CN118255666A

CN118255666A - Preparation method and application of vegetable oil polyol

Info

Publication number: CN118255666A
Application number: CN202211688475.5A
Authority: CN
Inventors: 郭凯; 方正
Original assignee: Institute of Corrosion Science and Technology
Current assignee: Institute of Corrosion Science and Technology
Filing date: 2022-12-27
Publication date: 2024-06-28

Abstract

The application discloses a preparation method and application of vegetable oil polyol, and belongs to the technical field of chemical materials and production thereof. A method for preparing a vegetable oil polyol, comprising the steps of: s1, mixing materials containing epoxy vegetable oil and an acid catalyst to obtain a first mixed solution; s2, respectively pumping a second mixed solution containing a cyclic hydrocarbon diol compound and the first mixed solution into a micro-channel reaction device, and performing ring opening reaction I to obtain a first reaction solution; s3, flowing the third mixed solution containing the hydroxy carboxylic ester and the first reaction solution into a microchannel reaction device, and performing ring opening reaction II to obtain the vegetable oil polyol. According to the application, two specific ring-opening reagents are adopted for series reaction, a polyester group is introduced, and cyclic hydrocarbon is introduced, so that the mechanical property of the polyurethane material is improved, meanwhile, the toughness of a polyurethane product is maintained, the prepared vegetable oil polyol has a novel structure, and the polyol is moderate and uniformly distributed and has lower viscosity.

Description

Preparation method and application of vegetable oil polyol

Technical Field

The application relates to a preparation method and application of vegetable oil polyol, belonging to the technical field of chemical materials and production thereof.

Background

Polyurethane is a polymer having urethane segment repeating structural units made from the reaction of an isocyanate with a polyol. Polyurethane products are classified into two main categories, foamed products and non-foamed products. The foaming product is soft, hard and semi-hard polyurethane foam plastic; non-foamed articles include coatings, adhesives, synthetic leather, elastomers, elastic fibers, and the like.

The development of vegetable oil polyol is considered as an effective way for the development of biological base materials, is an important monomer of biological base polyurethane materials, is derived from the molecular structure of vegetable oil serving as a raw material through chemical modification, is an important renewable resource, reacts with isocyanate compounds to generate polyurethane, has potential application in various fields, and is a good substitute raw material of petroleum base polyol. In many research reports, the oxidation of vegetable oil to epoxy vegetable oil and the subsequent ring opening reaction to produce polyhydroxy compound is one main path, and the scheme has high atom economy, high flexibility, controllable structure and molecular diversity and is one main method of developing biological polyol. However, the selection of ring-opening reagents, the parameter index control of the process, the arrangement and proportion of various ring-opening reagents and the like affect the quality of the polyol and the downstream application, so that the development of a bio-based polyol product which has market potential and does not need to be compatible with petrochemical polyol is a challenging problem.

The long-chain groups in the vegetable oil structure replace the repeating units of the traditional petrochemical polyol polyether or polyester, the basic parent nucleus of the triglyceride in the structure has a star-shaped space conformation, and more functional attributes and application space are provided for the downstream polyurethane, however, the vegetable oil polyol often has performance defects, mainly because the reaction process is uncontrollable, and a plurality of epoxy groups and ester groups often participate in a plurality of side reaction processes in the functional group conversion process, so that the designed molecular structure is difficult to construct by the traditional chemical method, the quality of the polyol is greatly limited, and the vegetable oil polyol often needs to be mixed with the traditional petrochemical polyol to have a certain application effect. Through reaction mechanism analysis, the main reason is that the miscibility of the oil ester and the reactant is often poor, but the reactivity is lower, so that long-time high-strength reaction is required, but the influence of a plurality of functional groups in the structure causes difficulty in considering the reaction selectivity and the conversion rate, and the poor process control property causes that the obtained product has poor molecular uniformity, high viscosity and large difference between macroscopic indexes and microscopic indexes of single molecules. Therefore, even though vegetable oils tend to be less expensive than monomers of petrochemical repeating units, it is difficult to obtain a vegetable oil polyol product that has both cost and quality advantages. It is necessary to control the quality of the product by controlling the chemical process, and in the reaction system, strengthening and continuous precise control of the chemical reaction process by adopting the micro-reaction technology are effective solutions.

Generally, polyurethane products formed from polyester polyols are mechanically stronger than polyurethane products formed from polyether polyols, possibly due to the potential effect of the hydrogen bonding of the ester groups in the polyol with the ammonia in the isocyanate. In addition, in order to enhance the rigidity of the polyester/polyether polyol, a rigid group can be introduced into the ring-opening reagent, and early experiments show that the introduction of phenyl and pyridine groups can cause the increase of the hardness of the product, but the reduction of the toughness, and the introduction of cycloalkanes can cause the improvement of the strength and the maintenance of the toughness. Then adding a certain proportion of ester groups and rigid groups in the molecular structure, adjusting the distribution of the suspension chains, controlling the ring-opening efficiency, keeping the viscosity controllable and other coordination aspects are the main problems to be solved. Under the condition that the components of the vegetable oil are not single and the structure-activity relationship is not clear at present, the quality control of the polyol product can be carried out only through the reaction process control and the macro index regulation and control, so that the control of the product uniformity is carried out through the process control, and the method has important effects on the development and downstream application of new products of the polyol.

Disclosure of Invention

According to a first aspect of the present application, there is provided a process for the preparation of a vegetable oil polyol. In order to improve the mechanical property of a downstream product of the polyester polyol, and simultaneously, the product has the quality of rigidity and toughness, a ring-opening reagent with certain functionality and rigidity but non-aromatic structure is adopted as a first ring-opening reagent, the ring-opening reaction of partial easily-reacted epoxy groups is completed through process control, and then the ring-opening reaction of residual epoxy groups with weaker reactivity is carried out by adopting high-activity primary alcohol containing long-chain ester groups, so that a vegetable oil polyol product with the epoxy value of about 10% is obtained. In order to avoid the cross-linking side reaction generated by nonselective ring opening of secondary hydroxyl and other epoxy groups generated in the ring opening reaction, the inventor adopts a micro-reaction technology, selects a micro-channel reaction device as reaction equipment, and further controls the ring opening groups.

A method for preparing a vegetable oil polyol, comprising the steps of:

s1, mixing materials containing epoxy vegetable oil and an acid catalyst to obtain a first mixed solution;

S2, respectively pumping a second mixed solution containing a cyclic hydrocarbon diol compound and the first mixed solution into a micro-channel reaction device, and performing ring opening reaction I to obtain a first reaction solution;

s3, flowing the third mixed solution containing the hydroxy carboxylic ester and the first reaction solution into a microchannel reaction device, and performing ring opening reaction II to obtain the vegetable oil polyol.

Optionally, the hydroxy carboxylic acid ester is selected from at least one of methyl 4-hydroxybutyrate, ethyl 4-hydroxybutyrate, methyl 6-hydroxycaproate, ethyl 6-hydroxycaproate, methyl 8-hydroxycaprate, ethyl 8-hydroxycaprate, methyl 10-hydroxycaprate and ethyl 10-hydroxycaprate.

Optionally, the cyclic hydrocarbon diol compound is selected from at least one of cyclopentanediol and cyclohexanediol.

Optionally, the epoxidized vegetable oil is at least one selected from epoxidized olive oil, epoxidized peanut oil, epoxidized rapeseed oil, epoxidized cottonseed oil, epoxidized soybean oil, epoxidized coconut oil, epoxidized palm oil, epoxidized sesame oil, epoxidized corn oil, and epoxidized sunflower oil.

Optionally, the acidic catalyst is selected from at least one of fluoboric acid, concentrated sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid.

Optionally, the epoxy degree of the epoxy vegetable oil is 4.5% -6.2%.

Optionally, the second mixed solution and the third mixed solution further comprise an organic solvent.

Optionally, the organic solvent is at least one selected from ethyl acetate, dichloromethane, dichloroethane, chloroform, n-hexane, tetrahydrofuran, 1, 4-dioxane, carbon tetrachloride, toluene and xylene.

Optionally, the mass percentage of the acid catalyst to the epoxy vegetable oil is 0.02-0.1%.

Alternatively, the mass percent of the acidic catalyst to the epoxidized vegetable oil is independently selected from any value or range of values between any two of 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.10%.

Optionally, the molar ratio of the cyclic hydrocarbon diol compound to the epoxy groups in the epoxidized vegetable oil is 0.4 to 0.6.

Alternatively, the molar ratio of the cyclic hydrocarbon diol compound to the epoxide groups in the epoxidized vegetable oil is independently selected from any value or range of values between any two of 0.40、0.41、0.42、0.43、0.44、0.45、0.46、0.47、0.48、0.49、0.50、0.51、0.52、0.53、0.54、0.55、0.56、0.57、0.58、0.59、0.60.

Optionally, the molar ratio of the hydroxy carboxylic ester to the epoxy groups in the epoxidized vegetable oil is from 0.3 to 0.5.

Alternatively, the molar ratio of the hydroxy carboxylic ester to the epoxide groups in the epoxidized vegetable oil is independently selected from any value or range of values between any two of 0.30、0.31、0.32、0.33、0.34、0.35、0.36、0.37、0.38、0.39、0.40、0.41、0.42、0.43、0.44、0.45、0.46、0.47、0.48、0.49、0.50.

Optionally, in the second mixed solution, the mass volume ratio of the cyclic hydrocarbon diol compound to the organic solvent is 0.17 g/mL-0.27 g/mL.

Optionally, in the third mixed solution, the mass-volume ratio of the hydroxy carboxylic ester to the organic solvent is 0.1 g/m-0.19 g/mL.

Optionally, the pumping rate of the first mixed solution is 0.5 mL/min-2 mL/min.

Optionally, the pumping rate of the second mixed solution is 0.55 mL/min-2.2 mL/min.

Optionally, the pumping rate of the third mixed solution is 1.05 mL/min-4.2 mL/min.

Alternatively, the conditions for ring opening reaction I and ring opening reaction II are as follows:

The temperature is 80-100 ℃;

the time is 3 min-15 min.

Alternatively, the temperature is independently selected from any value or range of values between any two of 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃.

Alternatively, the time is independently selected from any value or range of values between any two of 3min, 5min, 7min, 10min, 11min, 12min, 13min, 14min, 15 min.

Optionally, the microchannel reaction device comprises a first feed pump, a second feed pump, a third feed pump, a microreaction conduit, a micromixer, a microreactor, and a receiver; the first feed pump and the second feed pump are connected to the micromixer; the first reaction liquid and the third feed pump are connected to the micromixer; wherein the micromixer, the microreactor and the receiver are all connected in series through pipelines in sequence.

Wherein the micro mixer is a conventional Y-type mixer or T-type mixer; the microreactor is Vapotech in type and adopts a microstructure heat exchanger coaxial heat exchanger.

Wherein, separating the reaction effluent of the microreactor, neutralizing the organic phase, separating the liquid, drying, and rotary steaming to obtain the vegetable oil polyol.

Optionally, the volume of the microreactor is 5 mL-15 mL.

According to a second aspect of the present application there is provided the use of a vegetable oil polyol.

The vegetable oil polyol obtained by the preparation method is applied to the preparation of polyurethane paint.

The preparation of the vegetable oil-based polyurethane coating comprises the following steps:

Mixing vegetable oil polyol and isocyanate MDI (according to the molar ratio of NCO to OH functional groups of 1.20:1-1.05), adding a catalyst, and reacting for 1-3 hours to obtain a prepolymer mixed solution. Adding a hydrophilic chain extender into the prepolymer mixed solution, reacting for 2-5 hours to obtain a polymer mixed solution, adding a neutralizing agent to neutralize the polymer mixed solution to be neutral, and adding a diluent to perform high-speed shearing and emulsification to form polyurethane emulsion. The substrate is a steel plate, and the dry film thickness is 70-90 microns.

The application has the beneficial effects that:

According to the preparation method of the vegetable oil polyol, provided by the application, the polyester group is introduced into the vegetable oil polyol prepared by adopting a novel ring-opening reagent reaction, and the cyclic hydrocarbon is introduced, so that the mechanical property of the polyurethane material is improved, and meanwhile, the toughness of a polyurethane product is maintained. The vegetable oil polyol prepared by adopting the serial reaction of the specific two ring-opening reagents has novel structure, is moderate and uniformly distributed, has lower viscosity, can replace the traditional petrochemical polyol, can be used for preparing polyurethane paint, and has the advantages of obviously improved performance and certain anti-corrosion performance.

Drawings

FIG. 1 is a schematic diagram of a microchannel reactor.

Detailed Description

The present application is described in detail below with reference to examples, but the present application is not limited to these examples.

The starting materials and catalysts in the examples of the present application were purchased commercially, unless otherwise specified.

The method for relevant determination of the prepared vegetable oil polyol and polyurethane material is as follows:

(1) Hydroxyl number according to GB/T12008.3 2009;

(2) Viscosity was measured according to GB/T12008.7 2010;

(3) Measuring the surface drying time of the paint according to GB/T1728-2020 (method B);

(4) The real drying time of the coating is determined according to GB/T1728-1979 (A method);

(5) VOC content was determined according to GB/T23985-2009 (8.3);

(6) Measuring the surface hardness of the coating according to GB/T6739-2006;

(7) Impact resistance of the coating was determined according to GB/T1732-2020;

(8) The flexibility of the coating was determined according to GB/T1731-2020 (4);

(9) Measuring the paint adhesion according to GB/T5210-2006;

(10) And (3) measuring a neutral salt spray resistance corrosion prevention experiment according to GB/T1771-2007.

Example 1

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.1mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.89 g,15.4 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.1mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, wherein the hydroxyl value is 187mgKOH/g, the epoxy value is 0.6, and the viscosity is 986 mPa.s.

(2) Preparing a vegetable oil-based polyurethane coating: mixing a certain amount of vegetable oil polyol with isocyanate MDI (according to the molar ratio of NCO to OH functional groups of 1.20:1-1.05), adding a catalyst (polyol mass of 3%o), and reacting for 2 hours to obtain a prepolymer mixed solution. Adding a certain amount of hydrophilic chain extender and other assistants into the prepolymer mixed solution, reacting for 3 hours to obtain a polymer mixed solution, adding a proper amount of neutralizer to neutralize the polymer mixed solution to be neutral, and adding a diluent to perform high-speed shearing and emulsification to form polyurethane emulsion. And (3) spraying the steel plate on the substrate once, wherein the dry film thickness is 70-90 micrometers, and testing after placing for 168 hours in a laboratory environment.

Example 2

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (1.78 g,15.3 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the rates of 1mL/min and 1.07mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (3.61 g,19.2 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.16mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, wherein the hydroxyl value is 172mgKOH/g, the epoxy value is 0.5, and the viscosity is 787 mPa.s.

(2) Preparing a vegetable oil-based polyurethane coating: polyurethane coatings were prepared according to the general procedure of example 1 (2).

Example 3

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.68 g,23.1 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.14mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.17 g,11.5 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.07mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, and obtaining the hydroxyl value of 198mgKOH/g, the epoxy value of 0.6 and the viscosity of 1227 mPa.s.

Example 4

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (1.78 g,15.3 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the rates of 1mL/min and 1.07mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.17 g,11.5 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.07mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol with the hydroxyl value of 152mgKOH/g, the epoxy value of 1.5 and the viscosity of 456 mPa.s.

Example 5

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.68 g,23.1 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.14mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (3.61 g,19.2 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.16mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, and having a hydroxyl value of 236mgKOH/g, an epoxy value of 0.1 and a viscosity of 3370 mPa.s.

Example 6

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 80 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.1mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.89 g,15.4 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 80 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.1mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, wherein the hydroxyl value is 170mgKOH/g, the epoxy value is 0.9, and the viscosity is 796 mPa.s.

Example 7

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.1mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.89 g,15.4 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 100 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.1mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, and obtaining the hydroxyl value of 177mgKOH/g, the epoxy value of 0.3 and the viscosity of 1352 mPa.s.

Example 8

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 2mL/min and the speed of 2.2mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.89 g,5.4 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 4.2mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, wherein the hydroxyl value is 160mgKOH/g, the epoxy value is 1.0, and the viscosity is 664 mPa.s.

Example 9

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoroboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL of a micro-channel reaction device at the speed of 0.5mL/min and the speed of 0.55mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.89 g,15.4 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1.05mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, wherein the hydroxyl value is 190mgKOH/g, the epoxy value is 0.5, and the viscosity is 1011 mPa.s.

Example 10

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclopentanediol (1.96 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.1mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.89 g,15.4 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.1mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, wherein the hydroxyl value is 192mgKOH/g, the epoxy value is 0.6, and the viscosity is 961 mPa.s.

Example 11

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.1mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; ethyl 4-hydroxybutyrate (2.04 g,15.4 mmol) and ethyl acetate (20 mL) were mixed to obtain a third mixed solution, the temperature of the reactor was adjusted to 90 ℃, the third mixed solution was pumped into a micro-reactor having a volume of 20mL of a micro-channel reaction apparatus with a first reaction liquid at a rate of 2.12mL/min to carry out a ring-opening reaction, the obtained reaction solution was washed with a sodium bicarbonate solution (30 mL, 10%) and water (30 mL. Times.2) in this order, and the organic phase was dried and concentrated to obtain a soybean oil polyol having a hydroxyl value of 187mgKOH/g, an epoxy value of 0.6 and a viscosity of 986 mPa.s.

Example 12

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.1mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; methyl 6-hydroxycaproate (2.2 g,15.4 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 90 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.11mL/min for ring-opening reaction, the obtained reaction solution is washed by sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, and the organic phase is dried and concentrated to obtain soybean oil polyol with the hydroxyl value of 192mgKOH/g, the epoxy value of 0.6 and the viscosity of 1057 mPa.s.

Example 13

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.2 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.1mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; 10-hydroxy ethyl decanoate (3.12 g,15.4 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 90 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.17mL/min for ring-opening reaction, the obtained reaction solution is washed by sodium bicarbonate solution (30 mL,10 percent) and water (30 mL multiplied by 2) in sequence, and the organic phase is dried and concentrated to obtain soybean oil polyol with the hydroxyl value of 183mgKOH/g, the epoxy value of 0.6 and the viscosity of 1009 mPa.s.

Example 14

(1) Preparation of vegetable oil polyol: mixing epoxy cottonseed oil (13 mL, epoxy value 5.1%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1.3mL/min and 1.1mL/min respectively for ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.89 g,15.4 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.1mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, wherein the hydroxyl value is 145mgKOH/g, the epoxy value is 0.6, and the viscosity is 892 mPa.s.

Example 15

(1) Preparation of vegetable oil polyol: mixing epoxy sunflower seed oil (10 mL, epoxy value 6.0%, epoxy group 38.2 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.1mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.89 g,15.4 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.1mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, wherein the hydroxyl value is 180mgKOH/g, the epoxy value is 0.5, and the viscosity is 911 mPa.s.

Example 16

(1) Preparation of vegetable oil polyol: epoxy rapeseed oil (13.5 mL, epoxy value 4.9%, epoxy 38.4 mmol) and fluoboric acid (20 mg, 50%) are mixed to obtain a first mixed solution, cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (10 mL) are mixed to obtain a second mixed solution, the temperature of the reactor is regulated to 90 ℃, and the first mixed solution and the second mixed solution are pumped into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1.35mL/min and the speed of 1.1mL/min respectively for ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.89 g,15.4 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.1mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, wherein the hydroxyl value is 141mgKOH/g, the epoxy value is 0.6, and the viscosity is 1051 mPa.s.

Example 17

(1) Preparation of vegetable oil polyol: mixing epoxy corn oil (12.3 mL, epoxy value 5.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1.23mL/min and the speed of 1.1mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.89 g,15.4 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.1mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, wherein the hydroxyl value is 157mgKOH/g, the epoxy value is 0.5, and the viscosity is 1123 mPa.s.

Example 18

(1) Preparation of vegetable oil polyol: mixing epoxy peanut oil (14.4 mL, epoxy value 4.5%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.1mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.89 g,15.4 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.1mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, wherein the hydroxyl value is 130mgKOH/g, the epoxy value is 0.6, and the viscosity is 1438 mPa.s.

Comparative example 1

(1) Preparation of vegetable oil polyol: epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy 38.4 mmol), fluoroboric acid (20 mg, 50%), cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (30 mL) were reacted at 90℃for 6h, ethyl 8-hydroxyoctanoate (2.89 g,15.4 mmol) was added and the reaction was continued for 4h, cooled to room temperature, the reaction solution was washed successively with sodium hydrogencarbonate solution (30 mL, 10%), water (30 mL. Times.2), and the organic phase was dried and concentrated to give soybean oil polyol having a hydroxyl value of 156mgKOH/g, an epoxy value of 0.2 and a viscosity of 4507 mPa.s.

Comparative example 2

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (0.89 g,7.7 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.02mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (5.06 g,26.9 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.23mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, and obtaining the hydroxyl value of 117mgKOH/g, the epoxy value of 0.5 and the viscosity of 424 mPa.s.

Comparative example 3

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (3.12 g,26.9 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.18mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (1.46 g,7.8 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 90 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.05mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, wherein the hydroxyl value is 241mgKOH/g, the epoxy value is 0.7, and the viscosity is 1360 mPa.s.

Comparative example 4

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing cyclohexanediol (2.23 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 110 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.1mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing 8-hydroxy ethyl octoate (2.89 g,15.4 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 110 ℃, pumping the third mixed solution and the first reaction solution into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2.1mL/min for ring-opening reaction, washing the obtained reaction solution with sodium bicarbonate solution (30 mL, 10%) and water (30 mL multiplied by 2) in sequence, drying and concentrating an organic phase to obtain soybean oil polyol, wherein the hydroxyl value is 154mgKOH/g, the epoxy value is 0.3, and the viscosity is 2671 mPa.s.

Comparative example 5

(1) Preparation of vegetable oil polyol: epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoroboric acid (20 mg, 50%) were mixed to obtain a first mixed solution, cyclohexanediol (4 g,34.6 mmol) and ethyl acetate (10 mL) were mixed to obtain a second mixed solution, the temperature of the reactor was adjusted to 90 ℃, the first mixed solution and the second mixed solution were pumped into a micro-reactor having a micro-channel reaction device volume of 15mL at a rate of 1mL/min and a rate of 1.3mL/min, respectively, to carry out a ring-opening reaction, the obtained reaction solution was washed with sodium bicarbonate solution (30 mL, 10%) and water (30 mL. Times.2), and the organic phase was dried and concentrated to obtain soybean oil polyol having a hydroxyl value of 162mgKOH/g, an epoxy value of 1.6, and a viscosity of 742 mPa.s.

Comparative example 6

(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy group 38.4 mmol) and fluoroboric acid (20 mg, 50%) to obtain a first mixed solution, mixing 1, 2-dimethyl-1, 2-cyclohexanediol (2.57 g,19.2 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, regulating the temperature of the reactor to 90 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 15mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.12mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; methanol (0.49 g,15.4 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 90 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 20mL of a micro-channel reaction device at the speed of 2mL/min for ring-opening reaction, the obtained reaction solution is washed by sodium bicarbonate solution (30 mL,10 percent) and water (30 mL multiplied by 2) in sequence, and the organic phase is dried and concentrated to obtain soybean oil polyol with the hydroxyl value of 174mgKOH/g, the epoxy value of 1 and the viscosity of 840 mPa.s.

The performance index of the polyurethane coatings prepared in examples 1 to 18 and comparative examples 1 to 4 is shown in the following table.

Performance index of vegetable oil-based polyurethane coating prepared in Table examples 1 to 18

While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims

1. A method for preparing a vegetable oil polyol, comprising the steps of:

2. The method according to claim 1, wherein the hydroxycarboxylic acid ester is at least one selected from the group consisting of methyl 4-hydroxybutyrate, ethyl 4-hydroxybutyrate, methyl 6-hydroxycaproate, ethyl 6-hydroxycaproate, methyl 8-hydroxycaprate, ethyl 8-hydroxycaprate, methyl 10-hydroxydecanoate, and ethyl 10-hydroxydecanoate.

3. The method according to claim 1, wherein the cyclic hydrocarbon diol compound is at least one selected from the group consisting of cyclopentanediol and cyclohexanediol.

4. The preparation method according to claim 1, wherein the epoxidized vegetable oil is at least one selected from the group consisting of epoxidized olive oil, epoxidized peanut oil, epoxidized rapeseed oil, epoxidized cottonseed oil, epoxidized soybean oil, epoxidized coconut oil, epoxidized palm oil, epoxidized sesame oil, epoxidized corn oil, and epoxidized sunflower oil;

preferably, the epoxy degree of the epoxy vegetable oil is 4.5% -6.2%.

5. The method according to claim 1, wherein the acidic catalyst is at least one selected from the group consisting of fluoroboric acid, concentrated sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid.

6. The preparation method according to claim 1, wherein the second mixed solution and the third mixed solution further comprise an organic solvent;

Preferably, the organic solvent is at least one selected from ethyl acetate, dichloromethane, dichloroethane, chloroform, n-hexane, tetrahydrofuran, 1, 4-dioxane, carbon tetrachloride, toluene, and xylene.

7. The preparation method of claim 1, wherein the mass percentage of the acidic catalyst to the epoxidized vegetable oil is 0.02% -0.1%;

preferably, the molar ratio of the cyclic hydrocarbon diol compound to the epoxy group in the epoxidized vegetable oil is 0.4 to 0.6;

Preferably, the molar ratio of the hydroxy carboxylic acid ester to the epoxy group in the epoxidized vegetable oil is 0.3 to 0.5.

8. The method according to claim 6, wherein the mass/volume ratio of the cyclic hydrocarbon diol compound to the organic solvent in the second mixed solution is 0.17g/mL to 0.27g/mL;

Preferably, in the third mixed solution, the mass-volume ratio of the hydroxy carboxylic ester to the organic solvent is 0.1 g/m-0.19 g/mL;

Preferably, the pumping rate of the first mixed solution is 0.5 mL/min-2 mL/min;

preferably, the pumping rate of the second mixed solution is 0.55-2.2 mL/min;

Preferably, the pumping rate of the third mixed solution is 1.05 mL/min-4.2 mL/min.

9. The preparation method according to claim 1, wherein the conditions of the ring-opening reaction I and the ring-opening reaction II are as follows:

The temperature is 80-100 ℃;

the time is 3 min-15 min;

Preferably, the microchannel reaction device comprises a first feed pump, a second feed pump, a third feed pump, a microreaction conduit, a micromixer, a microreactor, and a receiver; the first feed pump and the second feed pump are connected to the micromixer; the first reaction liquid and the third feed pump are connected to the micromixer; wherein the micro mixer, the micro reactor and the receiver are all connected in series through pipelines in sequence;

Preferably, the volume of the microreactor is 5 mL-15 mL.

10. Use of the vegetable oil polyol obtained by the preparation method according to any one of claims 1 to 9 for preparing polyurethane paint.