阅读说明：本技术 一种植物油多元醇与制备方法及其在聚氨酯材料中的应用 (Vegetable oil polyalcohol, preparation method and application thereof in polyurethane material ) 是由 郭凯 方正 陈可泉 陶俊杰 何伟 陈昌主 谭伟民 刘福建 黄益平 马仁 于 2021-01-25 设计创作，主要内容包括：本发明公开了一种植物油多元醇与制备方法及其在聚氨酯材料中的应用,将植物油与乙烯、Grubbs 2代催化剂在反应釜中反应得到去除悬吊链的植物油,然后与7-氧杂双环[4,1,0]-2,4-庚二烯分别同时泵入微通道模块化反应装置的第一微混合器中进行混合,混合后泵入第一微反应器进行反应得到环氧植物油,再与开环试剂、催化剂制成的混合液分别同时泵入微通道模块化反应装置的第二微混合器中进行混合,混合后泵入第二微反应器进行开环反应,得到开环产物,最后与Pd/C催化剂、氢气在反应釜中进行氢化反应即得。本发明首先成功的去除了植物油中的悬吊链,使多元醇羟值和粘度适中,采用微通道技术制备得到的植物油多元醇可替代传统多元醇,用于聚氨酯结构胶和聚氨酯涂料的制备。(The invention discloses a vegetable oil polyalcohol, a preparation method and application thereof in polyurethane materials, wherein vegetable oil is reacted with ethylene and Grubbs 2-generation catalyst in a reaction kettle to obtain vegetable oil without suspension chains, then the vegetable oil and 7-oxabicyclo [4,1,0] -2, 4-heptadiene are respectively pumped into a first micro mixer of a microchannel modular reaction device to be mixed, the mixture is pumped into a first micro reactor to react to obtain epoxy vegetable oil, the epoxy vegetable oil and mixed liquid prepared from a ring-opening reagent and the catalyst are respectively pumped into a second micro mixer of the microchannel modular reaction device to be mixed, the mixture is pumped into a second micro reactor to carry out ring-opening reaction to obtain a ring-opening product, and finally the ring-opening product is hydrogenated with a Pd/C catalyst and hydrogen in the reaction kettle to obtain the polyurethane material. The invention firstly successfully removes the suspension chain in the vegetable oil, so that the hydroxyl value and the viscosity of the polyol are moderate, and the vegetable oil polyol prepared by adopting the microchannel technology can replace the traditional polyol and be used for preparing the polyurethane structural adhesive and the polyurethane coating.)

1. The preparation method of the vegetable oil polyol is characterized by comprising the following steps:

(1) reacting vegetable oil with ethylene and Grubbs 2-generation catalyst in a reaction kettle to obtain vegetable oil with a suspension chain removed;

(2) respectively and simultaneously pumping the vegetable oil without the suspension chain obtained in the step (1) and 7-oxabicyclo [4,1,0] -2, 4-heptadiene into a first micro mixer of a microchannel modular reaction device for mixing, and pumping the mixed oil into a first micro reactor for reaction to obtain epoxy vegetable oil;

(3) respectively and simultaneously pumping the epoxy vegetable oil obtained in the step (2), a mixed solution prepared from an open-loop reagent and a catalyst into a second micro mixer of the microchannel modular reaction device for mixing, and pumping the mixed solution into a second micro reactor for an open-loop reaction to obtain an open-loop product;

(4) and (4) carrying out hydrogenation reaction on the ring-opening product obtained in the step (3), a Pd/C catalyst and hydrogen in a reaction kettle to obtain the catalyst.

2. The method for preparing vegetable oil polyol as claimed in claim 1, wherein in the step (1), the vegetable oil is any one of soybean oil, corn oil, peanut oil and castor oil; the molar ratio of double bonds, ethylene and Grubbs 2-generation catalyst in the vegetable oil is 1: (1-2): (0:05-0.2), the reaction temperature is 50-70 ℃, and the reaction time is 2-4 h.

3. The method for preparing vegetable oil polyol as claimed in claim 1, wherein in the step (2), the 7-oxabicyclo [4,1,0] -2, 4-heptadiene is synthesized from 3, 4-dibromo-7-oxabicyclo [4,1,0] heptane, 1, 8-diazabicycloundec-7-ene and diethyl ether; the reaction molar ratio of the vegetable oil without the suspension chain obtained in the step (1) to the 7-oxabicyclo [4,1,0] -2, 4-heptadiene is 1:2.

4. The method for preparing vegetable oil polyol according to claim 1, wherein in the step (2), the vegetable oil without the suspension chain obtained in the step (1) is pumped into the microchannel modular reaction device at a flow rate of 0.6-1.2 mL/min; the flow rate of the 7-oxabicyclo [4,1,0] -2, 4-heptadiene micro-channel modular reaction device is 3-5 mL/min; the volume of the first micro-reactor is 7.2-31mL, the reaction temperature is controlled at 170-200 ℃, and the reaction residence time is 2-5 min.

5. The method for preparing vegetable oil polyol as claimed in claim 1, wherein in the step (3), the ring-opening reagent is any one of methanol, ethanol, n-propanol and 2-butanol; the catalyst is fluoroboric acid; the reaction molar ratio of the epoxy vegetable oil obtained in the step (2), the ring-opening reagent and the catalyst is 1: (2-3): (0.05-0.12).

6. The method for preparing vegetable oil polyol according to claim 1, wherein in the step (3), the flow rate of the mixed liquid prepared from the ring-opening reagent and the catalyst pumped into the microchannel modular reaction device is 5.5-10.0 mL/min; the volume of the second micro-reactor is 45.5-129.6 mL; controlling the reaction temperature of the ring-opening reaction to be 80-130 ℃, and keeping the reaction for 5-8 min.

7. The process for preparing vegetable oil polyol as claimed in claim 1, wherein in the step (4), the reaction molar ratio of the ring-opening product obtained in the step (3) to the Pd/C catalyst is 1: (0.3-0.5), introducing hydrogen, and keeping the pressure of the reaction kettle at 1MPa for 8-12 h.

8. A vegetable oil polyol prepared by the method of any one of claims 1 to 7.

9. Use of the vegetable oil polyol of claim 8 in the preparation of a polyurethane structural adhesive.

10. Use of the vegetable oil polyol of claim 8 in the preparation of a polyurethane coating.

Technical Field

The invention relates to the technical field of vegetable oil polyols, and in particular relates to a vegetable oil polyol, a preparation method and application thereof in a polyurethane material.

Background

Polyurethanes are polymers having repeating structural units of urethane segments made by reacting an isocyanate with a polyol. Polyurethane products are classified into two broad categories, foamed products and non-foamed products. The foaming product is soft, hard and semi-hard polyurethane foaming plastic; non-foamed articles include coatings, adhesives, synthetic leather, elastomers, and elastic fibers, among others. The polyurethane material has excellent performance, wide application and various products.

At present, polyurethane polyols are various, and the polyols which are dominant in the market are mainly polyether polyols obtained by reacting certain hydroxyl compounds and amine compounds with higher functionality with propylene oxide or ethylene oxide, and in addition, polyester polyols, modified graft polyether polyols and the like, and the polyol products are downstream products of petroleum, and have the advantages of strong resource dependence, higher price and poor process safety. Therefore, the method replaces petrochemical resources with bio-based raw materials, develops the vegetable oil polyol, improves the product quality, reduces the resource dependence and improves the process safety, and is an important trend of polyurethane polyol research and industrial development.

The vegetable oil polyalcohol is a substitute of petroleum-based polyalcohol, and has outstanding environmental protection value. The vegetable oil polyalcohol has wide raw material sources, and the vegetable oil comprises edible oil such as peanut oil, rapeseed oil, soybean oil, castor oil, olive oil, palm oil and the like, and non-edible oil such as jatropha curcas oil, pistacia chinensis bunge oil and the like.

However, most of the currently synthesized vegetable oil polyols contain a suspension chain, so that the iodine value of the polyol is low, and the epoxy value of the polyol is high, thereby affecting the performance of the synthesized polyurethane material.

Disclosure of Invention

The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art, and provides a vegetable oil polyol and a preparation method thereof, so as to solve the problems of large hydroxyl value and high viscosity of the generated polyol product caused by a suspension chain in the conventional vegetable oil, thereby improving the performance of a polyurethane material.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a preparation method of vegetable oil polyalcohol comprises the following steps:

(1) reacting vegetable oil with ethylene and Grubbs 2-generation catalyst in a reaction kettle to obtain vegetable oil with a suspension chain removed;

(2) respectively and simultaneously pumping the vegetable oil without the suspension chain obtained in the step (1) and 7-oxabicyclo [4,1,0] -2, 4-heptadiene into a first micro mixer of a microchannel modular reaction device for mixing, and pumping the mixed oil into a first micro reactor for reaction to obtain epoxy vegetable oil;

(3) respectively and simultaneously pumping the epoxy vegetable oil obtained in the step (2), a mixed solution prepared from an open-loop reagent and a catalyst into a second micro mixer of the microchannel modular reaction device for mixing, and pumping the mixed solution into a second micro reactor for an open-loop reaction to obtain an open-loop product;

(4) and (4) carrying out hydrogenation reaction on the ring-opening product obtained in the step (3), a Pd/C catalyst and hydrogen in a reaction kettle to obtain the catalyst.

Specifically, in the step (1), the vegetable oil is any one of soybean oil, corn oil, peanut oil and castor oil, preferably peanut oil; the molar ratio of double bonds, ethylene and Grubbs 2-generation catalyst in the vegetable oil is 1: (1-2): (0:05-0.2), preferably 1:2: 0.05; the reaction temperature is 50-70 ℃, preferably 60 ℃; the reaction time is 2-4h, preferably 3 h. When the polyol has a suspension chain, the polyol is too rigid, so that the performance and the mechanical property of the prepared partial polyurethane material are poor, and the requirement cannot be met, and therefore, the suspension chain in the vegetable oil needs to be removed. The principle of the reaction in the step (1) is that the addition of metal ruthenium can form a complex under the attraction of an olefinic bond, ethylene is coordinated with the complex to enable two olefins to form a four-membered ring through ruthenium, the four-membered ring is opened under the heating condition, long-chain hydrocarbon leaves to form long-chain terminal olefin with the olefins, and the vegetable oil forms a terminal olefin structure.

Specifically, in the step (2), the 7-oxabicyclo [4,1,0] -2, 4-heptadiene is synthesized from 3, 4-dibromo-7-oxabicyclo [4,1,0] heptane, 1, 8-diazabicycloundecen-7-ene and diethyl ether (reference: Direct laser writing of poly (phenylene vinylene) on poly (barlene), DOI:10.1039/d0py00869 a); the reaction molar ratio of the vegetable oil without the suspension chain obtained in the step (1) to the 7-oxabicyclo [4,1,0] -2, 4-heptadiene is 1:2. The purpose of step (2) is to introduce an epoxy structure in the product by the occurrence of diels-alder reaction.

Preferably, in the step (2), the plant oil without the suspension chains obtained in the step (1) is pumped into the microchannel modular reaction device at a flow rate of 0.6-1.2mL/min, preferably 0.8 mL/min; the flow rate of the 7-oxabicyclo [4,1,0] -2, 4-heptadiene micro-channel modular reaction device is 3-5mL/min, preferably 4.5 mL/min; the volume of the first microreactor is 7.2-31mL, preferably 15.9 mL; the reaction temperature is controlled at 170-200 ℃, and preferably 180 ℃; the reaction residence time is 2-5min, preferably 3 min.

Specifically, in the step (3), the ring-opening reagent is any one of methanol, ethanol, n-propanol and 2-butanol, preferably 2-butanol; the catalyst is fluoroboric acid; the reaction molar ratio of the epoxy vegetable oil obtained in the step (2), the ring-opening reagent and the catalyst is 1: (2-3): (0.05-0.12), preferably 1:2.5: 0.1. The purpose of step (3) is to introduce a hydroxyl structure into the product by an epoxy ring-opening reaction.

Preferably, in the step (3), the flow rate of the mixed liquid made of the ring-opening reagent and the catalyst pumped into the microchannel modular reaction device is 5.5-10.0mL/min, preferably 8.6 mL/min; the volume of the second microreactor is 45.5-129.6mL, preferably 83.4 mL; controlling the reaction temperature of the ring-opening reaction to be 80-130 ℃, and preferably 120 ℃; the reaction is maintained for 5-8min, preferably 6 min.

Preferably, in the step (4), the reaction molar ratio of the ring-opening product obtained in the step (3) to the Pd/C catalyst is 1: (0.3-0.5), preferably 1: 0.46; introducing hydrogen, and keeping the pressure of the reaction kettle at about 1 MPa; the reaction time is 8-12h, preferably 10 h. Step (4) is intended to reduce the double bond in the product by hydrogenation.

Further, the vegetable oil polyol prepared by the preparation method is also in the protection scope of the invention.

Furthermore, the invention also claims the application of the vegetable oil polyalcohol in preparing polyurethane structural adhesive.

Specifically, the preparation method of the polyurethane structural adhesive (the use amount of the raw materials is "part by weight"):

(1) the preparation method of the first component comprises the following steps: adding 100 parts of vegetable oil polyalcohol and 10 parts of trimethylolpropane into a reaction kettle, heating to 110 ℃, stirring and dehydrating for 2 hours under the vacuum degree of less than or equal to-0.09 Mpa at the rotating speed of 1200r/min, then cooling to below 60 ℃, transferring into a stirring machine at the rotating speed of 1200r/min, then adding 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KH-550, 4 parts of silicon dioxide-supported organotin ii and 2 parts of molecular sieve, stirring for 30 minutes under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a first component;

(2) the preparation method of the second component comprises the following steps: toluene Diisocyanate (TDI): adding polymethylene polyphenyl polyisocyanate (PAPI) of 7:3 into a stirrer at the rotation speed of 1200r/min, stirring for 30min under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a second component;

(3) the sizing is carried out: and mixing the first component and the second component according to the mass ratio of 1:0.8 to obtain the polyurethane structural adhesive.

Wherein the plasticizer i and the organotin ii have the following structural formulas:

furthermore, the invention also claims the application of the vegetable oil polyalcohol in preparing polyurethane coating.

Specifically, the preparation method of the polyurethane coating comprises the following steps (the used amount of the raw materials is "part by weight"):

65 parts of vegetable oil polyol and 60 parts of isophorone diisocyanate (IPDI) are mixed in 5 parts of acetone, 2 parts of dibutyltin dilaurate is added, and the mixture reacts for 2 hours at the temperature of 50 ℃ to obtain prepolymer mixed liquid. And adding 15 parts of epoxy resin iii, 18 parts of flame retardant casein and 9 parts of hydrophilic chain extender dihydroxy half ester into the prepolymer mixed solution, and reacting at the temperature of 50 ℃ for 3 hours to obtain polymer mixed solution. And cooling the polymer mixed solution to 30 ℃, adding 25 parts of neutralizing agent triethylamine to neutralize the polymer mixed solution to be neutral, and adding 30 parts of deionized water to perform high-speed shearing emulsification to form polyurethane emulsion. And distilling the polyurethane emulsion under reduced pressure to remove acetone to obtain the flame-retardant vegetable oil-based waterborne polyurethane coating.

Wherein the structural formula of the epoxy resin iii is as follows:

has the advantages that:

1. the invention firstly successfully removes the suspension chain in the vegetable oil, so that the hydroxyl value and the viscosity of the polyol are moderate, the vegetable oil polyol prepared by adopting the microchannel technology can replace the traditional polyol and be used for preparing the polyurethane structural adhesive and the polyurethane coating, and meanwhile, the preparation process is simple, the operation is convenient, the energy consumption is low, the side reaction is less, and the reaction efficiency is high.

2. The polyurethane structural adhesive prepared by the invention has the advantages of high curing speed, high hardness and high strength.

3. The vegetable oil polyalcohol prepared by the invention has good miscibility, and the amount of organic solvent required for preparing polyurethane coating is greatly reduced; the prepared polyurethane coating has the advantages of increased hardness, improved impact resistance and good glossiness.

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 flow chart of the process for the synthesis of vegetable oil polyols of example 2.

FIG. 2 is a nuclear magnetic hydrogen spectrum of soybean oil in example 2.

FIG. 3 is a nuclear magnetic hydrogen spectrum of soybean oil with the pendant chains removed in example 2.

Detailed Description

The invention will be better understood from the following examples.

Example 1

Synthesizing vegetable oil polyol according to the process flow diagram shown in figure 1:

(1) preparation of vegetable oil polyols

265g peanut oil (containing 1mol of double bond), 56g ethylene (2mol), 42.45g Grubbs 2-substituted catalyst (0.05mol) were reacted in a 60 ℃ reaction kettle for 3 hours to obtain a vegetable oil with the pendant chains removed as component I. 188g of 7-oxabicyclo [4,1,0] -2, 4-heptadiene (2mol) were used as component II. Simultaneously pumping the component I and the component II into a first micro-back mixer 1 at a sample injection rate of 0.8mL/min and 4.5mL/min, mixing, pumping into a first microreactor 2(15.9mL), keeping the reaction for 3min, and reacting at the normal pressure and 180 ℃ to obtain the epoxy vegetable oil. Simultaneously pumping a mixture of epoxy vegetable oil and 185g of 2-butanol (2.5mol) with the sample injection rate of 8.6mL/min and 8.8g of fluoroboric acid (0.1mol) into a second micro-mixer 3, pumping the mixture into a second micro-reactor 4(83.4mL) after mixing, keeping the reaction for 6min, reacting at normal pressure and 120 ℃, reacting the obtained product with 48.76g of Pd/C (0.46mol) under the condition of continuously introducing hydrogen for 10h, and washing with water to obtain the peanut oil polyol (the hydroxyl value is 125 mgKOH/g).

(2) Preparation of polyurethane structural adhesive

The preparation method of the first component comprises the following steps: adding 100 parts of peanut oil polyalcohol and 10 parts of trimethylolpropane into a reaction kettle, heating to 110 ℃, stirring and dehydrating for 2 hours under the vacuum degree of less than or equal to-0.09 Mpa at the rotating speed of 1200r/min, then cooling to below 60 ℃, transferring into a stirring machine at the rotating speed of 1200r/min, then adding 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KH-550, 4 parts of silicon dioxide-supported organotin ii and 2 parts of molecular sieve, stirring for 30 minutes under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a first component; the preparation method of the second component comprises the following steps: toluene Diisocyanate (TDI): adding polymethylene polyphenyl polyisocyanate (PAPI) of 7:3 into a stirrer at the rotation speed of 1200r/min, stirring for 30min under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a second component; the sizing is carried out: and mixing the first component and the second component according to the mass ratio of 1:0.8 to obtain the polyurethane structural adhesive.

(3) Preparation of polyurethane coatings

65 parts of peanut oil polyol and 60 parts of isophorone diisocyanate (IPDI) are mixed in 5 parts of acetone, 2 parts of dibutyltin dilaurate is added, and the mixture reacts for 2 hours at the temperature of 50 ℃ to obtain prepolymer mixed liquid. And adding 15 parts of epoxy resin iii, 18 parts of flame retardant casein and 9 parts of hydrophilic chain extender dihydroxy half ester into the prepolymer mixed solution, and reacting at the temperature of 50 ℃ for 3 hours to obtain polymer mixed solution. And cooling the polymer mixed solution to 30 ℃, adding 25 parts of neutralizing agent triethylamine to neutralize the polymer mixed solution to be neutral, and adding 30 parts of deionized water to perform high-speed shearing emulsification to form polyurethane emulsion. And distilling the polyurethane emulsion under reduced pressure to remove acetone to obtain the waterborne polyurethane coating.

Example 2

The plant polyol was prepared according to the process flow shown in figure 1:

200g of soybean oil (containing 1mol of double bond), 28g of ethylene (1mol), 84.9g of Grubbs 2-substituted catalyst (0.1mol) were reacted in a 50 ℃ reaction vessel for 2 hours to obtain a vegetable oil from which pendant chains were removed as component I. FIG. 2 shows the nuclear magnetic hydrogen spectrum of soybean oil without the suspension chain removed, and the nuclear magnetic hydrogen spectrum is shown in FIG. 3 after the suspension chain is removed. The removal of the pendant chains is demonstrated by comparing nuclear magnetic hydrogen spectra of the starting material with that of the product, and finding that the high-field alkyl hydrogen number is reduced and the ethylenic hydrogen peak between chemical shifts 5.0 and 5.5 produces more splits due to the leaving of the pendant chains.

188g of 7-oxabicyclo [4,1,0] -2, 4-heptadiene (2mol) were used as component II. Simultaneously pumping the component I and the component II into a first micro-anti-mixer 1 at a sample injection rate of 0.6mL/min and 3.0mL/min, mixing, pumping into a first micro-reactor 2(9mL), keeping the reaction for 2.5min, and reacting at the normal pressure and 170 ℃ to obtain the epoxy vegetable oil. Simultaneously pumping a mixture of epoxy vegetable oil and 64g (2mol) of methanol and 4.4g (0.05mol) of fluoroboric acid with the sample injection rate of 6mL/min into a second micro-mixer 3, pumping the mixture into a second micro-reactor 4(48mL) after mixing, keeping the reaction for 5min, reacting at normal pressure and 90 ℃, reacting the obtained product with 31.8g of Pd/C (0.3mol) under the condition of continuously introducing hydrogen for 8h, and washing with water to obtain the soybean oil polyol (hydroxyl value is 137 mgKOH/g).

(2) Preparation of polyurethane structural adhesive

The preparation method of the first component comprises the following steps: adding 100 parts of soybean oil polyalcohol and 10 parts of trimethylolpropane into a reaction kettle, heating to 110 ℃, stirring and dehydrating for 2 hours under the vacuum degree of less than or equal to-0.09 Mpa at the rotating speed of 1200r/min, then cooling to below 60 ℃, transferring into a stirring machine at the rotating speed of 1200r/min, then adding 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KH-550, 4 parts of silicon dioxide-supported organotin ii and 2 parts of molecular sieve, stirring for 30 minutes under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a first component; the preparation method of the second component comprises the following steps: toluene Diisocyanate (TDI): adding polymethylene polyphenyl polyisocyanate (PAPI) of 7:3 into a stirrer at the rotation speed of 1200r/min, stirring for 30min under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a second component; the sizing is carried out: and mixing the first component and the second component according to the mass ratio of 1:0.8 to obtain the polyurethane structural adhesive.

(3) Preparation of polyurethane coatings

65 parts of soybean oil polyol and 60 parts of isophorone diisocyanate (IPDI) are mixed in 5 parts of acetone, 2 parts of dibutyltin dilaurate is added, and the mixture reacts for 2 hours at the temperature of 50 ℃ to obtain prepolymer mixed liquid. And adding 15 parts of epoxy resin iii, 18 parts of flame retardant casein and 9 parts of hydrophilic chain extender dihydroxy half ester into the prepolymer mixed solution, and reacting at the temperature of 50 ℃ for 3 hours to obtain polymer mixed solution. And cooling the polymer mixed solution to 30 ℃, adding 25 parts of neutralizing agent triethylamine to neutralize the polymer mixed solution to be neutral, and adding 30 parts of deionized water to perform high-speed shearing emulsification to form polyurethane emulsion. And distilling the polyurethane emulsion under reduced pressure to remove acetone to obtain the waterborne polyurethane coating.

Example 3

(1) Preparation of vegetable oil polyols

212g of corn oil (containing 1mol of double bonds), 42g of ethylene (1.5mol) and 127.35g of Grubbs 2-substituted catalyst (0.15mol) were reacted in a reaction vessel at 65 ℃ for 3.5 hours to obtain a vegetable oil from which pendant chains were removed as component I. 188g of 7-oxabicyclo [4,1,0] -2, 4-heptadiene (2mol) were used as component II. Simultaneously pumping the component I and the component II into a first micro-anti-mixer 1 at a sample injection rate of 1.0mL/min and 4.0mL/min, mixing, pumping into a first micro-reactor 2(20mL), keeping the reaction for 4min, and reacting at the normal pressure and 190 ℃ to obtain the epoxy vegetable oil. Simultaneously pumping a mixture of epoxy vegetable oil and 138g of ethanol (3mol) and 7.04g of fluoroboric acid (0.08mol) with the sample injection rate of 7.3mL/min into a second micro mixer 3, pumping the mixture into a second micro reactor 4(86.1mL) after mixing, keeping the reaction for 7min, reacting at normal pressure and 100 ℃, reacting the obtained product with 42.4g of Pd/C (0.4mol) under the condition of continuously introducing hydrogen for 9h, and washing with water to obtain the corn oil polyol (the hydroxyl value is 148 mgKOH/g).

(2) Preparation of polyurethane structural adhesive

The preparation method of the first component comprises the following steps: adding 100 parts of corn oil polyol and 10 parts of trimethylolpropane into a reaction kettle, heating to 110 ℃, stirring and dehydrating for 2 hours under the vacuum degree of less than or equal to-0.09 Mpa at the rotating speed of 1200r/min, then cooling to below 60 ℃, transferring into a stirring machine at the rotating speed of 1200r/min, then adding 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KH-550, 4 parts of silicon dioxide-supported organotin ii and 2 parts of molecular sieve, stirring for 30 minutes under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a first component; the preparation method of the second component comprises the following steps: toluene Diisocyanate (TDI): adding polymethylene polyphenyl polyisocyanate (PAPI) of 7:3 into a stirrer at the rotation speed of 1200r/min, stirring for 30min under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a second component; the sizing is carried out: and mixing the first component and the second component according to the mass ratio of 1:0.8 to obtain the polyurethane structural adhesive.

(3) Preparation of polyurethane coatings

65 parts of corn oil polyol and 60 parts of isophorone diisocyanate (IPDI) are mixed in 5 parts of acetone, 2 parts of dibutyltin dilaurate is added, and the mixture reacts for 2 hours at the temperature of 50 ℃ to obtain prepolymer mixed liquid. And adding 15 parts of epoxy resin iii, 18 parts of flame retardant casein and 9 parts of hydrophilic chain extender dihydroxy half ester into the prepolymer mixed solution, and reacting at the temperature of 50 ℃ for 3 hours to obtain polymer mixed solution. And cooling the polymer mixed solution to 30 ℃, adding 25 parts of neutralizing agent triethylamine to neutralize the polymer mixed solution to be neutral, and adding 30 parts of deionized water to perform high-speed shearing emulsification to form polyurethane emulsion. And distilling the polyurethane emulsion under reduced pressure to remove acetone to obtain the waterborne polyurethane coating.

Example 4

(1) Preparation of vegetable oil polyols

303g of castor oil (containing 1mol of double bonds), 50.4g of ethylene (1.8mol) and 169.8g of Grubbs 2-substituted catalyst (0.2mol) were reacted in a reaction vessel at 70 ℃ for 4 hours to obtain a vegetable oil from which pendant chains were removed as component I. 188g of 7-oxabicyclo [4,1,0] -2, 4-heptadiene (2mol) were used as component II. Simultaneously pumping the component I and the component II into a first micro-anti-mixer 1 at a sample injection rate of 1.2mL/min and a sample injection rate of 5.0mL/min, mixing, pumping into a first micro-reactor 2(31mL), keeping the reaction for 5min, and reacting at normal pressure and 200 ℃ to obtain the epoxy vegetable oil. Simultaneously pumping a mixture of epoxy vegetable oil and 180g of n-propanol (3.0mol) and 10.56g of fluoroboric acid (0.12mol) with the sample injection rate of 10.0mL/min into a second micro-mixer 3, pumping the mixture into a second microreactor 4(129.6mL) after mixing, keeping the reaction for 8min, reacting at the normal pressure and 130 ℃, reacting the obtained product with 53g of Pd/C (0.5mol) under the condition of continuously introducing hydrogen for 12h, and washing with water to obtain castor oil polyol (the hydroxyl value is 153 mgKOH/g).

(2) Preparation of polyurethane structural adhesive

The preparation method of the first component comprises the following steps: adding 100 parts of castor oil polyol and 10 parts of trimethylolpropane into a reaction kettle, heating to 110 ℃, stirring and dehydrating for 2 hours under the vacuum degree of less than or equal to-0.09 Mpa at the rotating speed of 1200r/min, then cooling to below 60 ℃, transferring into a stirring machine at the rotating speed of 1200r/min, then adding 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KH-550, 4 parts of silicon dioxide-supported organotin ii and 2 parts of molecular sieve, stirring for 30 minutes under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a first component; the preparation method of the second component comprises the following steps: toluene Diisocyanate (TDI): adding polymethylene polyphenyl polyisocyanate (PAPI) of 7:3 into a stirrer at the rotation speed of 1200r/min, stirring for 30min under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a second component; the sizing is carried out: and mixing the first component and the second component according to the mass ratio of 1:0.8 to obtain the polyurethane structural adhesive.

(3) Preparation of polyurethane coatings

65 parts of castor oil polyol and 60 parts of isophorone diisocyanate (IPDI) are mixed in 5 parts of acetone, 2 parts of dibutyltin dilaurate is added, and the mixture reacts for 2 hours at the temperature of 50 ℃ to obtain prepolymer mixed liquid. And adding 15 parts of epoxy resin iii, 18 parts of flame retardant casein and 9 parts of hydrophilic chain extender dihydroxy half ester into the prepolymer mixed solution, and reacting at the temperature of 50 ℃ for 3 hours to obtain polymer mixed solution. And cooling the polymer mixed solution to 30 ℃, adding 25 parts of neutralizing agent triethylamine to neutralize the polymer mixed solution to be neutral, and adding 30 parts of deionized water to perform high-speed shearing emulsification to form polyurethane emulsion. And distilling the polyurethane emulsion under reduced pressure to remove acetone to obtain the waterborne polyurethane coating.

Example 5

(1) Preparation of vegetable oil polyols

265g peanut oil (containing 1mol of double bond), 56g ethylene (2mol), 42.45g Grubbs 2-substituted catalyst (0.05mol) were reacted in a 60 ℃ reaction kettle for 3 hours to obtain a vegetable oil with the pendant chains removed as component I. 188g of 7-oxabicyclo [4,1,0] -2, 4-heptadiene (2mol) were used as component II. Simultaneously pumping the component I and the component II into a first micro-anti-mixer 1 at a sample injection rate of 1.0mL/min and a sample injection rate of 4.0mL/min, mixing, pumping into a first micro-reactor 2(20mL), keeping the reaction for 4min, and reacting at the normal pressure and 190 ℃ to obtain the epoxy vegetable oil. Simultaneously pumping a mixture of epoxy vegetable oil and 138g of ethanol (3mol) and 7.04g of fluoroboric acid (0.08mol) with the sample injection rate of 7.3mL/min into a second micro-mixer 3, pumping the mixture into a second microreactor 4(86.1mL) after mixing, keeping the reaction for 7min, reacting at normal pressure and 100 ℃, reacting the obtained product with 42.4g of Pd/C (0.4mol) under the condition of continuously introducing hydrogen for 9h, and washing with water to obtain the peanut oil polyol (the hydroxyl value is 132 mgKOH/g).

(2) Preparation of polyurethane structural adhesive

The preparation method of the first component comprises the following steps: adding 100 parts of peanut oil polyalcohol and 10 parts of trimethylolpropane into a reaction kettle, heating to 110 ℃, stirring and dehydrating for 2 hours under the vacuum degree of less than or equal to-0.09 Mpa at the rotating speed of 1200r/min, then cooling to below 60 ℃, transferring into a stirring machine at the rotating speed of 1200r/min, then adding 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KH-550, 4 parts of silicon dioxide-supported organotin ii and 2 parts of molecular sieve, stirring for 30 minutes under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a first component; the preparation method of the second component comprises the following steps: toluene Diisocyanate (TDI): adding polymethylene polyphenyl polyisocyanate (PAPI) of 7:3 into a stirrer at the rotation speed of 1200r/min, stirring for 30min under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a second component; the sizing is carried out: and mixing the first component and the second component according to the mass ratio of 1:0.8 to obtain the polyurethane structural adhesive.

(3) Preparation of polyurethane coatings

65 parts of peanut oil polyol and 60 parts of isophorone diisocyanate (IPDI) are mixed in 5 parts of acetone, 2 parts of dibutyltin dilaurate is added, and the mixture reacts for 2 hours at the temperature of 50 ℃ to obtain prepolymer mixed liquid. And adding 15 parts of epoxy resin iii, 18 parts of flame retardant casein and 9 parts of hydrophilic chain extender dihydroxy half ester into the prepolymer mixed solution, and reacting at the temperature of 50 ℃ for 3 hours to obtain polymer mixed solution. And cooling the polymer mixed solution to 30 ℃, adding 25 parts of neutralizing agent triethylamine to neutralize the polymer mixed solution to be neutral, and adding 30 parts of deionized water to perform high-speed shearing emulsification to form polyurethane emulsion. And distilling the polyurethane emulsion under reduced pressure to remove acetone to obtain the waterborne polyurethane coating.

Comparative example

(1) Preparation of vegetable oil polyols

265g of peanut oil (containing 1mol of double bonds) were taken as component I. 188g of 7-oxabicyclo [4,1,0] -2, 4-heptadiene (2mol) were used as component II. Simultaneously pumping the component I and the component II into a first micro-back mixer 1 at a sample injection rate of 0.8mL/min and 4.5mL/min, mixing, pumping into a first microreactor 2(15.9mL), keeping the reaction for 3min, and reacting at the normal pressure and 180 ℃ to obtain the epoxy vegetable oil. Simultaneously pumping a mixture of epoxy vegetable oil and 185g of 2-butanol (2.5mol) with the sample injection rate of 8.6mL/min and 8.8g of fluoroboric acid (0.1mol) into a second micro-mixer 3, pumping the mixture into a second micro-reactor 4(83.4mL) after mixing, keeping the reaction for 6min, reacting at normal pressure and 120 ℃, reacting the obtained product with 48.76g of Pd/C (0.46mol) under the condition of continuously introducing hydrogen for 10h, and washing with water to obtain the peanut oil polyol (hydroxyl value is 195 mgKOH/g).

(2) Preparation of polyurethane structural adhesive

The preparation method of the first component comprises the following steps: adding 100 parts of peanut oil polyalcohol and 10 parts of trimethylolpropane into a reaction kettle, heating to 110 ℃, stirring and dehydrating for 2 hours under the vacuum degree of less than or equal to-0.09 Mpa at the rotating speed of 1200r/min, then cooling to below 60 ℃, transferring into a stirring machine at the rotating speed of 1200r/min, then adding 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KH-550, 4 parts of silicon dioxide-supported organotin ii and 2 parts of molecular sieve, stirring for 30 minutes under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a first component; the preparation method of the second component comprises the following steps: toluene Diisocyanate (TDI): adding polymethylene polyphenyl polyisocyanate (PAPI) of 7:3 into a stirrer at the rotation speed of 1200r/min, stirring for 30min under the vacuum degree of less than or equal to-0.09 Mpa, and discharging to obtain a second component; the sizing is carried out: and mixing the first component and the second component according to the mass ratio of 1:0.8 to obtain the polyurethane structural adhesive.

(3) Preparation of polyurethane coatings

65 parts of peanut oil polyol and 60 parts of isophorone diisocyanate (IPDI) are mixed in 5 parts of acetone, 2 parts of dibutyltin dilaurate is added, and the mixture reacts for 2 hours at the temperature of 50 ℃ to obtain prepolymer mixed liquid. And adding 15 parts of epoxy resin iii, 18 parts of flame retardant casein and 9 parts of hydrophilic chain extender dihydroxy half ester into the prepolymer mixed solution, and reacting at the temperature of 50 ℃ for 3 hours to obtain polymer mixed solution. And cooling the polymer mixed solution to 30 ℃, adding 25 parts of neutralizing agent triethylamine to neutralize the polymer mixed solution to be neutral, and adding 30 parts of deionized water to perform high-speed shearing emulsification to form polyurethane emulsion. And distilling the polyurethane emulsion under reduced pressure to remove acetone to obtain the waterborne polyurethane coating.

The invention relates to a relative determination method of vegetable oil polyol, polyurethane structural adhesive and polyurethane coating prepared by the embodiments, which comprises the following steps:

(1) determining the hydroxyl value of the vegetable oil polyol according to GB/T12008.3-2009;

(2) determining the Shore hardness of the polyurethane structural adhesive according to GB/T531.1-2008;

(3) the right-angle tear strength of the polyurethane structural adhesive is determined according to GB/T529 and 2008;

(4) the shear strength of the polyurethane structural adhesive is determined according to GB/T7124-;

(5) the tensile strength of the polyurethane structural adhesive was determined according to GB/T528-2009.

(6) The actual drying time of the coating is determined according to GB/T1728-1979 (1989);

(7) the 60 ℃ gloss of the coatings was determined according to GB/T9754-1988;

(8) the swing rod hardness of the coating is determined according to GB/T1730-1993;

(9) impact resistance of the coatings was determined according to GB/T1732-1993;

(10) the water resistance of the coatings was determined according to GB/T1733-1993.

The performance indexes of the vegetable oil-based polyurethane structural adhesives prepared in examples 1 to 5 and the comparative example are shown in table 1, and the performance indexes of the vegetable oil-based polyurethane coating prepared in the comparative example are shown in table 2.

TABLE 1

As can be seen from table 1: comparative example the procedure for removing the vegetable oil pendant chain in the reaction step was omitted, and the other procedures were the same as in example 1. It can be known from examples 1 to 5 and comparative examples that the curing speed, shore hardness, right-angle tear strength, shear strength and tensile strength of the polyurethane structural adhesive can be remarkably improved after the suspension chains in the vegetable oil are removed. Wherein, the embodiment 1 is the best embodiment, the performance of the polyurethane structural adhesive is optimal: the curing speed is fastest, and the Shore hardness, the right-angle tear strength, the shear strength and the tensile strength are all the greatest.

TABLE 2

As can be seen from table 2: comparative example the procedure for removing the vegetable oil pendant chain in the reaction step was omitted, and the other procedures were the same as in example 1. It is understood from examples 1 to 5 and comparative examples that the removal of the pendant chains from the vegetable oil significantly improves the dry time, 60 ° gloss, pendulum hardness, impact resistance, and water resistance of the polyurethane coating. Among them, example 1 is the best example, and the performance of the polyurethane coating is the best: the dry time is shortest, the gloss is best, the hardness is highest, the impact resistance is best, and the water resistance is good.

The present invention provides a vegetable oil polyol, a preparation method thereof and an application thereof in polyurethane materials, and a method and a way for realizing the technical scheme are numerous, the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the present invention, and the improvements and decorations should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.