CN118255665A

CN118255665A - Preparation method of vegetable oil polyalcohol and application of vegetable oil polyalcohol in anticorrosive paint

Info

Publication number: CN118255665A
Application number: CN202211686999.0A
Authority: CN
Inventors: 郭凯; 方正
Original assignee: Institute of Corrosion Science and Technology
Current assignee: Institute of Corrosion Science and Technology
Priority date: 2022-12-27
Filing date: 2022-12-27
Publication date: 2024-06-28

Abstract

The application discloses a preparation method of vegetable oil polyol and application of the vegetable oil polyol in anticorrosive paint, 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 the 2, 3-dihydroxysuccinic diester 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 lower alkane primary alcohol and the first reaction solution into a micro-channel reaction device, and performing ring opening reaction II to obtain the vegetable oil polyol. The prepared vegetable oil polyol has novel structure by adopting the serial reaction of two specific ring-opening reagents, is moderate in polyol, uniform in distribution and low in viscosity, and can replace the traditional petrochemical polyol.

Description

Preparation method of vegetable oil polyalcohol and application of vegetable oil polyalcohol in anticorrosive paint

Technical Field

The application relates to a preparation method of vegetable oil polyol and application thereof in anticorrosive paint, 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 a polyol with an isocyanate. 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; the non-foaming products comprise paint, adhesive, synthetic leather, elastomer, elastic fiber and the like, one of two types of isocyanate products of polyurethane synthesis is relatively few, mainly MDI, TDI and the like, and the other type of monomer polyol is various in variety, different in quality and diversified in downstream application, so that the polyurethane synthesis has a further research space.

The development of vegetable oil polyol is considered as an effective way for the development of biological base materials, the vegetable oil polyol is taken as an important monomer of the biological base polyurethane material, is obtained by chemical modification of a molecular structure derived from vegetable oil serving as a raw material, is an important renewable resource, reacts with isocyanate compounds to generate polyurethane, and is a good substitute raw material of petroleum base polyol. At present, in the field of foaming products of bio-based polyurethane, a plurality of brands exist on the market, however, in the field of paint, the development of bio-based polyol derived from vegetable oil is relatively slow, especially in the aspect of anticorrosive paint, the performance of polyurethane paint developed through the bio-based polyol at present is difficult to cooperate in the aspects of hardness, toughness, corrosion resistance and the like.

Scientific researchers have made a great deal of research in this field, and the method for mainly synthesizing vegetable oil polyol mainly comprises the following steps: 1) The basic parent nucleus of triglyceride is utilized to carry out alcoholysis reaction on vegetable oil and polyol to generate polyhydroxy compound, and the scheme can obtain high-functionality polyol monomer, but the hydroxyl distribution is non-uniform and uncontrollable, thus limiting the application of the polyol monomer; 2) The proposal can obtain high-activity hydroxyl-terminated groups by utilizing unsaturated double bonds in the ozone oxidation vegetable oil to generate polyhydroxy compounds with hydroxyl-terminated groups, but has poor atom economy and lower functionality, and greatly limits the downstream application; 3) The scheme has high atom economy, has the advantages of flexibility, structural controllability and molecular diversity, and becomes a main method for developing bio-based polyol at present.

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. Therefore, it is considered that the epoxy vegetable oil undergoes a ring-opening reaction with a ring-opening agent having an ester group, and the hydroxyl value is adjusted by the ring-opening agent structure to give it a certain functionality, of course, the increase of the hydroxyl value contributes to the increase of strength and hardness, but may result in the increase of the polyol viscosity and the decrease of toughness, and in addition, the earlier study shows that the epoxy group has a residue, contributes to the increase of the corrosion resistance, but leads to the decrease of the functionality. In summary, the adjustment of functionality, the ratio of epoxy residue, the number and spatial arrangement of ester groups, hydroxyl number and spatial arrangement of hydroxyl groups in the structure have great influence on the result, and these parameters are mutually influenced, but lack of perfect structure-activity relationship, which is a main reason for limited development in the field. 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 properties of the downstream product of the polyester polyol, the product mainly comprises hardness, strength and the like, a ring-opening reagent with a polyhydroxy and polyester group structure is used as a first ring-opening reagent, so that the improvement of functionality and the easy regulation of hydroxyl value are ensured, the ring-opening reaction of most of the easily-reacted epoxy groups is finished through process control, and the ring-opening reaction of the residual epoxy groups with weaker reaction is carried out by adopting high-activity low-molecular-weight primary alcohol, so that the vegetable oil polyol product with the epoxy value residual of about 0.5-1 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 the 2, 3-dihydroxysuccinic diester 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 lower alkane primary alcohol and the first reaction solution into a micro-channel reaction device, and performing ring opening reaction II to obtain the vegetable oil polyol.

Optionally, the 2, 3-dihydroxysuccinic diester compound is selected from at least one of dimethyl 2, 3-dihydroxysuccinic acid and diisobutyl 2, 3-dihydroxysuccinic acid.

Optionally, the lower alkane primary alcohol is selected from at least one of methanol, ethanol, n-propanol and n-butanol.

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

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 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-DD220749I0.1%.

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 epoxy group in the epoxy vegetable oil to the 2, 3-dihydroxysuccinic diester compound is 1:0.7 to 0.8.

Alternatively, the molar ratio of epoxide groups in the epoxidized vegetable oil to the 2, 3-dihydroxysuccinic diester compound is independently selected from 1:0.7, 1:0.71, 1:0.72, 1:0.73, 1:0.74, 1:0.75, 1:0.76, 1:0.77, 1:0.78, 1:0.79, 1: any value in 0.80 or a range value between any two.

Optionally, the molar ratio of epoxide groups in the epoxidized vegetable oil to the lower alkane primary alcohol is 1:0.1 to 0.2.

Alternatively, the molar ratio of epoxide groups in the epoxidized vegetable oil to the lower alkane primary alcohol is independently selected from 1:0.1, 1:0.11, 1:0.12, 1:0.13, 1:0.14, 1:0.15, 1:0.16, 1:0.17, 1:0.18, 1:0.19, 1: any value in 0.20 or a range value between any two.

Optionally, in the second mixed solution, the volume ratio of the mass of the 2, 3-dihydroxysuccinic diester compound to the organic solvent is 0.47 g/mL-0.76 g/mL.

Optionally, in the third mixed solution, the mass-volume ratio of the lower alkane primary alcohol to the organic solvent is 0-0.03.

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 0.58 mL/min-2.3 mL/min.

Optionally, the pumping rate of the third mixed solution is 1 mL/min-4 mL/min.

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

The temperature is 80-110 ℃;

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 ℃, 105 ℃, 110 ℃.

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 acid, separating the liquid, drying and rotary steaming to obtain the vegetable oil polyol.

Optionally, the volume of the microreactor is 5 mL-20 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 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 multi-type ring-opening reagent serial ring-opening reaction, a higher hydroxyl value is kept, and meanwhile, the residue of a certain epoxy value is realized, so that the mechanical property of a polyurethane material is increased, the certain toughness of a polyurethane product is kept, and the vegetable oil polyol has a good anti-corrosion property. 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 anti-corrosion paint, has stronger mechanical property and higher toughness, and has obviously improved comprehensive 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 2, 3-dihydroxysuccinic acid dimethyl ester (5.13 g,28.8 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 10mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.15mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; methanol (0.23 mL,5.7 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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 230mgKOH/g, the epoxy value of 0.6 and the viscosity of 861 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 1.25:1-1.05), 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 60-80 microns, 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 2, 3-dihydroxysuccinic acid dimethyl ester (4.78 g,26.9 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 10mL 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; methanol (0.31 mL,7.7 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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 211mgKOH/g, the epoxy value of 0.7 and the viscosity of 672 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 2, 3-dihydroxysuccinic acid dimethyl ester (5.47 g,30.7 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 10mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.16mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; methanol (0.16 mL,4.0 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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 238mgKOH/g, the DD220749I epoxy value of 0.6 and the viscosity of 1276 mPa.s.

Example 4

(1) Preparation of vegetable oil polyol: epoxidized soybean oil (10 mL, epoxy value 6.2%, epoxy 38.4 mmol) and fluoboric acid (20 mg, 50%) are mixed to obtain a first mixed solution, dimethyl 2, 3-dihydroxysuccinate (4.78 g,26.9 mmol) and ethyl acetate (10 mL) are mixed to obtain a second mixed solution, the temperature of the reactor is regulated to 100 ℃, and the first mixed solution and the second mixed solution are pumped into a micro-reactor with the volume of 10mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.14mL/min respectively for ring-opening reaction to obtain a first reaction solution; methanol (0.16 mL,4.0 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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 186mgKOH/g, the epoxy value of 1.1 and the viscosity of 496 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 2, 3-dihydroxysuccinic acid dimethyl ester (5.47 g,30.7 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 10mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.16mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing methanol (0.31 mL,7.7 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 15mL of a micro-channel reaction device at a speed of 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 the organic phase to obtain soybean oil polyol with a hydroxyl value of 256mgKOH/g and DD220749I

Epoxy value 0.2, viscosity 2164 mPas.

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 2, 3-dihydroxysuccinic acid dimethyl ester (5.13 g,28.8 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 10mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.15mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; methanol (0.23 mL,5.7 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 80 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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 202mgKOH/g, the epoxy value of 0.9 and the viscosity of 743 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 2, 3-dihydroxysuccinic acid dimethyl ester (5.13 g,28.8 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 10mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.15mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing methanol (0.23 mL,5.7 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 15mL of a micro-channel reaction device at a speed of 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 the organic phase to obtain soybean oil polyol with a hydroxyl value of 218mgKOH/g and DD220749I

Epoxy value 0.3, viscosity 1763 mPas.

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 2, 3-dihydroxysuccinic acid dimethyl ester (5.13 g,28.8 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 10mL of a micro-channel reaction device at the speed of 2mL/min and the speed of 2.3mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; methanol (0.23 mL,5.7 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, 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 4mL/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 156mgKOH/g, the epoxy value of 1.3 and the viscosity of 476 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 fluoboric acid (20 mg, 50%) to obtain a first mixed solution, mixing 2, 3-dihydroxysuccinic acid dimethyl ester (5.13 g,28.8 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 10mL of a micro-channel reaction device at the speed of 0.5mL/min and the speed of 0.58mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing methanol (0.23 mL,5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 100deg.C, pumping the third mixed solution into a micro-reactor with 15mL of micro-channel reaction device at 1mL/min with the first reaction liquid, subjecting the obtained reaction liquid to ring-opening reaction, washing with sodium bicarbonate solution (30 mL, 10%), water (30 mL×2), drying the organic phase, concentrating to obtain soybean oil polyol, hydroxyl value of 233mgKOH/g, DD220749I

The epoxy value was 0.5 and the viscosity was 965 mPas.

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 2, 3-dihydroxysuccinic acid diisobutyl ester (7.55 g,28.8 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 10mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.16mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; methanol (0.23 mL,5.7 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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 204mgKOH/g, the epoxy value of 0.6 and the viscosity of 1033 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 2, 3-dihydroxysuccinic acid dimethyl ester (5.13 g,28.8 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 10mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.15mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; ethanol (0.34 mL,5.7 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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, the organic phase is dried and concentrated to obtain soybean oil polyol with the hydroxyl value of 221mgKOH/g and DD220749I

Epoxy value 0.7 and viscosity 902 mPas.

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 2, 3-dihydroxysuccinic acid dimethyl ester (5.13 g,28.8 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 10mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.15mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; propanol (0.43 mL,5.7 mmol) and ethyl acetate (20 mL) were mixed to obtain a third mixed solution, the temperature of the reactor was adjusted to 100 ℃, the third mixed solution was pumped into a micro-reactor with a volume of 15mL of a micro-channel reaction device with a first reaction liquid at a rate of 2mL/min to carry out ring-opening reaction, the obtained reaction liquid was washed with sodium bicarbonate solution (30 mL, 10%) and water (30 mL. Times.2) in sequence, and the organic phase was dried and concentrated to obtain soybean oil polyol with a hydroxyl value of 218mgKOH/g, an epoxy value of 0.6 and a viscosity of 940 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 2, 3-dihydroxysuccinic acid dimethyl ester (5.13 g,28.8 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 10mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.15mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing n-butanol (0.50 mL,5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 100deg.C, pumping the third mixed solution into a micro-reactor with 15mL of micro-channel reaction device at 2mL/min with the first reaction liquid, subjecting the obtained reaction liquid to ring-opening reaction, washing with sodium bicarbonate solution (30 mL, 10%), water (30 mL×2), drying the organic phase, concentrating to obtain soybean oil polyol with hydroxyl value of 219mgKOH/g, DD220749I

Epoxy value 0.6, viscosity 932 mPas.

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 2, 3-dihydroxysuccinic acid dimethyl ester (5.13 g,28.8 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 10mL of a micro-channel reaction device at the speed of 1.3mL/min and the speed of 1.15mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; methanol (0.23 mL,5.7 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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 190mgKOH/g, the epoxy value of 0.6 and the viscosity of 789 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 2, 3-dihydroxysuccinic acid dimethyl ester (5.13 g,28.8 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 10mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.15mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing methanol (0.23 mL,5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 100deg.C, pumping the third mixed solution into a micro-reactor with 15mL of micro-channel reaction device volume with the first reaction liquid at 2mL/min rate for ring-opening reaction, washing the obtained reaction liquid with sodium bicarbonate solution (30 mL, 10%), water (30 mL×2), drying the organic phase, concentrating to obtain soybean oil polyol with hydroxyl value of 231mgKOH/g, DD220749I

Epoxy value 0.5, viscosity 812 mPas.

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, dimethyl 2, 3-dihydroxysuccinate (5.13 g,28.8 mmol) and ethyl acetate (10 mL) are mixed to obtain a second mixed solution, the temperature of the reactor is regulated to 100 ℃, and the first mixed solution and the second mixed solution are pumped into a micro-reactor with the volume of 10mL of a micro-channel reaction device at the speed of 1.35mL/min and the speed of 1.15mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; methanol (0.23 mL,5.7 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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 186mgKOH/g, the epoxy value of 0.5 and the viscosity of 1011 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 2, 3-dihydroxysuccinic acid dimethyl ester (5.13 g,28.8 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 10mL of a micro-channel reaction device at the speed of 1.23mL/min and the speed of 1.15mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; mixing methanol (0.23 mL,5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, regulating the temperature of the reactor to 100deg.C, pumping the third mixed solution into a micro-reactor with 15mL of micro-channel reaction device volume with the first reaction liquid at 2mL/min rate for ring-opening reaction, washing the obtained reaction liquid with sodium bicarbonate solution (30 mL, 10%), water (30 mL×2), drying the organic phase, concentrating to obtain soybean oil polyol with hydroxyl value of 210mgKOH/g, DD220749I

Epoxy value 0.5, viscosity 892 mPas.

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 2, 3-dihydroxysuccinic acid dimethyl ester (5.13 g,28.8 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 10mL of a micro-channel reaction device at the speed of 1.44mL/min and the speed of 1.15mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; methanol (0.23 mL,5.7 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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 172mgKOH/g, the epoxy value of 0.6 and the viscosity of 765 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%), dimethyl 2, 3-dihydroxysuccinate (5.13 g,28.8 mmol) and ethyl acetate (30 mL) were reacted at 100℃for 6 hours, methanol (0.23 mL,5.7 mmol) was added for further reaction for 4 hours, cooled to room temperature, the obtained 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 obtain soybean oil polyol having a hydroxyl value of 210mgKOH/g, an epoxy value of 0.5 and a viscosity of 1650 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 2, 3-dihydroxysuccinic acid dimethyl ester (4.10 g,23.0 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 10mL 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; methanol (0.23 mL,5.7 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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 189mgKOH/g, the epoxy value of 1.6 and the viscosity of 450 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 2, 3-dihydroxysuccinic acid dimethyl ester (6.15 g,34.6 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 10mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.17mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; methanol (0.16 mL,4.0 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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 276mgKOH/g, the epoxy value of 0.1 and the viscosity of 2156 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 2, 3-dihydroxysuccinic acid dimethyl ester (5.13 g,28.8 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 10mL of a micro-channel reaction device at the speed of 1mL/min and the speed of 1.15mL/min respectively to carry out ring-opening reaction to obtain a first reaction solution; methanol (0.47 mL,11.6 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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 249mgKOH/g, the epoxy value of 0.1 and the viscosity of 2011 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), fluoroboric acid (20 mg, 50%), methanol (1.4 mL,34.5 mmol) and ethyl acetate (30 mL) were reacted at 100℃for 10 hours, cooled to room temperature, the obtained reaction solution was washed with sodium hydrogencarbonate solution (30 mL, 10%), water (30 mL. Times.2) in this order, and the organic phase was dried and concentrated to obtain soybean oil polyol having a hydroxyl value of 153mgKOH/g, an epoxy value of 1.2 and a viscosity of 2683 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 2, 3-butanediol (2.10 g,23.0 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 10mL 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; isopropyl alcohol (0.43 mL,5.7 mmol) and ethyl acetate (20 mL) are mixed to obtain a third mixed solution, the temperature of the reactor is regulated to 100 ℃, the third mixed solution and the first reaction solution are pumped into a micro-reactor with the volume of 15mL 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 170mgKOH/g, the epoxy value of 1.3 and the viscosity of 1020 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 2, 3-dihydroxysuccinic diester compound is at least one selected from the group consisting of dimethyl 2, 3-dihydroxysuccinate and diisobutyl 2, 3-dihydroxysuccinate.

3. The method according to claim 1, wherein the lower alkane primary alcohol is at least one selected from the group consisting of methanol, ethanol, n-propanol and n-butanol.

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 epoxy group in the epoxy vegetable oil to the 2, 3-dihydroxysuccinic diester compound is 1:0.7 to 0.8;

preferably, the molar ratio of epoxide groups in the epoxidized vegetable oil to the primary lower alkane alcohols is 1:0.1 to 0.2.

8. The method according to claim 6, wherein the volume ratio of the mass of the 2, 3-dihydroxysuccinic diester compound to the organic solvent in the second mixed solution is 0.47g/mL to 0.76g/mL;

Preferably, in the third mixed solution, the volume ratio of the lower alkane primary alcohol to the organic solvent is 0-0.03;

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 0.58 mL/min-2.3 mL/min;

Preferably, the pumping rate of the third mixed solution is 1 mL/min-4 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 80-110 ℃;

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-20 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.