°C to 75°C, more preferably 70°C; and / or the aging time is 30 min; and / or the flow rate at which the aging reaction liquid in the first collector is pumped into the second microreactor of the microreactor is 5.0 to 10.0 mL / min, more preferably 6.0 to 10.0 mL / min; and / or the flow rate at which the aging reaction liquid in the second collector is pumped into the second microreactor of the microreactor is 5.0 to 10.0 mL / min, more preferably 6.0 to 10.0 mL / min; and / or the flow rate at which the aging reaction liquid in the third collector is pumped into the second microreactor of the microreactor is 5.0 to 10.0 mL / min, more preferably 6.0 to 10.0 mL / min; and / or the flow rate at which the third mixed liquid is pumped into the second microreactor of the microreactor is 2.0 to 5.0 mL / min.

[0023] In some embodiments, in step (2), in the second ring-opening reaction, based on the epoxy groups in the epoxidized vegetable oil in the first mixed solution, the reaction molar ratio of the epoxy groups in the epoxidized vegetable oil to the hydroxyl groups in the alcohol ring-opening reagent is controlled to be 1.0:(0.5~0.8); and / or, the reaction temperature of the second ring-opening reaction is 70℃~95℃; and / or, the reaction time of the second ring-opening reaction is 1.0 min~20.0 min.

[0024] In some embodiments, in step (2), the reaction temperature of the second ring-opening reaction is 80°C to 95°C; and / or the reaction time of the second ring-opening reaction is 2.0 min to 10.0 min, more preferably 2.0 min to 6.0 min.

[0025] In some embodiments, the microreactor includes a connecting pipeline, a first syringe pump, a second syringe pump, a third syringe pump, a fourth syringe pump, a fifth syringe pump, a sixth syringe pump, a first micromixer, a second micromixer, a first microreactor, a second microreactor, a first collector, a second collector, a third collector, a first collector front valve, a second collector front valve, a third collector front valve and a receiver; wherein, the first syringe pump and the second syringe pump are connected in parallel to the first micromixer; the first micromixer is connected to the first microreactor; the first pipeline, the second pipeline and the third pipeline are connected in parallel between the first microreactor and the second micromixer, the first pipeline is connected in series with the first collector front valve, the first collector, and the third syringe pump, the second pipeline is connected in series with the second collector front valve, the second collector, and the fourth syringe pump, and the third pipeline is connected in series with the third collector front valve, the third collector, and the fifth syringe pump; the sixth syringe pump is connected to the first feed port of the second micromixer; the second micromixer is connected in series with the second microreactor and the receiver.

[0026] Wherein, the micro mixer is Y-shaped or T-shaped, preferably Y-shaped.

[0027] Wherein, the microreactor is a tubular reactor, and the inner diameter of the tube is 0.1 mm to 10.0 mm, preferably 0.1 mm to 1.0 mm, more preferably 0.2 mm to 0.5 mm, and even more preferably 0.5 mm.

[0028] After the second ring-opening reaction is completed, the reaction effluent in the second microreactor is cooled to 20° C. to 25° C., and then washed with 5 wt% sodium bicarbonate aqueous solution. The organic layer is taken and washed twice with water. The organic phases are combined, dried, filtered to remove the desiccant, and concentrated to obtain bio-based polyols.

[0029] The bio-based polyols prepared by the above-mentioned preparation method are also within the protection scope of the present invention.

[0030] In some embodiments, the epoxy value of the bio-based polyol is 0% to 1.10%; and / or the hydroxyl value of the bio-based polyol is 100 to 180 mg KOH / g.

[0031] The use of the above-mentioned bio-based polyols in the preparation of polyurethane coatings and / or polyurethane structural adhesives is also within the scope of protection of the present invention.

[0032] Beneficial effects: (1) The present invention adopts a simple ring-opening reagent to regulate the ratio of ester groups introduced by acid ring-opening and ether groups introduced by alcohol ring-opening, and combines the appropriate residual epoxy groups to achieve the regulation of polyol parameters and material properties. The problem of difficult liquid-liquid mass transfer during the ring-opening process is solved through a micro-reaction continuous process, making the ring-opening reaction more controllable.

[0033] (2) The present invention uses micro-reaction technology to achieve the controlled introduction of ester and ether groups, control the residual epoxy groups, and achieve precise development of polyols, thereby providing guidance for the summary of the structure-activity relationship of vegetable oil polyols.

[0034] (3) The bio-based polyols provided by the present invention can be used to prepare high-performance polyurethane coatings and / or polyurethane structural adhesives. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, and the above and / or other advantages of the present invention will become more apparent.

[0036] Figure 1 Flow chart of the micro-reaction device used in the embodiments of the present invention. DETAILED DESCRIPTION

[0037] The present invention can be better understood according to the following examples. However, it is easy for those skilled in the art to understand that the contents described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

[0038] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.

[0039] 1. The testing standards for the relevant parameters in the embodiments of the present invention are as follows: (1) Determination of the hydroxyl value of vegetable oil polyols according to GB / T 12008.3-2009; (2) Measure the viscosity of vegetable oil polyols according to GB / T 12008.7-2010; (3) Determine the surface drying time and through drying time of polyurethane coatings according to GB / T 1728-2020; (4) Measure the adhesion of polyurethane coatings according to GB / T 5210-2006; (5) Measure the salt spray resistance of polyurethane coatings according to GB / T 10125-2021; (6) Determination of tensile strength of polyurethane structural adhesive according to GB / T 528-2009; (7) The shear strength of polyurethane structural adhesive was determined according to GB / T 7124-2008.

[0040] 2. The formula for preparing the polyurethane coating in the embodiment of the present invention is as follows: Component A: 31 parts by mass of the vegetable oil polyol prepared in the embodiment of the present invention; 12 parts by mass of titanium dioxide; 2 parts by mass of black iron oxide; 11 parts by mass of ion-exchanged silica; 9 parts by mass of aluminum tripolyphosphate; 21 parts by mass of barium sulfate; 1 part by mass of dispersant; 1 part by mass of organobentonite; 10 parts by mass of toluene; and 2 parts by mass of butyl acetate. Component B: diphenylmethane diisocyanate; the mass ratio of Component A to Component B is 8:2.

[0041] Component A and component B were mixed and stirred according to the mass ratio for 10 minutes to polymerize to obtain a polyurethane coating primer. The polyurethane coating primer was sprayed onto a steel plate substrate. The spraying was performed once to obtain a dry film thickness of 25 μm. The surface setting and through-drying times were measured. After standing for 48 hours, adhesion and salt spray resistance tests were performed in a laboratory environment.

[0042] 3. The method for preparing the polyurethane structural adhesive in the embodiment of the present invention is as follows: the preparation method of the first component is as follows: 100 parts of the vegetable oil polyol prepared in the embodiment of the present invention and 10 parts of trimethylolpropane are added to a reactor and heated to 110° C., and stirred and dehydrated for 2 hours at a vacuum degree of ≤-0.09 MPa at a speed of 1200 r / min, then cooled to below 60° C., transferred to a stirring motor at a speed of 1200 r / min, and then added 15 parts of plasticizer phthalate, 3 parts of KH-560, 3 parts of KH-550, 4 parts of silica-supported organic tin (2valent), and 2 parts of molecular sieves, stirred for 30 minutes at a vacuum degree of ≤-0.09 MPa, and discharged to obtain the first component; the preparation method of the second component is as follows: toluene diisocyanate (TDI): polymethylene polyphenyl polyisocyanate (PAPI) = 7:3 are added to a stirrer at a speed of 1200 r / min, and stirred at a vacuum degree of ≤-0.09 Mpa, stirred for 30 minutes, and then discharged to obtain the second component. For adhesive application, the first and second components were mixed in a mass ratio of 1:0.8 to obtain a polyurethane structural adhesive. The tensile strength and shear strength of the polyurethane structural adhesive were measured.

[0043] 4. Figure 1 Flow chart of the microreactor used in the embodiment of the present invention. The microreactor comprises a first syringe pump (pump 1), a second syringe pump (pump 2), a third syringe pump (pump 3), a fourth syringe pump (pump 4), a fifth syringe pump (pump 5), a sixth syringe pump (pump 6), a first micromixer, a second micromixer, a first microreactor, a second microreactor, a first collector (collector 1), a second collector (collector 2), a third collector (collector 3), a valve before the first collector (valve 1), a valve before the second collector (valve 2), a valve before the third collector (valve 3), and a receiver; wherein the first syringe pump and the second syringe pump are connected in parallel to the first microreactor. On the mixer; the first micromixer is connected to the first microreactor; the first pipeline, the second pipeline and the third pipeline are connected in parallel between the first microreactor and the second micromixer, the first pipeline is connected in series with the first collector front valve, the first collector, and the third injection pump, the second pipeline is connected in series with the second collector front valve, the second collector, and the fourth injection pump, and the third pipeline is connected in series with the third collector front valve, the third collector, and the fifth injection pump; the sixth injection pump is connected to the first feed port of the second micromixer; the second micromixer, the second microreactor and the receiver are connected in series in sequence.

[0044] Wherein, the micro mixer is Y-shaped.

[0045] Wherein, the microreactor is a tubular reactor, and the inner diameter of the tube is 0.5 mm.

[0046] Wherein, the model of the microreactor is Vapotech.

[0047] Example 1: 1000 g of epoxidized cottonseed oil (epoxy value 5.7%) and 10 g of a fluoroboric acid aqueous solution (40 wt %) were mixed to obtain a first mixed solution; 130 g of cyclohexanecarboxylic acid was dissolved in 500 mL of ethyl acetate and mixed to obtain a second mixed solution; 200 g of furfuryl alcohol was dissolved in 500 mL of ethyl acetate and mixed to obtain a third mixed solution.

[0048] The first mixed liquid and the second mixed liquid were both preheated to 40°C, and the first mixed liquid and the second mixed liquid were simultaneously pumped into the first micromixer through syringe pump 1 and syringe pump 2 for mixing. Then, they were continuously pumped into the first microreactor (40 mL) of the microreactor for the first ring-opening reaction. The pumping flow rate of the first mixed liquid was 5.2 mL / min, the pumping flow rate of the second mixed liquid was 3.1 mL / min, the temperature of the first ring-opening reaction was 80°C, and the reaction residence time was 4.82 min.

[0049] The third mixed liquid was preheated to 40° C. The collectors 1, 2, and 3 equipped with a stirrer and a reflux condenser were all kept at 70° C. Open the valve 3 in front of the collector 1, and the reaction effluent of the first microreactor flows continuously into the collector 1. After a certain period of time, close the valve 3 in front of the collector 1; then open the valve 4 in front of the collector 2, and the reaction effluent of the first microreactor flows into the collector 2. After a certain period of time, close the valve 4 in front of the collector 2; then open the valve 5 in front of the collector 3, and the reaction effluent of the first microreactor flows into the collector 3. After a certain period of time, close the valve 5 in front of the collector 3; during the period of collecting the reaction liquid into each collector in sequence, after the reaction liquid in each collector has been matured for a certain period of time, the matured reaction liquid in the collector 1, collector 2, and collector 3 is pumped into the second micromixer in sequence through the injection pump, and at the same time, the third mixed liquid is pumped into the second micromixer through the injection pump 6 to mix with the matured reaction liquid, and then continues to be pumped into the second microreactor (60 mL) for the second ring-opening reaction; wherein, the aging time of the reaction liquid in each collector is 30 The reaction mixture was aged for 10 min and the aging temperature was 70°C. The matured reaction liquid in each collector was pumped into the second micromixer at a flow rate of 8 mL / min. The third mixed liquid was pumped into the second micromixer at a flow rate of 3.5 mL / min. The temperature of the second ring-opening reaction was 80°C, and the reaction residence time was 5.22 min. The reaction effluent from the second microreactor was cooled to 20°C and washed with 500 mL of a 5wt% sodium bicarbonate solution. The organic layer was washed twice with water, each time with 500 mL. The organic phases were combined, dried, filtered to remove the desiccant, and concentrated to obtain a vegetable oil polyol with a yield of 96.9%, an epoxy value of 0.46%, a hydroxyl value of 131 mg KOH / g, and a viscosity of 561 mPa·s.

[0050] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 19 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 16.2 MPa and a shear strength of 8.7 MPa.

[0051] Example 2: The experimental method was the same as in Example 1, except that 1000 g of epoxidized cottonseed oil (epoxy value 5.7%) was replaced with 1000 g of epoxidized rapeseed oil (epoxy value 5.6%). The resulting vegetable oil polyol had a yield of 97.10%, an epoxy value of 0.41%, a hydroxyl value of 139 mg KOH / g, and a viscosity of 579 mPa·s.

[0052] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 2 hours, a through drying time of 4.5 hours, an adhesion of 17 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 14.2 MPa and a shear strength of 6.9 MPa.

[0053] Example 3: The experimental method was the same as in Example 1, except that 1000 g of epoxidized cottonseed oil (epoxy value 5.7%) was replaced with 1000 g of epoxidized sesame oil (epoxy value 5.9%). The resulting vegetable oil polyol had a yield of 95.00%, an epoxy value of 0.50%, a hydroxyl value of 120 mg KOH / g, and a viscosity of 515 mPa·s.

[0054] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 17 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 14.3 MPa and a shear strength of 6.5 MPa.

[0055] Example 4: The experimental method was the same as in Example 1, except that 1000 g of epoxidized cottonseed oil (epoxy value 5.7%) was replaced with 1000 g of epoxidized soybean oil (epoxy value 6.1%). The resulting vegetable oil polyol had a yield of 96.00%, an epoxy value of 1.00%, a hydroxyl value of 125 mg KOH / g, and a viscosity of 562 mPa·s.

[0056] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 17 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 15.6 MPa and a shear strength of 7.2 MPa.

[0057] Example 5: The experimental method was the same as in Example 1, except that 1000 g of epoxidized cottonseed oil (epoxy value 5.7%) was replaced with 1000 g of epoxidized rice bran oil (epoxy value 5.5%). The resulting vegetable oil polyol had a yield of 97.1%, an epoxy value of 0.23%, a hydroxyl value of 145 mg KOH / g, and a viscosity of 619 mPa·s.

[0058] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 2 hours, a through drying time of 5 hours, an adhesion of 17 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 13.9 MPa and a shear strength of 6.5 MPa.

[0059] Example 6: The experimental method was the same as Example 1, except that 130 g of benzoic acid was replaced with 130 g of cyclohexanecarboxylic acid. The resulting vegetable oil polyol had a yield of 96.78%, an epoxy value of 0.36%, a hydroxyl value of 137 mg KOH / g, and a viscosity of 570 mPa·s.

[0060] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 20 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 12.0 MPa and a shear strength of 5.3 MPa.

[0061] Example 7: The experimental method was the same as Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-furancarboxylic acid. The resulting vegetable oil polyol had a yield of 96.90%, an epoxy value of 0.16%, a hydroxyl value of 149 mg KOH / g, and a viscosity of 582 mPa·s.

[0062] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 18 MPa, and a salt spray resistance of greater than 300 hours. The polyurethane structural adhesive had a tensile strength of 11.0 MPa and a shear strength of 6.2 MPa.

[0063] Example 8: The experimental method was the same as Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 3-thiophenecarboxylic acid. The resulting vegetable oil polyol had a yield of 96.72%, an epoxy value of 0.46%, a hydroxyl value of 136 mg KOH / g, and a viscosity of 552 mPa·s.

[0064] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 15 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 11.5 MPa and a shear strength of 6.0 MPa.

[0065] Example 9: The experimental method was the same as Example 1, except that 130 g of cyclopentanecarboxylic acid was used instead of 130 g of cyclohexanecarboxylic acid. The resulting vegetable oil polyol had a yield of 95.83%, an epoxy value of 0.20%, a hydroxyl value of 146 mg KOH / g, and a viscosity of 575 mPa·s.

[0066] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 17 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 12.0 MPa and a shear strength of 5.9 MPa.

[0067] Example 10: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-tetrahydrofurancarboxylic acid. The resulting vegetable oil polyol had a yield of 97.90%, an epoxy value of 0.26%, a hydroxyl value of 135 mg KOH / g, and a viscosity of 563 mPa·s.

[0068] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 18 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 11.5 MPa and a shear strength of 6.1 MPa.

[0069] Example 11: The experimental method was the same as Example 1, except that 46 g of formic acid was used instead of 130 g of cyclohexanecarboxylic acid. The resulting vegetable oil polyol had a yield of 98.00%, an epoxy value of 0.53%, a hydroxyl value of 124 mg KOH / g, and a viscosity of 536 mPa·s.

[0070] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 13 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.0 MPa and a shear strength of 5.7 MPa.

[0071] Example 12: The experimental method was the same as Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 60 g of acetic acid. The resulting vegetable oil polyol had a yield of 95.59%, an epoxy value of 0.49%, a hydroxyl value of 127 mg KOH / g, and a viscosity of 543 mPa·s.

[0072] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 1.5 hours, a through dry time of 4 hours, an adhesion of 14 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.8 MPa and a shear strength of 6.0 MPa.

[0073] Example 13: The experimental method was the same as Example 1, except that 102 g of n-valeric acid was used instead of 130 g of cyclohexanecarboxylic acid. The resulting vegetable oil polyol had a yield of 93.39%, an epoxy value of 0.47%, a hydroxyl value of 123 mg KOH / g, and a viscosity of 544 mPa·s.

[0074] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 12 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.1 MPa and a shear strength of 6.0 MPa.

[0075] Example 14: The experimental method was the same as Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 116 g of n-hexanoic acid. The resulting vegetable oil polyol had a yield of 98.90%, an epoxy value of 0.52%, a hydroxyl value of 125 mg KOH / g, and a viscosity of 551 mPa·s.

[0076] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 11 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.6 MPa and a shear strength of 5.3 MPa.

[0077] Example 15: The experimental method was the same as Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 116 g of n-propionic acid. The resulting vegetable oil polyol had a yield of 96.69%, an epoxy value of 0.50%, a hydroxyl value of 130 mg KOH / g, and a viscosity of 540 mPa·s.

[0078] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 10 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.8 MPa and a shear strength of 6.5 MPa.

[0079] Example 16: The experimental method was the same as Example 1, except that 200 g of furfuryl alcohol was replaced with 65 g of methanol. The resulting vegetable oil polyol had a yield of 97.80%, an epoxy value of 0.49%, a hydroxyl value of 125 mg KOH / g, and a viscosity of 560 mPa·s.

[0080] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4 hours, an adhesion of 12 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 13.6 MPa and a shear strength of 7.0 MPa.

[0081] Example 17: The experimental method was the same as Example 1, except that 93 g of ethanol was used instead of 200 g of furfuryl alcohol. The resulting vegetable oil polyol had a yield of 95.59%, an epoxy value of 0.48%, a hydroxyl value of 127 mg KOH / g, and a viscosity of 555 mPa·s.

[0082] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4 hours, an adhesion of 11 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 13.7 MPa and a shear strength of 6.5 MPa.

[0083] Example 18: The experimental method was the same as Example 1, except that 200 g of furfuryl alcohol was replaced with 120 g of n-propanol. The resulting vegetable oil polyol had a yield of 97.78%, an epoxy value of 0.54%, a hydroxyl value of 122 mg KOH / g, and a viscosity of 548 mPa·s.

[0084] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 2 hours, a through drying time of 4 hours, an adhesion of 10 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.9 MPa and a shear strength of 6.8 MPa.

[0085] Example 19: The experimental method was the same as Example 1, except that 200 g of furfuryl alcohol was replaced with 145 g of n-butanol. The resulting vegetable oil polyol had a yield of 97.76%, an epoxy value of 0.60%, a hydroxyl value of 117 mg KOH / g, and a viscosity of 543 mPa·s.

[0086] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 12 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.7 MPa and a shear strength of 6.9 MPa.

[0087] Example 20: The experimental method was the same as Example 1, except that 200 g of furfuryl alcohol was replaced with 178 g of n-pentanol. The resulting vegetable oil polyol had a yield of 97.80%, an epoxy value of 0.50%, a hydroxyl value of 125 mg KOH / g, and a viscosity of 552 mPa·s.

[0088] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 12 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 13.0 MPa and a shear strength of 7.2 MPa.

[0089] Example 21: The experimental method was the same as Example 1, except that 200 g of furfuryl alcohol was replaced with 102 g of n-hexanol. The resulting vegetable oil polyol had a yield of 95.58%, an epoxy value of 0.50%, a hydroxyl value of 128 mg KOH / g, and a viscosity of 561 mPa·s.

[0090] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 12 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.9 MPa and a shear strength of 7.0 MPa.

[0091] Example 22: The experimental method was the same as Example 1, except that 200 g of furfuryl alcohol was replaced with 200 g of cyclopentylmethanol. The resulting vegetable oil polyol had a yield of 96.67%, an epoxy value of 0.53%, a hydroxyl value of 125 mg KOH / g, and a viscosity of 558 mPa·s.

[0092] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 14 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.6 MPa and a shear strength of 5.3 MPa.

[0093] Example 23: The experimental method was the same as Example 1, except that 200 g of furfuryl alcohol was replaced with 230 g of cyclohexylmethanol. The resulting vegetable oil polyol had a yield of 92.28%, an epoxy value of 0.46%, a hydroxyl value of 118 mg KOH / g, and a viscosity of 533 mPa·s.

[0094] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned formula. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 15 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.6 MPa and a shear strength of 5.5 MPa.

[0095] Example 24: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of benzoic acid, and 200 g of furfuryl alcohol was replaced with 65 g of methanol. The resulting vegetable oil polyol had a yield of 97.85%, an epoxy value of 0.39%, a hydroxyl value of 133 mg KOH / g, and a viscosity of 545 mPa·s.

[0096] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 18 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 10.8 MPa and a shear strength of 4.3 MPa.

[0097] Example 25: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-furancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 93 g of ethanol. The resulting vegetable oil polyol had a yield of 95.84%, an epoxy value of 0.18%, a hydroxyl value of 154 mg KOH / g, and a viscosity of 615 mPa·s.

[0098] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 16 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 10.6 MPa and a shear strength of 4.6 MPa.

[0099] Example 26: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 3-thiophenecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 120 g of n-propanol. The resulting vegetable oil polyol had a yield of 97.78%, an epoxy value of 0.54%, a hydroxyl value of 122 mg KOH / g, and a viscosity of 550 mPa·s.

[0100] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 1.5 hours, a through dry time of 4 hours, an adhesion of 16 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.0 MPa and a shear strength of 4.2 MPa.

[0101] Example 27: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of cyclopentanecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 145 g of n-butanol. The resulting vegetable oil polyol had a yield of 97.86%, an epoxy value of 0.34%, a hydroxyl value of 136 mg KOH / g, and a viscosity of 549 mPa·s.

[0102] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 16 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.2 MPa and a shear strength of 5.3 MPa.

[0103] Example 28: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-tetrahydrofurancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 178 g of n-pentanol. The resulting vegetable oil polyol had a yield of 97.89%, an epoxy value of 0.29%, a hydroxyl value of 138 mg KOH / g, and a viscosity of 545 mPa·s.

[0104] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 15 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.6 MPa and a shear strength of 4.9 MPa.

[0105] Example 29: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 46 g of formic acid, and 200 g of furfuryl alcohol was replaced with 205 g of n-hexanol. The resulting vegetable oil polyol had a yield of 95.55%, an epoxy value of 0.53%, a hydroxyl value of 126 mg KOH / g, and a viscosity of 557 mPa·s.

[0106] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4 hours, an adhesion of 10 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 13.2 MPa and a shear strength of 7.4 MPa.

[0107] Example 30: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 60 g of acetic acid, and 200 g of furfuryl alcohol was replaced with 200 g of cyclopentylmethanol. The resulting vegetable oil polyol had a yield of 96.65%, an epoxy value of 0.56%, a hydroxyl value of 118 mg KOH / g, and a viscosity of 548 mPa·s.

[0108] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 2 hours, a through drying time of 4 hours, an adhesion of 11 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 13.0 MPa and a shear strength of 7.5 MPa.

[0109] Example 31: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 102 g of n-valeric acid, and 200 g of furfuryl alcohol was replaced with 230 g of cyclohexylmethanol. The resulting vegetable oil polyol had a yield of 92.23%, an epoxy value of 0.49%, a hydroxyl value of 130 mg KOH / g, and a viscosity of 568 mPa·s.

[0110] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4 hours, an adhesion of 12 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.0 MPa and a shear strength of 4.9 MPa.

[0111] Example 32: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of benzoic acid, and 200 g of furfuryl alcohol was replaced with 93 g of ethanol. The resulting vegetable oil polyol had a yield of 95.68%, an epoxy value of 0.38%, a hydroxyl value of 134 mg KOH / g, and a viscosity of 550 mPa·s.

[0112] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 15 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.5 MPa and a shear strength of 5.3 MPa.

[0113] Example 33: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-furancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 120 g of n-propanol. The resulting vegetable oil polyol had a yield of 97.91%, an epoxy value of 0.24%, a hydroxyl value of 135 mg KOH / g, and a viscosity of 571 mPa·s.

[0114] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 15 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 12.0 MPa and a shear strength of 5.1 MPa.

[0115] Example 34: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 3-thiophenecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 145 g of n-butanol. The resulting vegetable oil polyol had a yield of 97.76%, an epoxy value of 0.60%, a hydroxyl value of 115 mg KOH / g, and a viscosity of 538 mPa·s.

[0116] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 14 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.9 MPa and a shear strength of 5.2 MPa.

[0117] Example 35: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of cyclopentanecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 178 g of n-pentanol. The resulting vegetable oil polyol had a yield of 97.90%, an epoxy value of 0.25%, a hydroxyl value of 138 mg KOH / g, and a viscosity of 570 mPa·s.

[0118] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4 hours, an adhesion of 13 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.8 MPa and a shear strength of 5.4 MPa.

[0119] Example 36: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-tetrahydrofurancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 205 g of n-hexanol. The resulting vegetable oil polyol had a yield of 95.76%, an epoxy value of 0.29%, a hydroxyl value of 130 mg KOH / g, and a viscosity of 552 mPa·s.

[0120] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4 hours, an adhesion of 14 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.0 MPa and a shear strength of 4.9 MPa.

[0121] Example 37: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 46 g of formic acid, and 200 g of furfuryl alcohol was replaced with 200 g of cyclopentylmethanol. The resulting vegetable oil polyol had a yield of 96.65%, an epoxy value of 0.56%, a hydroxyl value of 125 mg KOH / g, and a viscosity of 542 mPa·s.

[0122] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 2 hours, a through drying time of 4 hours, an adhesion of 12 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.4 MPa and a shear strength of 4.5 MPa.

[0123] Example 38: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 60 g of acetic acid, and 200 g of furfuryl alcohol was replaced with 230 g of cyclohexylmethanol. The resulting vegetable oil polyol had a yield of 92.23%, an epoxy value of 0.49%, a hydroxyl value of 132 mg KOH / g, and a viscosity of 563 mPa·s.

[0124] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4 hours, an adhesion of 9 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.8 MPa and a shear strength of 4.5 MPa.

[0125] Example 39: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 102 g of n-valeric acid, and 200 g of furfuryl alcohol was replaced with 65 g of methanol. The resulting vegetable oil polyol had a yield of 97.79%, an epoxy value of 0.52%, a hydroxyl value of 128 mg KOH / g, and a viscosity of 558 mPa·s.

[0126] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 2 hours, a through drying time of 4.5 hours, an adhesion of 10 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.6 MPa and a shear strength of 4.9 MPa.

[0127] Example 40: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of benzoic acid, and 200 g of furfuryl alcohol was replaced with 120 g of n-propanol. The resulting vegetable oil polyol had a yield of 97.83%, an epoxy value of 0.43%, a hydroxyl value of 135 mg KOH / g, and a viscosity of 575 mPa·s.

[0128] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 2 hours, a through drying time of 4.5 hours, an adhesion of 13 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.7 MPa and a shear strength of 5.0 MPa.

[0129] Example 41: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-furancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 145 g of n-butanol. The resulting vegetable oil polyol had a yield of 97.88%, an epoxy value of 0.30%, a hydroxyl value of 140 mg KOH / g, and a viscosity of 560 mPa·s.

[0130] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 12 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 12.0 MPa and a shear strength of 6.5 MPa.

[0131] Example 42: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 3-thiophenecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 178 g of n-pentanol. The resulting vegetable oil polyol had a yield of 97.80%, an epoxy value of 0.50%, a hydroxyl value of 122 mg KOH / g, and a viscosity of 520 mPa·s.

[0132] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 12 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 13.0 MPa and a shear strength of 5.6 MPa.

[0133] Example 43: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of cyclopentanecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 205 g of n-hexanol. The resulting vegetable oil polyol had a yield of 95.79%, an epoxy value of 0.24%, a hydroxyl value of 143 mg KOH / g, and a viscosity of 615 mPa·s.

[0134] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 2 hours, a through drying time of 4.5 hours, an adhesion of 12 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.7 MPa and a shear strength of 6.8 MPa.

[0135] Example 44: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-tetrahydrofurancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 200 g of cyclopentylmethanol. The resulting vegetable oil polyol had a yield of 96.81%, an epoxy value of 0.31%, a hydroxyl value of 138 mg KOH / g, and a viscosity of 563 mPa·s.

[0136] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 15 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 13.9 MPa and a shear strength of 7.4 MPa.

[0137] Example 45: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 46 g of formic acid, and 200 g of furfuryl alcohol was replaced with 230 g of cyclohexanemethanol. The resulting vegetable oil polyol had a yield of 92.23%, an epoxy value of 0.49%, a hydroxyl value of 124 mg KOH / g, and a viscosity of 528 mPa·s.

[0138] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 9 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.9 MPa and a shear strength of 7.4 MPa.

[0139] Example 46: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 60 g of acetic acid, and 200 g of furfuryl alcohol was replaced with 65 g of methanol. The resulting vegetable oil polyol had a yield of 97.79%, an epoxy value of 0.52%, a hydroxyl value of 120 mg KOH / g, and a viscosity of 524 mPa·s.

[0140] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 8 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 14.0 MPa and a shear strength of 7.5 MPa.

[0141] Example 47: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 102 g of n-valeric acid, and 200 g of furfuryl alcohol was replaced with 93 g of ethanol. The resulting vegetable oil polyol had a yield of 95.57%, an epoxy value of 0.52%, a hydroxyl value of 130 mg KOH / g, and a viscosity of 546 mPa·s.

[0142] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned formula. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 8 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 13.8 MPa and a shear strength of 7.8 MPa.

[0143] Example 48: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of benzoic acid, and 200 g of furfuryl alcohol was replaced with 145 g of n-butanol. The resulting vegetable oil polyol had a yield of 97.80%, an epoxy value of 0.50%, a hydroxyl value of 132 mg KOH / g, and a viscosity of 545 mPa·s.

[0144] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 10 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.9 MPa and a shear strength of 8.0 MPa.

[0145] Example 49: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-furancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 178 g of n-pentanol. The resulting vegetable oil polyol had a yield of 97.92%, an epoxy value of 0.20%, a hydroxyl value of 145 mg KOH / g, and a viscosity of 625 mPa·s.

[0146] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 10 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.7 MPa and a shear strength of 7.9 MPa.

[0147] Example 50: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 3-thiophenecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 205 g of n-hexanol. The resulting vegetable oil polyol had a yield of 95.58%, an epoxy value of 0.50%, a hydroxyl value of 134 mg KOH / g, and a viscosity of 557 mPa·s.

[0148] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 9 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.7 MPa and a shear strength of 6.4 MPa.

[0149] Example 51: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of cyclopentanecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 200 g of cyclopentylmethanol. The resulting vegetable oil polyol had a yield of 96.83%, an epoxy value of 0.27%, a hydroxyl value of 140 mg KOH / g, and a viscosity of 598 mPa·s.

[0150] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 14 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.5 MPa and a shear strength of 6.5 MPa.

[0151] Example 52: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-tetrahydrofurancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 230 g of cyclohexamethylol. The resulting vegetable oil polyol had a yield of 92.59%, an epoxy value of 0.24%, a hydroxyl value of 140 mg KOH / g, and a viscosity of 620 mPa·s.

[0152] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 15 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.8 MPa and a shear strength of 6.2 MPa.

[0153] Example 53: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 46 g of formic acid, and 200 g of furfuryl alcohol was replaced with 65 g of methanol. The resulting vegetable oil polyol had a yield of 97.79%, an epoxy value of 0.52%, a hydroxyl value of 129 mg KOH / g, and a viscosity of 545 mPa·s.

[0154] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 7 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 13.6 MPa and a shear strength of 8.0 MPa.

[0155] Example 54: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 60 g of acetic acid, and 200 g of furfuryl alcohol was replaced with 93 g of ethanol. The resulting vegetable oil polyol had a yield of 95.57%, an epoxy value of 0.52%, a hydroxyl value of 130 mg KOH / g, and a viscosity of 550 mPa·s.

[0156] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 7 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 13.4 MPa and a shear strength of 8.0 MPa.

[0157] Example 55: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 102 g of n-pentanoic acid, and 200 g of furfuryl alcohol was replaced with 120 g of n-propanol. The resulting vegetable oil polyol had a yield of 97.77%, an epoxy value of 0.57%, a hydroxyl value of 121 mg KOH / g, and a viscosity of 542 mPa·s.

[0158] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 9 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 12.9 MPa and a shear strength of 7.6 MPa.

[0159] Example 56: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of benzoic acid, and 200 g of furfuryl alcohol was replaced with 178 g of n-pentanol. The resulting vegetable oil polyol had a yield of 97.84%, an epoxy value of 0.40%, a hydroxyl value of 138 mg KOH / g, and a viscosity of 575 mPa·s.

[0160] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 2 hours, a through drying time of 4.5 hours, an adhesion of 11 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.5 MPa and a shear strength of 7.5 MPa.

[0161] Example 57: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-furancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 205 g of n-hexanol. The resulting vegetable oil polyol had a yield of 95.82%, an epoxy value of 0.20%, a hydroxyl value of 146 mg KOH / g, and a viscosity of 618 mPa·s.

[0162] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 10 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.7 MPa and a shear strength of 7.6 MPa.

[0163] Example 58: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 3-thiophenecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 200 g of cyclopentylmethanol. The resulting vegetable oil polyol had a yield of 96.67%, an epoxy value of 0.53%, a hydroxyl value of 128 mg KOH / g, and a viscosity of 548 mPa·s.

[0164] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 15 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.5 MPa and a shear strength of 7.5 MPa.

[0165] Example 59: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of cyclopentanecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 230 g of cyclohexanemethanol. The resulting vegetable oil polyol had a yield of 92.65%, an epoxy value of 0.20%, a hydroxyl value of 144 mg KOH / g, and a viscosity of 590 mPa·s.

[0166] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 1.5 hours, a through dry time of 4 hours, an adhesion of 16 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.7 MPa and a shear strength of 7.4 MPa.

[0167] Example 60: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-tetrahydrofurancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 65 g of methanol. The resulting vegetable oil polyol had a yield of 97.89%, an epoxy value of 0.27%, a hydroxyl value of 137 mg KOH / g, and a viscosity of 548 mPa·s.

[0168] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 10 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.0 MPa and a shear strength of 6.8 MPa.

[0169] Example 61: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 46 g of formic acid, and 200 g of furfuryl alcohol was replaced with 93 g of ethanol. The resulting vegetable oil polyol had a yield of 95.57%, an epoxy value of 0.52%, a hydroxyl value of 129 mg KOH / g, and a viscosity of 545 mPa·s.

[0170] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 6 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 13.5 MPa and a shear strength of 8.0 MPa.

[0171] Example 62: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 60 g of acetic acid, and 200 g of furfuryl alcohol was replaced with 120 g of n-propanol. The resulting vegetable oil polyol had a yield of 97.77%, an epoxy value of 0.57%, a hydroxyl value of 120 mg KOH / g, and a viscosity of 540 mPa·s.

[0172] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 6 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 13.8 MPa and a shear strength of 7.6 MPa.

[0173] Example 63: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 102 g of n-valeric acid, and 200 g of furfuryl alcohol was replaced with 145 g of n-butanol. The resulting vegetable oil polyol had a yield of 97.74%, an epoxy value of 0.63%, a hydroxyl value of 116 mg KOH / g, and a viscosity of 536 mPa·s.

[0174] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 7 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 13.6 MPa and a shear strength of 7.7 MPa.

[0175] Example 64: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of benzoic acid, and 200 g of furfuryl alcohol was replaced with 205 g of n-hexanol. The resulting vegetable oil polyol had a yield of 95.82%, an epoxy value of 0.20%, a hydroxyl value of 148 mg KOH / g, and a viscosity of 580 mPa·s.

[0176] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 2 hours, a through drying time of 4.5 hours, an adhesion of 10 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.7 MPa and a shear strength of 5.9 MPa.

[0177] Example 65: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-furancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 200 g of cyclopentylmethanol. The resulting vegetable oil polyol had a yield of 96.67%, an epoxy value of 0.53%, a hydroxyl value of 119 mg KOH / g, and a viscosity of 540 mPa·s.

[0178] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 12 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.9 MPa and a shear strength of 5.8 MPa.

[0179] Example 66: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 3-thiophenecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 230 g of cyclohexamethylol. The resulting vegetable oil polyol had a yield of 92.65%, an epoxy value of 0.20%, a hydroxyl value of 140 mg KOH / g, and a viscosity of 569 mPa·s.

[0180] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 13 MPa, and a salt spray resistance of 400 hours. The polyurethane structural adhesive had a tensile strength of 11.0 MPa and a shear strength of 4.7 MPa.

[0181] Example 67: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of cyclopentanecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 65 g of methanol. The resulting vegetable oil polyol had a yield of 97.89%, an epoxy value of 0.27%, a hydroxyl value of 142 mg KOH / g, and a viscosity of 582 mPa·s.

[0182] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 10 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.6 MPa and a shear strength of 5.2 MPa.

[0183] Example 68: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-tetrahydrofurancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 93 g of ethanol. The resulting vegetable oil polyol had a yield of 95.57%, an epoxy value of 0.52%, a hydroxyl value of 120 mg KOH / g, and a viscosity of 539 mPa·s.

[0184] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 9 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.5 MPa and a shear strength of 5.0 MPa.

[0185] Example 69: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 46 g of formic acid, and 200 g of furfuryl alcohol was replaced with 120 g of n-propanol. The resulting vegetable oil polyol had a yield of 97.77%, an epoxy value of 0.57%, a hydroxyl value of 119 mg KOH / g, and a viscosity of 542 mPa·s.

[0186] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 7 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 14.0 MPa and a shear strength of 7.5 MPa.

[0187] Example 70: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 60 g of acetic acid, and 200 g of furfuryl alcohol was replaced with 145 g of n-butanol. The resulting vegetable oil polyol had a yield of 97.74%, an epoxy value of 0.63%, a hydroxyl value of 112 mg KOH / g, and a viscosity of 528 mPa·s.

[0188] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 6 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 14.7 MPa and a shear strength of 7.9 MPa.

[0189] Example 71: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 102 g of n-pentanoic acid, and 200 g of furfuryl alcohol was replaced with 178 g of n-pentanol. The resulting vegetable oil polyol had a yield of 97.84%, an epoxy value of 0.40%, a hydroxyl value of 138 mg KOH / g, and a viscosity of 570 mPa·s.

[0190] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 7 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 13.2 MPa and a shear strength of 6.9 MPa.

[0191] Example 72: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of benzoic acid, and 200 g of furfuryl alcohol was replaced with 200 g of cyclopentylmethanol. The resulting vegetable oil polyol had a yield of 96.67%, an epoxy value of 0.53%, a hydroxyl value of 118 mg KOH / g, and a viscosity of 542 mPa·s.

[0192] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 14 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 11.2 MPa and a shear strength of 5.2 MPa.

[0193] Example 73: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-furancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 230 g of cyclohexamethylol. The resulting vegetable oil polyol had a yield of 92.65%, an epoxy value of 0.20%, a hydroxyl value of 139 mg KOH / g, and a viscosity of 570 mPa·s.

[0194] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 14 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 11.4 MPa and a shear strength of 5.0 MPa.

[0195] Example 74: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 3-thiophenecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 65 g of methanol. The resulting vegetable oil polyol had a yield of 97.89%, an epoxy value of 0.27%, a hydroxyl value of 140 mg KOH / g, and a viscosity of 590 mPa·s.

[0196] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 11 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.0 MPa and a shear strength of 6.3 MPa.

[0197] Example 75: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of cyclopentanecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 93 g of ethanol. The resulting vegetable oil polyol had a yield of 95.57%, an epoxy value of 0.52%, a hydroxyl value of 122 mg KOH / g, and a viscosity of 545 mPa·s.

[0198] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 10 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.4 MPa and a shear strength of 6.0 MPa.

[0199] Example 76: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-tetrahydrofurancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 120 g of n-propanol. The resulting vegetable oil polyol had a yield of 97.77%, an epoxy value of 0.57%, a hydroxyl value of 122 mg KOH / g, and a viscosity of 532 mPa·s.

[0200] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 11 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.9 MPa and a shear strength of 5.6 MPa.

[0201] Example 77: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 46 g of formic acid, and 200 g of furfuryl alcohol was replaced with 145 g of n-butanol. The resulting vegetable oil polyol had a yield of 97.74%, an epoxy value of 0.63%, a hydroxyl value of 116 mg KOH / g, and a viscosity of 532 mPa·s.

[0202] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 8 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 12.8 MPa and a shear strength of 7.1 MPa.

[0203] Example 78: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 60 g of acetic acid, and 200 g of furfuryl alcohol was replaced with 178 g of n-pentanol. The resulting vegetable oil polyol had a yield of 97.84%, an epoxy value of 0.40%, a hydroxyl value of 128 mg KOH / g, and a viscosity of 554 mPa·s.

[0204] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 7 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 12.7 MPa and a shear strength of 7.2 MPa.

[0205] Example 79: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 102 g of n-pentanoic acid, and 200 g of furfuryl alcohol was replaced with 205 g of n-hexanol. The resulting vegetable oil polyol had a yield of 95.82%, an epoxy value of 0.20%, a hydroxyl value of 137 mg KOH / g, and a viscosity of 577 mPa·s.

[0206] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 9 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.1 MPa and a shear strength of 6.9 MPa.

[0207] Example 80: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of benzoic acid, and 200 g of furfuryl alcohol was replaced with 230 g of cyclohexylmethanol. The resulting vegetable oil polyol had a yield of 92.65%, an epoxy value of 0.20%, a hydroxyl value of 135 mg KOH / g, and a viscosity of 573 mPa·s.

[0208] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 14 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 11.2 MPa and a shear strength of 4.9 MPa.

[0209] Example 81: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-furancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 65 g of methanol. The resulting vegetable oil polyol had a yield of 97.89%, an epoxy value of 0.27%, a hydroxyl value of 141 mg KOH / g, and a viscosity of 596 mPa·s.

[0210] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 8 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.9 MPa and a shear strength of 5.6 MPa.

[0211] Example 82: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 3-thiophenecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 93 g of ethanol. The resulting vegetable oil polyol had a yield of 95.57%, an epoxy value of 0.52%, a hydroxyl value of 120 mg KOH / g, and a viscosity of 550 mPa·s.

[0212] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 9 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.0 MPa and a shear strength of 5.7 MPa.

[0213] Example 83: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of cyclopentanecarboxylic acid, and 200 g of furfuryl alcohol was replaced with 120 g of n-propanol. The resulting vegetable oil polyol had a yield of 97.77%, an epoxy value of 0.57%, a hydroxyl value of 121 mg KOH / g, and a viscosity of 536 mPa·s.

[0214] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 9 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.1 MPa and a shear strength of 5.2 MPa.

[0215] Example 84: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 130 g of 2-tetrahydrofurancarboxylic acid, and 200 g of furfuryl alcohol was replaced with 145 g of n-butanol. The resulting vegetable oil polyol had a yield of 97.74%, an epoxy value of 0.63%, a hydroxyl value of 118 mg KOH / g, and a viscosity of 540 mPa·s.

[0216] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 8 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 13.0 MPa and a shear strength of 7.0 MPa.

[0217] Example 85: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 46 g of formic acid, and 200 g of furfuryl alcohol was replaced with 178 g of n-pentanol. The resulting vegetable oil polyol had a yield of 97.84%, an epoxy value of 0.40%, a hydroxyl value of 124 mg KOH / g, and a viscosity of 558 mPa·s.

[0218] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 6 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 12.9 MPa and a shear strength of 6.9 MPa.

[0219] Example 86: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 60 g of acetic acid, and 200 g of furfuryl alcohol was replaced with 205 g of n-hexanol. The resulting vegetable oil polyol had a yield of 95.82%, an epoxy value of 0.20%, a hydroxyl value of 132 mg KOH / g, and a viscosity of 580 mPa·s.

[0220] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1 hour, a through drying time of 1 hour, an adhesion of 6 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 13.9 MPa and a shear strength of 8.3 MPa.

[0221] Example 87: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 102 g of n-pentanoic acid, and 200 g of furfuryl alcohol was replaced with 200 g of cyclopentylmethanol. The resulting vegetable oil polyol had a yield of 96.67%, an epoxy value of 0.53%, a hydroxyl value of 115 mg KOH / g, and a viscosity of 543 mPa·s.

[0222] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the above formulations. Performance test results are as follows: the polyurethane coating had a surface drying time of 2 hours, a through drying time of 4.5 hours, an adhesion of 1000 MPa, and a salt spray resistance of 1000 h. The polyurethane structural adhesive had a tensile strength of 11.7 MPa and a shear strength of 5.6 MPa.

[0223] Example 88: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 116 g of n-hexanoic acid, and 200 g of furfuryl alcohol was replaced with 65 g of methanol. The resulting vegetable oil polyol had a yield of 97.79%, an epoxy value of 0.52%, a hydroxyl value of 116 mg KOH / g, and a viscosity of 540 mPa·s.

[0224] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 8 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 12.8 MPa and a shear strength of 6.5 MPa.

[0225] Example 89: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 74 g of propionic acid, and 200 g of furfuryl alcohol was replaced with 93 g of ethanol. The resulting vegetable oil polyol had a yield of 95.57%, an epoxy value of 0.52%, a hydroxyl value of 120 mg KOH / g, and a viscosity of 555 mPa·s.

[0226] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 6 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 13.9 MPa and a shear strength of 7.3 MPa.

[0227] Example 90: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 116 g of n-hexanoic acid, and 200 g of furfuryl alcohol was replaced with 93 g of ethanol. The resulting vegetable oil polyol had a yield of 95.57%, an epoxy value of 0.52%, a hydroxyl value of 118 mg KOH / g, and a viscosity of 559 mPa·s.

[0228] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 8 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 14.0 MPa and a shear strength of 7.2 MPa.

[0229] Example 91: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 74 g of propionic acid, and 200 g of furfuryl alcohol was replaced with 120 g of n-propanol. The resulting vegetable oil polyol had a yield of 97.77%, an epoxy value of 0.57%, a hydroxyl value of 122 mg KOH / g, and a viscosity of 548 mPa·s.

[0230] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 7 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 14.3 MPa and a shear strength of 7.0 MPa.

[0231] Example 92: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 116 g of n-hexanoic acid, and 200 g of furfuryl alcohol was replaced with 120 g of n-propanol. The resulting vegetable oil polyol had a yield of 97.77%, an epoxy value of 0.57%, a hydroxyl value of 120 mg KOH / g, and a viscosity of 542 mPa·s.

[0232] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 9 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 14.2 MPa and a shear strength of 7.1 MPa.

[0233] Example 93: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 74 g of propionic acid, and 200 g of furfuryl alcohol was replaced with 145 g of n-butanol. The resulting vegetable oil polyol had a yield of 97.74%, an epoxy value of 0.63%, a hydroxyl value of 117 mg KOH / g, and a viscosity of 533 mPa·s.

[0234] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 9 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 14.2 MPa and a shear strength of 6.9 MPa.

[0235] Example 94: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 116 g of n-hexanoic acid, and 200 g of furfuryl alcohol was replaced with 145 g of n-butanol. The resulting vegetable oil polyol had a yield of 97.74%, an epoxy value of 0.63%, a hydroxyl value of 119 mg KOH / g, and a viscosity of 538 mPa·s.

[0236] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 9 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 13.9 MPa and a shear strength of 6.9 MPa.

[0237] Example 95: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 74 g of propionic acid, and 200 g of furfuryl alcohol was replaced with 178 g of n-pentanol. The resulting vegetable oil polyol had a yield of 97.78%, an epoxy value of 0.54%, a hydroxyl value of 125 mg KOH / g, and a viscosity of 552 mPa·s.

[0238] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 7 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 14.2 MPa and a shear strength of 7.1 MPa.

[0239] Example 96: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 116 g of n-hexanoic acid, and 200 g of furfuryl alcohol was replaced with 178 g of n-pentanol. The resulting vegetable oil polyol had a yield of 97.78%, an epoxy value of 0.54%, a hydroxyl value of 120 mg KOH / g, and a viscosity of 546 mPa·s.

[0240] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 8 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 12.9 MPa and a shear strength of 5.7 MPa.

[0241] Example 97: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 74 g of propionic acid, and 200 g of furfuryl alcohol was replaced with 205 g of n-hexanol. The resulting vegetable oil polyol had a yield of 95.55%, an epoxy value of 0.54%, a hydroxyl value of 118 mg KOH / g, and a viscosity of 555 mPa·s.

[0242] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 8 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 12.6 MPa and a shear strength of 5.9 MPa.

[0243] Example 98: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 116 g of n-hexanoic acid, and 200 g of furfuryl alcohol was replaced with 205 g of n-hexanol. The resulting vegetable oil polyol had a yield of 95.55%, an epoxy value of 0.54%, a hydroxyl value of 126 mg KOH / g, and a viscosity of 563 mPa·s.

[0244] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 8 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 12.5 MPa and a shear strength of 5.7 MPa.

[0245] Example 99: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 74 g of propionic acid, and 200 g of furfuryl alcohol was replaced with 200 g of cyclopentylmethanol. The resulting vegetable oil polyol had a yield of 96.65%, an epoxy value of 0.56%, a hydroxyl value of 123 mg KOH / g, and a viscosity of 558 mPa·s.

[0246] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 7 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 11.6 MPa and a shear strength of 5.5 MPa.

[0247] Example 100: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 116 g of n-hexanoic acid, and 200 g of furfuryl alcohol was replaced with 200 g of cyclopentylmethanol. The resulting vegetable oil polyol had a yield of 96.65%, an epoxy value of 0.56%, a hydroxyl value of 125 mg KOH / g, and a viscosity of 548 mPa·s.

[0248] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 9 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 11.2 MPa and a shear strength of 4.6 MPa.

[0249] Example 101: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 74 g of propionic acid, and 200 g of furfuryl alcohol was replaced with 230 g of cyclohexanemethanol. The resulting vegetable oil polyol had a yield of 92.23%, an epoxy value of 0.49%, a hydroxyl value of 134 mg KOH / g, and a viscosity of 560 mPa·s.

[0250] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 7 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 11.8 MPa and a shear strength of 4.2 MPa.

[0251] Example 102: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 116 g of n-hexanoic acid, and 200 g of furfuryl alcohol was replaced with 230 g of cyclohexylmethanol. The resulting vegetable oil polyol had a yield of 92.23%, an epoxy value of 0.49%, a hydroxyl value of 138 mg KOH / g, and a viscosity of 562 mPa·s.

[0252] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 9 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 11.5 MPa and a shear strength of 4.6 MPa.

[0253] Example 103: The experimental method was the same as in Example 1, except that 130 g of cyclohexanecarboxylic acid was replaced with 74 g of propionic acid, and 200 g of furfuryl alcohol was replaced with 65 g of methanol. The resulting vegetable oil polyol had a yield of 97.79%, an epoxy value of 0.52%, a hydroxyl value of 130 mg KOH / g, and a viscosity of 560 mPa·s.

[0254] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 5 hours, an adhesion of 6 MPa, and a salt spray resistance of 200 hours. The polyurethane structural adhesive had a tensile strength of 13.0 MPa and a shear strength of 6.5 MPa.

[0255] Example 104: The experimental method was the same as in Example 1, except that the amount of fluoroboric acid aqueous solution (40 wt%) was 5 g. The resulting vegetable oil polyol had a yield of 93.40%, an epoxy value of 0.80%, a hydroxyl value of 116 mg KOH / g, and a viscosity of 520 mPa·s.

[0256] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 2 hours, a through drying time of 4.5 hours, an adhesion of 14 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 11.3 MPa and a shear strength of 4.8 MPa.

[0257] Example 105: The experimental method was the same as in Example 1, except that the amount of fluoroboric acid aqueous solution (40 wt%) was 20 g. The resulting vegetable oil polyol had a yield of 95.40%, an epoxy value of 0.36%, a hydroxyl value of 135 mg KOH / g, and a viscosity of 573 mPa·s.

[0258] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4 hours, an adhesion of 20 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 11.5 MPa and a shear strength of 4.3 MPa.

[0259] Example 106: The experimental method was the same as in Example 1, except that the second mixed liquid was pumped into the first microreactor at a flow rate of 1.8 mL / min. The resulting vegetable oil polyol had a yield of 93.60%, an epoxy value of 1.02%, a hydroxyl value of 110 mgKOH / g, and a viscosity of 532 mPa·s.

[0260] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 2 hours, a through drying time of 4.5 hours, an adhesion of 13 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 11.2 MPa and a shear strength of 4.5 MPa.

[0261] Example 107: The experimental method was the same as in Example 1, except that the third mixed liquid was pumped into the second microreactor at a flow rate of 5.0 mL / min. The resulting vegetable oil polyol had a yield of 91.60%, an epoxy value of 0.26%, a hydroxyl value of 136 gKOH / g, and a viscosity of 579 mPa·s.

[0262] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 1.5 hours, a through drying time of 4.5 hours, an adhesion of 18 MPa, and a salt spray resistance of greater than 600 hours. The polyurethane structural adhesive had a tensile strength of 10.9 MPa and a shear strength of 4.5 MPa.

[0263] Example 108: The experimental method was the same as in Example 1, except that furfuryl alcohol was replaced with 64 g of methanol. The third mixed liquid was pumped into the second microreactor at a flow rate of 5.0 mL / min, and the second ring-opening reaction temperature was 95°C. The resulting vegetable oil polyol had a yield of 93.80%, an epoxy value of 0, a hydroxyl value of 152 mg KOH / g, and a viscosity of 632 mPa·s.

[0264] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 2 hours, a through dry time of 4.5 hours, an adhesion of 16 MPa, and a salt spray resistance of 300 hours. The polyurethane structural adhesive had a tensile strength of 13.6 MPa and a shear strength of 6.6 MPa.

[0265] Comparative Example 1: No three parallel pipelines, namely, collector 1, collector 2, and collector 3, were set between the first microreactor and the second micromixer. The experiment found that the reaction could not proceed smoothly because the reaction pressure in the microreactor was too high and exceeded the load range.

[0266] Comparative Example 2: The reaction material ratios were the same as those in Example 1, except that a conventional reactor was used. 1000 g of epoxidized cottonseed oil (epoxy value 5.7%), 10 g of a 40 wt% aqueous fluoroboric acid solution, 168 g of cyclohexanecarboxylic acid, and 500 mL of ethyl acetate were mixed and reacted at 80°C for 6 h. After the reaction, the mixture was incubated at 70°C for 30 min. Subsequently, 188 g of furfuryl alcohol was added and reacted at 80°C for 6 h. After the reaction, the reaction solution was cooled to 20°C and washed with 5 wt% aqueous sodium bicarbonate solution. The organic layer was collected and washed twice with water. The combined organic phases were dried, filtered to remove the desiccant, and concentrated to yield a vegetable oil polyol with a yield of 63%, an epoxy value of 1.78%, a hydroxyl value of 316 mg KOH / g, and a viscosity of 1789 mPa·s.

[0267] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 3 hours, a through dry time of 6.5 hours, an adhesion of 6 MPa, and a salt spray resistance of 100 hours. The polyurethane structural adhesive had a tensile strength of 6.8 MPa and a shear strength of 2.7 MPa.

[0268] Comparative Example 3: Only cyclohexanecarboxylic acid was used for ring opening, and the material ratio of epoxidized cottonseed oil to cyclohexanecarboxylic acid was the same as the material ratio of epoxidized cottonseed oil to (cyclohexanecarboxylic acid + furfuryl alcohol) at the moment of reaction in Example 1.

[0269] 1000 g of epoxidized cottonseed oil (epoxy value 5.7%) and 10 g of a fluoroboric acid aqueous solution (40 wt%) were mixed to obtain a first mixed solution; 130 g of cyclohexanecarboxylic acid was dissolved in 500 mL of ethyl acetate and mixed to obtain a second mixed solution.

[0270] The first and second mixed liquids were preheated to 40°C and simultaneously pumped into the first micromixer via syringe pumps 1 and 2, respectively, for mixing. The first and second mixed liquids were then pumped into the first microreactor (40 mL) of the microreactor for the first ring-opening reaction. The first mixed liquid was pumped at a flow rate of 5.2 mL / min, and the second mixed liquid was pumped at a flow rate of 7.6 mL / min. The temperature of the first ring-opening reaction was 80°C, and the reaction residence time was 3.13 min. After the reaction, the reaction effluent was cooled to 20°C and washed with 500 mL of 5wt% sodium bicarbonate solution. The organic layer was then washed twice with 500 mL of water each time. The combined organic phases were dried, filtered to remove the desiccant, and concentrated to yield a vegetable oil polyol with a yield of 60.1%, an epoxy value of 2.18%, a hydroxyl value of 89 mg KOH / g, and a viscosity of 1829 mPa•s.

[0271] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface drying time of 3 hours, a through drying time of 6 hours, an adhesion of 10 MPa, and a salt spray resistance of 100 hours. The polyurethane structural adhesive had a tensile strength of 6.2 MPa and a shear strength of 3.0 MPa.

[0272] Comparative Example 4: Only furfuryl alcohol was used for ring opening, and the material ratio of epoxidized cottonseed oil to furfuryl alcohol was the same as the material ratio of epoxidized cottonseed oil to (cyclohexanecarboxylic acid + furfuryl alcohol) at the moment of reaction in Example 1.

[0273] 1000 g of epoxidized cottonseed oil (epoxy value 5.7%) and 10 g of a fluoroboric acid aqueous solution (40 wt%) were mixed to obtain a first mixed solution; 317 g of furfuryl alcohol was dissolved in 500 mL of ethyl acetate and mixed to obtain a second mixed solution.

[0274] The first and second mixed liquids were preheated to 40°C and simultaneously pumped into the first micromixer via syringe pumps 1 and 2, respectively, for mixing. The first and second mixed liquids were then pumped into the first microreactor (40 mL) of the microreactor for the first ring-opening reaction. The first mixed liquid was pumped at a flow rate of 5.2 mL / min, and the second mixed liquid was pumped at a flow rate of 7.6 mL / min. The temperature of the first ring-opening reaction was 80°C, and the reaction residence time was 3.13 min. After the reaction, the reaction effluent was cooled to 20°C and washed with 500 mL of 5wt% sodium bicarbonate solution. The organic layer was then washed twice with 500 mL of water each time. The combined organic phases were dried, filtered to remove the desiccant, and concentrated to yield a vegetable oil polyol with a yield of 68.2%, an epoxy value of 1.56%, a hydroxyl value of 110 mg KOH / g, and a viscosity of 1580 mPa•s.

[0275] Polyurethane coatings and polyurethane structural adhesives were prepared using the vegetable oil polyols according to the aforementioned recipes. Performance test results are as follows: the polyurethane coating had a surface dry time of 4 hours, a through dry time of 8 hours, an adhesion of 6 MPa, and a salt spray resistance of 100 hours. The polyurethane structural adhesive had a tensile strength of 6.4 MPa and a shear strength of 2.7 MPa.

[0276] The present invention provides a bio-based polyol, a method for its preparation, and a concept and method for its application in bio-based polyurethanes. There are numerous methods and approaches for implementing this technical solution. The foregoing merely represents a preferred embodiment of the present invention. It should be noted that those skilled in the art may make various improvements and modifications without departing from the principles of the present invention, and such improvements and modifications are also within the scope of protection of the present invention. Any components not specified in this embodiment may be implemented using existing technologies.

Claims

1. A method for preparing a bio-based polyol, characterized in that: The steps include: (1) mixing epoxidized vegetable oil and an acidic catalyst to obtain a first mixed solution; mixing a carboxylic acid ring-opening reagent and an organic solvent to obtain a second mixed solution; and mixing an alcohol ring-opening reagent and an organic solvent to obtain a third mixed solution; The first mixed liquid and the second mixed liquid are simultaneously pumped into a first micromixer for mixing, and then continuously pumped into a first microreactor of a microreactor device for a first ring-opening reaction to obtain a reaction effluent; (2) Open the valve in front of the first collector, and let the reaction effluent of the first microreactor flow continuously into the first collector. After the collection is completed, close the valve in front of the first collector; then open the valve in front of the second collector, and let the reaction effluent of the first microreactor flow into the second collector. After the collection is completed, close the valve in front of the second collector; then open the valve in front of the third collector, and let the reaction effluent of the first microreactor flow into the third collector. After the collection is completed, close the valve in front of the third collector; while the reaction effluent of the first microreactor is collected into each collector in turn, when the reaction effluent in each collector is matured, the matured reaction liquid in the first collector, the second collector, and the third collector is pumped into the second micromixer in turn, and the third mixed liquid is pumped into the second micromixer to mix with the matured reaction liquid, and then continues to be pumped into the second microreactor of the microreactor device for a second ring-opening reaction. After the reaction is completed, post-processing is performed to obtain bio-based polyol.

2. The preparation method according to claim 1, characterized in that In step (1), the epoxidized vegetable oil is any one or a combination of epoxidized vegetable oil, epoxidized cottonseed oil, epoxidized rapeseed oil, epoxidized sesame oil, epoxidized soybean oil, epoxidized rice bran oil, epoxidized olive oil, epoxidized peanut oil, epoxidized coconut oil, epoxidized palm oil, epoxidized corn oil and epoxidized sunflower oil; and / or the acidic catalyst is any one or a combination of fluoroboric acid, concentrated sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid; and / or the mass of the acidic catalyst accounts for 0.02% to 1.0% of the mass of the epoxidized vegetable oil.

3. The preparation method according to claim 1, characterized in that In step (1), the carboxylic acid ring-opening reagent is any one or a combination of benzoic acid, 2-furancarboxylic acid, 3-thiophenecarboxylic acid, cyclohexanecarboxylic acid, cyclopentanecarboxylic acid, 2-tetrahydrofurancarboxylic acid, formic acid, propionic acid, n-pentanoic acid and n-hexanoic acid; and / or, the alcohol ring-opening reagent is any one or a combination of methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, cyclopentylmethanol, cyclohexylmethanol and furfuryl alcohol; and / or, the organic solvent is any one or a combination of ethyl acetate, dichloromethane, dichloroethane, chloroform, n-hexane, tetrahydrofuran, 1,4-dioxane, carbon tetrachloride, toluene and xylene.

4. The preparation method according to claim 1, characterized in that In step (1), the concentration of the carboxylic acid ring-opening reagent in the second mixed solution is 0.001-0.010 mol / mL; and / or the concentration of the alcohol ring-opening reagent in the third mixed solution is 0.001-0.010 mol / mL.

5. The preparation method according to claim 1, characterized in that In step (1), the flow rate of the first mixed liquid pumped into the first microreactor of the microreactor is 1.0~10.0 mL / min; and / or, the flow rate of the second mixed liquid pumped into the first microreactor of the microreactor is 1.0~10.0 mL / min; and / or, in the first ring-opening reaction, the reaction molar ratio of the epoxy group in the epoxidized vegetable oil to the carboxylic acid group in the carboxylic acid ring-opening reagent is controlled to be 1.0:(0.2~0.4) during the reaction process.

6. The preparation method according to claim 1, characterized in that In step (1), the reaction temperature of the first ring-opening reaction is 70°C to 90°C; and / or the reaction time of the first ring-opening reaction is 2.0 min to 10.0 min.

7. The preparation method according to claim 1, characterized in that In step (2), the aging temperature is 60°C to 80°C; and / or the aging time is 20 to 40 min; and / or the flow rate at which the aging reaction liquid in the first collector is pumped into the second microreactor of the microreactor is 5.0 to 20.0 mL / min; and / or the flow rate at which the aging reaction liquid in the second collector is pumped into the second microreactor of the microreactor is 5.0 to 20.0 mL / min; and / or the flow rate at which the aging reaction liquid in the third collector is pumped into the second microreactor of the microreactor is 5.0 to 20.0 mL / min; and / or the flow rate at which the third mixed liquid is pumped into the second microreactor of the microreactor is 1.0 to 10.0 mL / min.

8. The preparation method according to claim 1, characterized in that In step (2), in the second ring-opening reaction, based on the epoxy groups in the epoxy vegetable oil in the first mixed solution, the reaction molar ratio of the epoxy groups in the epoxy vegetable oil to the hydroxyl groups in the alcohol ring-opening reagent is controlled to be 1.0:(0.5~0.8); and / or, the reaction temperature of the second ring-opening reaction is 70℃~95℃; and / or, the reaction time of the second ring-opening reaction is 1.0 min~20.0 min.

9. The preparation method according to claim 1, characterized in that The microreactor comprises a connecting pipeline, a first injection pump, a second injection pump, a third injection pump, a fourth injection pump, a fifth injection pump, a sixth injection pump, a first micromixer, a second micromixer, a first microreactor, a second microreactor, a first collector, a second collector, a third collector, a first collector front valve, a second collector front valve, a third collector front valve and a receiver; wherein, the first injection pump and the second injection pump are connected in parallel to the first micromixer; the first micromixer is connected to the first microreactor; a first pipeline, a second pipeline and a third pipeline are connected in parallel between the first microreactor and the second micromixer, the first pipeline is connected in series with the first collector front valve, the first collector and the third injection pump, the second pipeline is connected in series with the second collector front valve, the second collector and the fourth injection pump, the third pipeline is connected in series with the third collector front valve, the third collector and the fifth injection pump; the sixth injection pump is connected to the first feed port of the second micromixer; the second micromixer is connected in series with the second microreactor and the receiver.

10. The bio-based polyol prepared by the preparation method according to any one of claims 1 to 9.

11. The bio-based polyol according to claim 1, characterized in that The epoxy value of the bio-based polyol is 0% to 1.10%; and / or the hydroxyl value of the bio-based polyol is 100 to 180 mg KOH / g.

12. Use of the bio-based polyol according to claim 10 in the preparation of polyurethane coatings and / or polyurethane structural adhesives.

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