CN115784881A - Preparation method of vegetable oil polyalcohol and application of vegetable oil polyalcohol in polyurethane anticorrosive paint - Google Patents
Preparation method of vegetable oil polyalcohol and application of vegetable oil polyalcohol in polyurethane anticorrosive paint Download PDFInfo
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Abstract
The invention discloses a preparation method of vegetable oil polyalcohol and application thereof in polyurethane anticorrosive paint, wherein epoxy vegetable oil and an acid catalyst are mixed into a first mixed solution; dissolving 2, 3-dihydroxy succinic diester compounds in an organic solvent to obtain a second mixed solution; respectively pumping the first mixed solution and the second mixed solution into a microreactor to perform a first ring-opening reaction to obtain a first reaction solution; allowing a third mixed solution obtained by dissolving long-chain hydroxy fatty acid ester in an organic solvent and the first reaction solution to flow into the microreactor and continuously performing a second ring-opening reaction to obtain a second reaction solution; and simply post-treating the second reaction liquid to obtain the vegetable oil polyalcohol. The vegetable oil polyol prepared by adopting the novel ring-opening reagent and the continuous micro-reaction process has the advantages of novel structure, moderate molecular weight, uniform distribution and moderate viscosity, can replace the traditional petrochemical polyol, can be used for preparing the bio-based polyurethane coating through the vegetable oil polyol, and has stronger anti-corrosion performance.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to vegetable oil polyol, a preparation method thereof and application thereof in anticorrosive paint.
Background
Polyurethanes are polymers having repeating structural units of urethane segments made by reacting a polyol with an isocyanate. Polyurethane products are divided into two broad categories, foamed products and non-foamed products. The foaming product is soft, hard and semi-hard polyurethane foaming plastic; the non-foaming product comprises coating, adhesive, synthetic leather, elastomer, elastic fiber and the like, one of two types of monomers synthesized by polyurethane is relatively few in isocyanate product types, MDI, TDI and the like are mainly used, and the other type of monomer polyol has various varieties, different qualities and diversified downstream application and has further research space.
The long-chain group in the vegetable oil structure replaces a repeating unit of the traditional petrochemical polyol polyether or polyester, the basic parent nucleus of triglyceride in the structure has a star-shaped spatial conformation, more functional attributes and application spaces are endowed to downstream polyurethane, however, the vegetable oil polyol often has performance defects, the main reason is that 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 long-chain group often needs to be mixed with the traditional petrochemical polyol to have a certain application effect. Through reaction mechanism analysis, the main reasons are that the compatibility of the oil ester and a reaction reagent is poor, but the reaction activity is low, so that a long-time high-strength reaction is required, but the influence of a plurality of functional groups in the structure causes that the reaction selectivity and the conversion rate are difficult to be considered, the process control performance is poor, and the obtained product has poor molecular uniformity, high viscosity and large difference between a macroscopic index and a microscopic index of a single molecule. Therefore, even though the price of vegetable oil is often lower than that of monomers of petrochemical repeating units, it is difficult to obtain vegetable oil polyol products with superior cost and quality, and product quality control through chemical process control is necessary.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art, and provides a method for preparing vegetable oil polyalcohol by using a microchannel reaction device, which avoids cross-linking side reaction generated by non-selective ring opening of secondary hydroxyl and other epoxy groups generated in ring opening reaction.
In order to solve the technical problem, the invention discloses a preparation method of vegetable oil polyalcohol, which comprises the steps of mixing epoxy vegetable oil and an acid catalyst into a first mixed solution; dissolving 2, 3-dihydroxy succinic diester compounds in an organic solvent to obtain a second mixed solution; respectively and simultaneously pumping the first mixed solution and the second mixed solution into a first microreactor of a microchannel reaction device for carrying out a first ring-opening reaction to obtain a first reaction solution; and (3) dissolving the long-chain hydroxy fatty acid ester in an organic solvent to obtain a third mixed solution, pumping the third mixed solution and the first reaction solution into a second microreactor of the microchannel reaction device simultaneously to continue a second ring-opening reaction, and collecting the obtained reaction solution to obtain the final product.
Wherein the epoxy vegetable oil is any one or combination of more of epoxy olive oil, epoxy peanut oil, epoxy rapeseed oil, epoxy cottonseed oil, epoxy soybean oil, epoxy coconut oil, epoxy palm oil, epoxy sesame oil, epoxy corn oil and epoxy sunflower seed oil;
the acidic catalyst is one or a combination of more of fluoboric acid, concentrated sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid;
the 2, 3-dihydroxy succinic diester compound is 2, 3-dihydroxy succinic acid dimethyl ester or 2, 3-dihydroxy succinic acid diisobutyl ester;
the organic solvent is any one or combination of more of ethyl acetate, dichloromethane, dichloroethane, chloroform, normal hexane, tetrahydrofuran, 1, 4-dioxane, carbon tetrachloride, toluene and xylene;
the long-chain hydroxy fatty acid ester is 14-hydroxy methyl myristate and/or 14-hydroxy ethyl myristate.
Specifically, the mass percentage of the acidic catalyst to the epoxidized vegetable oil is 0.02-0.1%: 1.
specifically, in the second mixed solution, the mass volume ratio of the 2, 3-dihydroxy succinic acid diester compound to the organic solvent is 1:0.5 to 2.
Specifically, the mass volume ratio of the long-chain hydroxy fatty acid ester to the organic solvent is 1:1 to 4.
Specifically, the reaction 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.
Specifically, the reaction molar ratio of epoxy groups in the epoxy vegetable oil to long-chain hydroxy fatty acid ester is 1:0.1 to 0.2.
Specifically, the microchannel reaction device adopted by the invention comprises a first feeding pump, a second feeding pump, a third feeding pump, a micro-reaction pipeline, a first micro-mixer, a second micro-mixer, a first micro-reactor, a second micro-reactor and a receiver; the first feeding pump and the second feeding pump are connected to the first micromixer; the first reaction liquid and the third feeding pump are connected to the second micromixer; wherein the micro mixer, the micro reactor and the receiver are connected in series through pipelines.
Wherein, the micro mixer is a conventional Y-shaped mixer or a T-shaped mixer; the micro-reactor is of a Vapotech model and adopts a micro-structure heat exchanger.
Specifically, the volume of the first micro-reactor and the second micro-reactor is 5 mL-20 mL.
Preferably, in the invention, the reaction temperature of the first ring-opening reaction is 80-110 ℃, and the reaction time is 3-15 min; the reaction temperature of the second ring-opening reaction is 80-110 ℃, and the reaction time is 3-15 min.
And (3) carrying out liquid separation on reaction effluent liquid of the microreactor, neutralizing with organic phase acid, carrying out liquid separation, drying, and carrying out rotary evaporation to obtain the vegetable oil polyol.
Further, the vegetable oil polyol prepared by the preparation method is also within the protection scope of the invention.
Furthermore, the application of the vegetable oil polyol prepared in the above way in the preparation of polyurethane coatings is also within the protection scope of the invention.
Has the advantages that:
(1) The invention adopts a ring-opening reagent with polyhydroxy and polyester base structure as a first ring-opening reagent to ensure that the functionality is improved and the hydroxyl value is easy to regulate, finishes the ring-opening reaction of most of easy-to-react epoxy groups through process control, and then adopts high-activity long-chain hydroxy fatty acid ester to carry out the ring-opening reaction on the residual epoxy groups with weaker reactivity to obtain vegetable oil polyol products with the epoxy value of about 0.5-1. In order to avoid cross-linking side reaction caused by non-selective ring opening of secondary hydroxyl and other epoxy groups generated in the ring opening reaction, the inventor adopts a micro-reaction technology, selects a microchannel reaction device as reaction equipment, and further controls the ring opening group. In the prepared vegetable oil polyol, polyester-based groups are introduced, a higher hydroxyl value is kept, residues with a certain epoxy value are simultaneously realized, the mechanical property of the polyurethane material is improved, a certain toughness of a polyurethane product is kept, and the prepared vegetable oil polyol has a better corrosion resistance.
(2) The vegetable oil polyol prepared by the method has a novel structure, is moderate and uniform in distribution, has low viscosity, can replace the traditional petrochemical polyol, has high mechanical property and high toughness, and is remarkably improved in comprehensive performance.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a schematic view of a microchannel reactor apparatus used in the present invention.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
The related determination method of the prepared vegetable oil polyol and polyurethane material comprises the following steps:
(1) The hydroxyl number was determined according to GB/T12008.3-2009.
(2) The viscosity was measured according to GB/T12008.7-2010.
(3) The tack-free time of the coating was determined according to GB/T1728-2020 (method B).
(4) The actual dry time of the coating is determined according to GB/T1728-1979 (method A).
(5) VOC content was determined according to GB/T23985-2009 (8.3).
(6) The surface hardness of the coating is measured according to GB/T6739-2006.
(7) The impact resistance of the coatings was determined according to GB/T1732-2020.
(8) The flexibility of the coatings was determined according to GB/T1731-2020 (4).
(9) The paint adhesion was determined according to GB/T5210-2006.
(10) Neutral salt spray resistance preservation test was determined according to GB/T1771-2007.
Example 1
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value is 6.2 percent, and the epoxy group is 38.4 mmol) and fluoboric acid (20mg, 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (5.13g, 28.8mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL at the speed of 1mL/min and the speed of 1.15mL/min respectively to perform ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (1.47g, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying and concentrating an organic phase to obtain the soybean oil polyol with the hydroxyl value of 210mgKOH/g, the epoxy value of 0.6 and the viscosity of 808 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: mixing a certain amount of vegetable oil polyol and isocyanate MDI (isocyanate MDI) (according to the mol ratio of NCO to OH functional groups of 1.25: 1-1.05), adding a catalyst (the mass of the polyol is 3 per mill), and reacting for 2 hours to obtain prepolymer mixed liquor. Adding a certain amount of hydrophilic chain extender and other auxiliaries into the prepolymer mixed solution, reacting for 3 hours to obtain polymer mixed solution, adding a proper amount of neutralizing agent to neutralize the polymer mixed solution to be neutral, and adding a diluent to perform high-speed shearing emulsification to form polyurethane emulsion. And (3) spraying a steel plate as a substrate, wherein the thickness of the dry film is 60-80 microns, and testing after the steel plate is placed in a laboratory environment for 168 hours.
Example 2
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value is 6.2 percent, and the epoxy group is 38.4 mmol) and fluoboric acid (20mg, 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (4.78g, 26.9mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL at the speed of 1mL/min and the speed of 1.14mL/min respectively to perform ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (1.99g, 7.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying and concentrating an organic phase to obtain the soybean oil polyol with the hydroxyl value of 205mgKOH/g, the epoxy value of 0.7 and the viscosity of 692 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in the general manner of (2) in example 1.
Example 3
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value of which is 6.2 percent and the epoxy group of which is 38.4 mmol) and fluoboric acid (20mg and 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (5.47g and 30.7mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL of the 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 methyl 14-hydroxymyristate (1.03g, 4.0 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying an organic phase, and concentrating to obtain soybean oil polyol with the hydroxyl value of 220mgKOH/g, the epoxy value of 0.6 and the viscosity of 1026 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in the general manner of (2) in example 1.
Example 4
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value of which is 6.2 percent and the epoxy group of which is 38.4 mmol) and fluoroboric acid (20mg and 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (4.78g and 26.9mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL at the speed of 1mL/min and the speed of 1.14mL/min respectively to perform ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (1.47g, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying and concentrating an organic phase to obtain the soybean oil polyol with the hydroxyl value of 203mgKOH/g, the epoxy value of 0.8 and the viscosity of 653mPa & s.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in the general manner of (2) in example 1.
Example 5
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value of which is 6.2 percent and the epoxy group of which is 38.4 mmol) and fluoboric acid (20mg and 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (5.47g and 30.7mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL of the 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 methyl 14-hydroxymyristate (1.99g, 7.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying an organic phase, and concentrating to obtain soybean oil polyol with the hydroxyl value of 218mgKOH/g, the epoxy value of 0.5 and the viscosity of 988 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in the general manner of (2) in example 1.
Example 6
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value is 6.2 percent, and the epoxy group is 38.4 mmol) and fluoboric acid (20mg, 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (5.13g, 28.8mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 80 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL at the speed of 1mL/min and the speed of 1.15mL/min respectively to perform ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (1.47g, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 15mL at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying an organic phase, and concentrating to obtain the soybean oil polyol with the hydroxyl value of 201mgKOH/g, the epoxy value of 0.9 and the viscosity of 628 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in the general manner of (2) in example 1.
Example 7
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value is 6.2 percent, and the epoxy group is 38.4 mmol) and fluoboric acid (20mg, 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (5.13g, 28.8mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 110 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL at the speed of 1mL/min and the speed of 1.15mL/min respectively to perform ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (1.47, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting the temperature of the reactor to 110 ℃, pumping the third mixed solution and the first reaction solution into a micro-channel reaction device with the volume of 15mL at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying an organic phase, and concentrating to obtain the soybean oil polyol with the hydroxyl value of 208mgKOH/g, the epoxy value of 0.7 and the viscosity of 784 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in the general manner of (2) in example 1.
Example 8
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value is 6.2 percent, and the epoxy group is 38.4 mmol) and fluoboric acid (20mg, 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (5.13g, 28.8mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL at the speed of 2mL/min and the speed of 2.3mL/min respectively to perform ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (1.47g, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 4mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying and concentrating an organic phase to obtain the soybean oil polyol with the hydroxyl value of 200mgKOH/g, the epoxy value of 1 and the viscosity of 576 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in the general manner of (2) in example 1.
Example 9
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value is 6.2 percent, and the epoxy group is 38.4 mmol) and fluoboric acid (20mg, 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (5.13g, 28.8mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a 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 perform ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (1.47g, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 1mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying an organic phase, and concentrating to obtain soybean oil polyol with the hydroxyl value of 207mgKOH/g, the epoxy value of 0.5 and the viscosity of 792 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in accordance with the general method of (2) in example 1.
Example 10
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value is 6.2 percent, and the epoxy group is 38.4 mmol) and fluoboric acid (20mg, 50%) to obtain a first mixed solution, mixing 2, 3-dihydroxy succinic acid diisobutyl ester (7.55g, 28.8 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL of the 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 methyl 14-hydroxymyristate (1.47g, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying an organic phase, and concentrating to obtain soybean oil polyol with the hydroxyl value of 185mgKOH/g, the epoxy value of 0.6 and the viscosity of 558 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in the general manner of (2) in example 1.
Example 11
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value is 6.2 percent, and the epoxy group is 38.4 mmol) and fluoboric acid (20mg, 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (5.13g, 28.8mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL at the speed of 1mL/min and the speed of 1.15mL/min respectively to perform ring-opening reaction to obtain a first reaction solution; mixing 14-hydroxymyristic acid ethyl ester (1.55g, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying and concentrating an organic phase to obtain the soybean oil polyol with the hydroxyl value of 211mgKOH/g, the epoxy value of 0.7 and the viscosity of 853mPa & s.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in accordance with the general method of (2) in example 1.
Example 12
(1) Preparation of vegetable oil polyol: mixing epoxy cottonseed oil (13 mL, the epoxy value is 5.1%, and the epoxy group is 38.4 mmol) and fluoboric acid (20mg and 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxy succinate (5.13g and 28.8mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL of the micro-channel reaction device at the speed of 1.3mL/min and the speed of 1.15mL/min respectively to perform ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (1.47g, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying and concentrating an organic phase to obtain the soybean oil polyol with the hydroxyl value of 188mgKOH/g, the epoxy value of 0.6 and the viscosity of 789 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in accordance with the general method of (2) in example 1.
Example 13
(1) Preparation of vegetable oil polyol: mixing epoxy sunflower seed oil (10 mL, the epoxy value of which is 6.0 percent and the epoxy group of which is 38.2 mmol) and fluoroboric acid (20mg and 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (5.13g and 28.8mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL at the speed of 1mL/min and the speed of 1.15mL/min respectively to perform ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (1.47g, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying an organic phase, and concentrating to obtain soybean oil polyol with the hydroxyl value of 207mgKOH/g, the epoxy value of 0.5 and the viscosity of 812 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in accordance with the general method of (2) in example 1.
Example 14
(1) Preparation of vegetable oil polyol: mixing epoxy rapeseed oil (13.5 mL, the epoxy value is 4.9 percent, and the epoxy group is 38.4 mmol) and fluoboric acid (20mg, 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (5.13g, 28.8mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, pumping the first mixed solution and the second mixed solution into a micro-reactor with a micro-channel reaction device volume of 10mL at the speed of 1.35mL/min and the speed of 1.15mL/min respectively to perform ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (1.47, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying and concentrating an organic phase to obtain the soybean oil polyol with the hydroxyl value of 182mgKOH/g, the epoxy value of 0.5 and the viscosity of 991 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in the general manner of (2) in example 1.
Example 15
(1) Preparation of vegetable oil polyol: mixing epoxy corn oil (12.3 mL, the epoxy value of which is 5.2 percent and the epoxy group of which is 38.4 mmol) and fluoroboric acid (20mg and 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (5.13g and 28.8mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL of the micro-channel reaction device at the speed of 1.23mL/min and the speed of 1.15mL/min to carry out ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (1.47g, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying an organic phase, and concentrating to obtain soybean oil polyol with the hydroxyl value of 188mgKOH/g, the epoxy value of 0.5 and the viscosity of 792 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in accordance with the general method of (2) in example 1.
Example 16
(1) Preparation of vegetable oil polyol: mixing epoxy peanut oil (14.4 mL, the epoxy value is 4.5%, and the epoxy group is 38.4 mmol) and fluoboric acid (20mg, 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (5.13g, 28.8mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with a micro-channel reaction device volume of 10mL at the speed of 1.44mL/min and the speed of 1.15mL/min respectively to perform ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (1.47g, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying and concentrating an organic phase to obtain soybean oil polyol with the hydroxyl value of 168mgKOH/g, the epoxy value of 0.6 and the viscosity of 655 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in the general manner of (2) in example 1.
Comparative example 1
(1) Preparation of vegetable oil polyol: epoxidized soybean oil (10 mL, epoxy value of 6.2%, epoxy group of 38.4 mmol), fluoroboric acid (20mg, 50%), dimethyl 2, 3-dihydroxysuccinate (5.13g, 28.8mmol) and ethyl acetate (30 mL) were reacted at 100 ℃ for 6 hours, methyl 14-hydroxymyristate (1.47g, 5.7mmol) was added and the reaction was continued for 4 hours, and the reaction solution was cooled to room temperature, and then washed with sodium bicarbonate solution (30mL, 10%) and water (30 mL. Times.2), the organic phase was dried and concentrated to obtain soybean oil polyol having a hydroxyl value of 121mgKOH/g, epoxy value of 1.3 and viscosity of 1650 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in the general manner of (2) in example 1.
Comparative example 2
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value is 6.2 percent, and the epoxy group is 38.4 mmol) and fluoboric acid (20mg, 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxy succinate (4.10 g,23.0 mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL at the speed of 1mL/min and the speed of 1.14mL/min respectively to perform ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (1.47g, 5.7 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting the temperature of the reactor to 100 ℃, pumping the third mixed solution and the first reaction solution into a microreactor with the volume of 15mL in a microchannel reaction device at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying and concentrating an organic phase to obtain the soybean oil polyol with the hydroxyl value of 152mgKOH/g, the epoxy value of 1.6 and the viscosity of 512 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in accordance with the general method of (2) in example 1.
Comparative example 3
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value of which is 6.2 percent and the epoxy group of which is 38.4 mmol) and fluoroboric acid (20mg and 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxysuccinate (6.15g and 34.6mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL at the speed of 1mL/min and the speed of 1.17mL/min respectively to perform ring-opening reaction to obtain a first reaction solution; mixing methyl 14-hydroxymyristate (0.99g, 4.0 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying and concentrating an organic phase to obtain soybean oil polyol with the hydroxyl value of 160mgKOH/g, the epoxy value of 1.2 and the viscosity of 1856 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in the general manner of (2) in example 1.
Comparative example 4
(1) Preparation of vegetable oil polyol: mixing epoxidized soybean oil (10 mL, the epoxy value of which is 6.2 percent and the epoxy group of which is 38.4 mmol) and fluoroboric acid (20mg and 50%) to obtain a first mixed solution, mixing dimethyl 2, 3-dihydroxy succinate (5.13g and 28.8mmol) and ethyl acetate (10 mL) to obtain a second mixed solution, adjusting the temperature of a reactor to 100 ℃, and pumping the first mixed solution and the second mixed solution into a micro-reactor with the volume of 10mL of the 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 methyl 14-hydroxymyristate (3g, 11.6 mmol) and ethyl acetate (20 mL) to obtain a third mixed solution, adjusting 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 at the speed of 2mL/min for ring-opening reaction, sequentially washing the obtained reaction solution with sodium bicarbonate solution (30mL, 10%) and water (30 mL multiplied by 2), drying and concentrating an organic phase to obtain soybean oil polyol with the hydroxyl value of 158mgKOH/g, the epoxy value of 1.1 and the viscosity of 1711 mPas.
(2) Preparation of vegetable oil-based polyurethane coating: a polyurethane coating was prepared in the general manner of (2) in example 1.
The performance indexes of the polyurethane coatings prepared in examples 1 to 16 and comparative examples 1 to 4 are shown in Table 1.
TABLE 1 Performance index of vegetable oil-based polyurethane coatings prepared in examples and comparative examples
TABLE 1 (tables) Performance index of vegetable oil-based polyurethane coatings prepared in examples and comparative examples
As can be seen from the data in Table 1, in the conventional reaction flask, the hydroxyl value is seriously attenuated, the viscosity is high and the performance of the vegetable oil-based polyurethane coating is reduced due to uncontrollable process and more crosslinking side reactions. According to the invention, a micro-reaction technology is adopted, the dosage of a ring-opening reagent is controlled, a small amount of epoxy value is remained, a polyester group is introduced into the prepared vegetable oil polyol, the hydroxyl value is higher, the mechanical property and toughness of the polyurethane material are increased, and the polyurethane material has better corrosion resistance.
The invention provides a preparation method of vegetable oil polyalcohol and an application method thereof in polyurethane anticorrosive paint, and a method and a way for realizing the technical scheme are many, the above description is only a preferred embodiment of the invention, and it should be noted that for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and the improvements and decorations are also regarded as the protection scope of the invention. All the components not specified in this embodiment can be implemented by the prior art.
Claims (10)
1. A preparation method of vegetable oil polyalcohol is characterized in that epoxy vegetable oil and an acid catalyst are mixed into a first mixed solution; dissolving 2, 3-dihydroxy succinic diester compounds in an organic solvent to obtain a second mixed solution; respectively and simultaneously pumping the first mixed solution and the second mixed solution into a first microreactor of the microchannel reaction device for carrying out a first ring-opening reaction to obtain a first reaction solution; and (3) dissolving the long-chain hydroxy fatty acid ester in an organic solvent to obtain a third mixed solution, pumping the third mixed solution and the first reaction solution into a second microreactor of the microchannel reaction device simultaneously to continue to perform a second ring-opening reaction, and collecting the obtained reaction solution to obtain the final product.
2. The method for preparing the vegetable oil polyol according to claim 1, wherein the epoxidized vegetable oil is any one or a combination of several 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; the acid catalyst is one or a combination of more of fluoboric acid, concentrated sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid; the 2, 3-dihydroxy succinic acid diester compound is 2, 3-dihydroxy succinic acid dimethyl ester or 2, 3-dihydroxy succinic acid diisobutyl ester; the organic solvent is any one or combination of more of ethyl acetate, dichloromethane, dichloroethane, chloroform, normal hexane, tetrahydrofuran, 1, 4-dioxane, carbon tetrachloride, toluene and xylene; the long-chain hydroxy fatty acid ester is any one or combination of 14-hydroxy methyl myristate and/or 14-hydroxy ethyl myristate.
3. The method for preparing vegetable oil polyol according to claim 1, wherein the mass percentage of the acidic catalyst to the epoxidized vegetable oil is 0.02 to 0.1%:1.
4. the method for preparing vegetable oil polyol according to claim 1, wherein the mass-to-volume ratio of the 2, 3-dihydroxysuccinic diester compound to the organic solvent is 1:0.5 to 2.
5. The method for preparing vegetable oil polyol according to claim 1, wherein the mass volume ratio of the long-chain hydroxy fatty acid ester to the organic solvent is 1:1 to 4.
6. The method of claim 1, wherein the molar ratio of the epoxy group in the epoxidized vegetable oil to the 2, 3-dihydroxy succinic diester compound is 1:0.7 to 0.8.
7. The method of claim 1, wherein the molar ratio of the epoxy group to the long-chain hydroxy fatty acid ester in the epoxidized vegetable oil is 1:0.1 to 0.2.
8. The method for preparing the vegetable oil polyol according to claim 1, wherein the volumes of the first microreactor and the second microreactor are both 5 mL-20 mL; the reaction temperature of the first ring-opening reaction is 80-110 ℃, and the reaction time is 3-15 min; the reaction temperature of the second ring-opening reaction is 80-110 ℃, and the reaction time is 3-15 min.
9. A vegetable oil polyol prepared by the process of any one of claims 1 to 8.
10. Use of the vegetable oil polyol of claim 9 in the preparation of a polyurethane coating.
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| CN117285694B (en) * | 2023-09-20 | 2024-04-09 | 南京工业大学 | Vegetable oil polyol and preparation method and application thereof |
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