GB2589033A

GB2589033A - Vegetable oil polyol and preparation method and application thereof in polyurethane material

Info

Publication number: GB2589033A
Application number: GB2101898.1A
Authority: GB
Inventors: Guo Kai; Fang Zheng; He Wei; Ouyang Pingkai; Liu Fujian; Huang Yiping; Chen Changzhu; Ma Ren
Original assignee: Nanjing Tech University
Current assignee: Nanjing Tech University
Priority date: 2021-01-25
Filing date: 2021-02-11
Publication date: 2021-05-19
Anticipated expiration: 2041-02-11
Also published as: GB2589033B; CN112898160B; GB202101898D0; CN112898160A

Abstract

A vegetable oil polyol preparation method comprises of the following steps: [i] reacting vegetable oil with ethylene and a Grubbs Catalyst 2nd Generation to obtain vegetable oil with a suspension chain removed, [ii] respectively and simultaneously pumping the vegetable oil with the suspension chain removed obtained in step [i] and 7-azabicyclo(4,1,0)-2,4-heptadiene into a first micromixer of a micro channel modular reaction device for mixing, and pumping the mixture into a first microreactor for reaction after mixing to obtain epoxidised vegetable oil, [iii] respectively and simultaneously pumping the epoxidised vegetable oil obtained in step [ii] and a mixed solution made of a ring-opening reagent and a catalyst into a second micromixer of the micro channel modular reaction device for mixing, and pumping the mixture into a second microreactor for a ring-opening reaction after mixing to obtain a ring-opening product, and [iv] carrying out a hydrogenation reaction on the ring-opening product obtained in step [iii] with a Pd/C catalyst and hydrogen in the reaction kettle to obtain the vegetable oil polyol. Also disclosed is a vegetable oil polyol prepared using the method; and use of the vegetable oil polyol in a polyurethane structural adhesive and a polyurethane coating.

Description

VEGETABLE OIL POLYOL AND PREPARATION METHOD AND APPLICATION THEREOF IN POLYURETHANE MATERIAL

TECHNICAL FIELD

The present invention relates to the field of vegetable oil polyol technologies, and more particularly, relates to a vegetable oil polyol and a preparation method and an application thereof in a polyurethane material.

BACKGROUND

A polyurethane is a polymer with repeated structural units of carbamate chain segments, which is made by a reaction of an isocyanate and a polyol. Polyurethane products are divided into foaming products and non-foaming products. The foaming products comprise soft, hard and semi-hard polyurethane foam plastics; and the non-foaming products comprise coatings, adhesives, synthetic leather, elastomers, elastic fibers, and the like. Polyurethane materials have an excellent performance, a wide application, and many kinds of products.

At present, there are many kinds of polyurethane polyols, and dominant polyols in the market are mainly some polyether-type polyols obtained by a reaction of a high-functionality hydroxyl compound and an amine compound with propylene epoxide or ethylene oxide. In addition to the polyether-type polyols, there are also polyester polyols, modified graft polyether polyols, and the like. These polyols are all downstream products of petroleum, with a strong resource dependence, a high price, and a poor process safety. Therefore, it is an important trend in research and industrial development of the polyurethane polyol to replace petrochemical resources with bio-based raw materials, develop a vegetable oil polyol, improve a product quality, reduce a resource dependence, and improve a process safety.

The vegetable oil polyol is a substitute for a petroleum-based polyol, with an outstanding environmental protection value. The vegetable oil polyol has a wide range of raw materials, comprising edible oils such as peanut oil, rapeseed oil, soybean oil, castor oil, olive oil, palm oil, and the like, as well as non-edible oils such as jatropha oil, Pistacia chinensis oil, and the like.

However, most of the vegetable oil polyols synthesized currently contain a suspension chain, which leads to a low iodine value and a high epoxy value of the polyols, thus affecting a performance of synthesized polyurethane materials.

SUMMARY

Objective of the present invention: a technical problem to be solved by the present invention is to provide a vegetable oil polyol and a preparation method thereof aiming at the deficiencies of the prior art, so as to solve problems of a large hydroxyl value and a high viscosity of generated polyol products caused by a suspension chain in vegetable oil, thus improving a property of polyurethane materials.

In order to achieve the above objective, the technical solutions used in the present invention are as follows.

A preparation method of a vegetable oil polyol comprises the following steps of (1) reacting vegetable oil with ethylene and a Grubbs Catalyst 2114 Generation in a reaction kettle to obtain vegetable oil with a suspension chain removed; (2) respectively and simultaneously pumping the vegetable oil with the suspension chain removed obtained in step (1) and 7-azabicyclo[4,1,0]-2,4-heptadiene into a first micromixer of a micro channel modular reaction device for mixing, and pumping the mixture into a first microreactor for reaction after mixing to obtain epoxidized vegetable oil; (3) respectively and simultaneously pumping the epoxidized vegetable oil obtained in step (2) and a mixed solution made of a ring-opening reagent and a catalyst into a second micromixer of the micro channel modular reaction device for mixing, and pumping the mixture into a second microreactor for a ring-opening reaction after mixing to obtain a ring-opening product; and (4) carrying out a hydrogenation reaction on the ring-opening product obtained in step (3) with a Pd/C catalyst and hydrogen in the reaction kettle to obtain the vegetable oil polyol.

Specifically, in step (1), the vegetable oil is any one of soybean oil, corn oil, peanut oil, and castor oil, and is preferably the peanut oil; a molar ratio of a double bond in the vegetable oil to the ethylene and the Grubbs Catalyst 2"'l Generation is 1: (1 to 2): (0: 05 to 0.2), and is preferably 1: 2: 0.05; a reaction temperature is 50°C to 70°C, and is preferably 60°C; and the reaction lasts for 2 hours to 4 hours, and preferably lasts for 3 hours. When the polyol has the suspension chain, the polyol is too rigid, so that properties and mechanical properties of some polyurethane materials are not good enough to meet a demand. Therefore, it is necessary to remove the suspension chain in the vegetable oil. A principle of the reaction in step (1) is that a complex may be formed under attraction of an ethylenic bond by adding metallic ruthenium, the ethylene is coordinated with the complex to form a four-membered ring between two alkenes through ruthenium, the four-membered ring is subjected to ring-opening under a heating condition, a long-chain hydrocarbon is departed and forms a long-chain end olefin with an olefin, and a structure of a terminal olefin is formed in the vegetable oil.

Specifically, in step (2), the 7-azabicyclo[4,1,0]-2,4-heptadiene is synthesized from 3,4-dibromo-7-oxabicyclo[4,1,0]heptane, 1,8-diazabi cy clo [5.4.0] undec-7-ene, and diethyl ether (reference document: Direct laser writing of poly(phenylene vinylene) on poly(barrelene), DOI: 10.1039/dOpy00869a); and a reaction molar ratio of the vegetable oil with the suspension chain removed obtained in step (1) to the 7-azabicyclo[4,1,0]-2,4-heptadiene is 1: 2. Step (2) aims to introduce a structure of an epoxy group into a product through a Diels-Alder reaction.

Preferably, in step (2), a flow rate of the vegetable oil with the suspension chain removed obtained in step (1) pumped into the micro channel modular reaction device is 0.6 mL/min to 1.2 mL/min, and is preferably 0.8 mL/min; a flow rate of the 7-azabicyclo[4,1,0]-2,4-heptadiene pumped into the micro channel modular reaction device is 3 mL/min to 5 mL/min, and is preferably 4.5 mL/min; a volume of the first microreactor is 7.2 mL to 31 mL, and is preferably 15 9 mL; a reaction temperature is controlled to be 170°C to 200°C, and is preferably 180°C; and the reaction remains for 2 minutes to 5 minutes, and preferably remains for 3 minutes.

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

Preferably, in step (3), a flow rate of the mixed solution made of the ring-opening reagent and the catalyst pumped into the micro channel modular reaction device is 5.5 mL/min to 10.0 mL/min, and is preferably 8.6 mL/min; a volume of the second microreactor is 45.5 mL to 129.6 mL, and is preferably 83 4 mL; a reaction temperature of the ring-opening reaction is controlled to be 80°C to 130°C, and is preferably 120°C; and the reaction remains for 5 minutes to 8 minutes, and preferably remains for 6 minutes.

Preferably, in step (4), a reaction molar ratio of the ring-opening product obtained in step (3) to the Pd/C catalyst is 1: (0.3 to 0.5), and is preferably 1: 0.46; the hydrogen is introduced to keep a pressure of the reaction kettle at about 1 MPa; and the reaction lasts for 8 hours to 12 hours, and preferably lasts for 10 hours. Step (4) aims to restore double bond in a product through hydrogenation.

Further, the vegetable oil polyol prepared by the above preparation method also falls within the scope of protection of the present invention.

Further, the present invention also seeks to protect an application of the above vegetable oil polyol in preparing a polyurethane structural adhesive.

Specifically, a preparation method of the polyurethane structural adhesive is as follows (the amount "part" of each raw material is "part by weight").

(1) A preparation method of an ingredient 1 is as follows: 100 parts of vegetable oil polyol and 10 parts of trimethylolpropane are added into a reaction kettle, heated to 110°C, stirred and dehydrated at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 NIPa for 2 hours, then cooled to less than 60°C, and transferred to a stirrer at a rotating speed of 1,200 r/min, and then, 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KH-550, 4 parts of organotin ii immobilized on silicon dioxide, and 2 pans of molecular sieve are added, stirred under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient I. (2) A preparation method of an ingredient ^ is as follows: toluene diisocyanate (TDI) and polyaryl polymethylene isocyanate (PAPI) are added into a stirrer according to a ratio of 7: 3, stirred at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient II.

(3) Sizing for use: the ingredient I and the ingredient II are mixed according to a mass ratio of 1: 0.8 to obtain the polyurethane structural adhesive.

Structural formulas of the plasticizer i and the organotin ii are as follows: Si 0-Si--SnCI3 Si CC "gy 1 ii Further, the present invention also seeks to protect an application of the above vegetable oil polyol in preparing a polyurethane coating.

Specifically, a preparation method of the polyurethane coating is as follows (the amount "part" of each raw material is "part by weight").

parts of vegetable oil polyol and 60 parts of isophorone diisocyanate (IPDI) are mixed in 5 parts of acetone, and 2 parts of dibutyltin dilaurate is added to react at 50°C for 2 hours to obtain a prepolymer mixed solution. 15 parts of epoxy resin iii, 18 parts of casein protein as flame retardant, and 9 parts of dihydroxy half-ester as hydrophilic chain-extending agent are added into the prepolymer mixed solution, and reacted at 50°C for 3 hours to obtain a polymer mixed solution. After cooling the polymer mixed solution to 30°C, 25 parts of triethylamine as neutralizer is added to neutralize the polymer mixed solution to be neutral, and 30 parts of deionized water is added for high-speed shearing and emulsification to form a polyurethane emulsion. The polyurethane emulsion is distilled under a reduced pressure to remove the acetone to obtain a flame-retardant vegetable oil-based waterborne polyurethane coating.

A structural formula of the epoxy resin iii is as follows: 0 0 ia ),Lcyk \ 0 0 iii Beneficial effects: 1. According to the present invention, the suspension chain in the vegetable oil is successfully removed first, so that the polyol has moderate hydroxyl value and viscosity, and the vegetable oil polyol prepared by a micro channel technology can replace a traditional polyol to be applied to prepare a polyurethane structural adhesive and a polyurethane coating. Meanwhile, the preparation process is simple, and has a convenient operation, low energy consumption, few side reactions, and a high reaction efficiency.

2. A curing speed, a hardness, and a strength of the polyurethane structural adhesive prepared by the present invention are improved.

3. The vegetable oil polyol prepared by the present invention has a good miscibility, and a volume of an organic solvent required for preparing the polyurethane coating is greatly reduced; and a hardness and an impact resistance of the prepared polyurethane coating are improved with a good gloss.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention is further described in detail with reference to the accompanying drawings and the specific embodiments, and the advantages of the above and/or other aspects of the present invention will become clearer.

FIG. I is a flow chart of a synthesis process of a vegetable oil polyol in Embodiment 2. FIG. 2 is a H1 NMR spectrum of soybean oil in Embodiment 2.

FIG. 3 is a W NMR spectrum of soybean oil with a suspension chain removed in Embodiment 2.

DETAILED DESCRIPTION

The present invention can be better understood according to the following embodiments.

Embodiment 1 A vegetable oil polyol was synthesized according to a process flow chart shown in FIG. (1) Preparation of vegetable oil polyol 265 g of peanut oil (containing 1 mol of double bonds), 56 g of ethylene (2 mol), and 42.45 g of Grubbs Catalyst 2"d Generation (0.05 mol) were reacted in a reaction kettle at 60°C for 3 hours to obtain vegetable oil with a suspension chain removed, which was used as an ingredient I. 188 g of 7-azabicyclo[4,1,0]-2,4-heptadiene (2 mol) was used as an ingredient II. The ingredient I and the ingredient II were simultaneously pumped into a first micromixer 1 at an introduction rate of 0.8 mL/min and an introduction rate of 4.5 mL/min respectively, and pumped into a first microreactor 2 (15 9 mL) after mixing, and the reaction remained for 3 minutes. Epoxidized vegetable oil was obtained by the reaction under a normal pressure at 180°C. The epoxidized vegetable oil and a mixture of 185 g of 2-butanol (2.5 mol) and 8.8 g of fluoroboric acid (0.1 mol) with an introduction rate of 8 6 mL/min were simultaneously pumped into a second micromixer 3, and pumped into a second microreactor 4 (83 4 mL) after mixing, the reaction remained for 6 minutes, and the reaction was carried out under a normal pressure at 120°C. An obtained product was reacted with 48.76 g of Pd/C (0.46 mol) under a condition of continuously introducing hydrogen for 10 hours, and then washed with water to obtain a peanut oil polyol (with a hydroxyl value of 125 mgKOH/g).

(2) Preparation of polyurethane structural adhesive A preparation method of the ingredient I was as follows: 100 parts of peanut oil polyol and 10 parts of trimethylolpropane were added into a reaction kettle, heated to 110°C, stirred and dehydrated at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 M1Pa for 2 hours, then cooled to less than 60°C, and transferred to a stirrer at a rotating speed of 1,200 r/min. Then, 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KH-550, 4 parts of organotin ii immobilized on silicon dioxide, and 2 parts of molecular sieve were added, stirred under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient I. A preparation method of the ingredient II was as follows: toluene diisocyanate (TDI) and polyaryl polymethylene isocyanate (PAPI) were added into a stirrer according to a ratio of 7: 3, stirred at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient II. Sizing for use was carried out: the ingredient I and the ingredient II were mixed according to a mass ratio of 1: 0.8 to obtain the polyurethane structural adhesive. (3) Preparation of polyurethane coating parts of peanut oil polyol and 60 parts of isophorone diisocyanate (IPDI) were mixed in 5 parts of acetone, and 2 parts of dibutyltin dilaurate was added to react at 50°C for 2 hours to obtain a prepolymer mixed solution. 15 parts of epoxy resin iii, 18 parts of casein protein as flame retardant, and 9 parts of dihydroxy half-ester as hydrophilic chain-extending agent were added into the prepolymer mixed solution, and reacted at 50°C for 3 hours to obtain a polymer mixed solution. After cooling the polymer mixed solution to 30°C, 25 parts of triethylamine as neutralizer was added to neutralize the polymer mixed solution to be neutral, and 30 parts of deionized water was added for high-speed shearing and emulsification to form a polyurethane emulsion. The polyurethane emulsion was distilled under a reduced pressure to remove the acetone to obtain a waterborne polyurethane coating.

Embodiment 2 A vegetable oil polyol was synthesized according to the process shown in FIG. 1.

g of soybean oil (containing I mol of double bonds), 28 g of ethylene (I mol), and 84.9 g of Grubbs Catalyst 2"d Generation (0.1 mol) were reacted in a reaction kettle at 50°C for 2 hours to obtain vegetable oil with a suspension chain removed, which was used as an ingredient I. FIG. 2 was a H1 NMR spectrum of the soybean oil with a suspension chain not removed, and the H' NMR spectrum after the suspension chain removed was shown in FIG. 3. Comparing the H1 NMR spectra of raw materials with that of products, it was found that a number of alkyl hydrogens in high field decreased, and a peak of olefinic hydrogen between chemical shifts 5.0 to 5.5 produced more cleavage due to the departure of the suspension chain, which proved the removal of the suspension chain.

188 g of 7-azabicyclo[4,1,0]-2,4-heptadiene (2 mol) was used as an ingredient II. The ingredient I and the ingredient II were simultaneously pumped into a first micromixer 1 at an introduction rate of 0.6 mL/min and an introduction rate of 3 0 mL/min respectively, and pumped into a first microreactor 2 (9 mL) after mixing, and the reaction remained for 2.5 minutes. Epoxidized vegetable oil was obtained by the reaction under a normal pressure at 170°C. The epoxidized vegetable oil and a mixture of 64 g of methanol (2 mol) and 4.4 g of fluoroboric acid (0.05 mol) with an introduction rate of 6 mL/min were simultaneously pumped into a second micromixer 3, and pumped into a second microreactor 4 (48 mL) after mixing, the reaction remained for 5 minutes, and the reaction was carried out under a normal pressure at 90°C. An obtained product was reacted with 31.8 g of Pd/C (0.3 mol) under a condition of continuously introducing hydrogen for 8 hours, and then washed with water to obtain a soybean oil polyol (with a hydroxyl value of 137 mgKOH/g).

(2) Preparation of polyurethane structural adhesive A preparation method of the ingredient I was as follows: 100 parts of soybean oil polyol and 10 parts of trimethylolpropane were added into a reaction kettle, heated to 110°C, stirred and dehydrated at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 MiPa for 2 hours, then cooled to less than 60°C, and transferred to a stirrer at a rotating speed of 1,200 r/min. Then, 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KM-550, 4 parts of organotin ii immobilized on silicon dioxide, and 2 parts of molecular sieve were added, stirred under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient I. A preparation method of the ingredient II was as follows: toluene diisocyanate (TDI) and polyaryl polymethylene isocyanate (PAPI) were added into a stirrer according to a ratio of 7: 3, stirred at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient II. Sizing for use was carried out: the ingredient I and the ingredient II were mixed according to a mass ratio of 1:0.8 to obtain the polyurethane structural adhesive.

(3) Preparation of polyurethane coating parts of soybean oil polyol and 60 parts of isophorone diisocyanate (IPDI) were mixed in 5 parts of acetone, and 2 parts of dibutyltin dilaurate was added to react at 50°C for 2 hours to obtain a prepolymer mixed solution. 15 parts of epoxy resin iii, 18 parts of casein protein as flame retardant, and 9 parts of dihydroxy half-ester as hydrophilic chain-extending agent were added into the prepolymer mixed solution, and reacted at 50°C for 3 hours to obtain a polymer mixed solution. After cooling the polymer mixed solution to 30°C, 25 parts of triethylamine as neutralizer was added to neutralize the polymer mixed solution to be neutral, and 30 parts of deionized water was added for high-speed shearing and emulsification to form a polyurethane emulsion. The polyurethane emulsion was distilled under a reduced pressure to remove the acetone to obtain a waterborne polyurethane coating. Embodiment 3 (1) Preparation of vegetable oil polyol 212 g of corn oil (containing 1 mol of double bonds), 42 g of ethylene (1.5 mol), and 127.35 g of Grubbs Catalyst T'd Generation (0.15 mol) were reacted in a reaction kettle at 65°C for 3.5 hours to obtain vegetable oil with a suspension chain removed, which was used as an ingredient I. 188 g of 7-azabicyclo[4,1,0]-2,4-heptadiene (2 mol) was used as an ingredient II. The ingredient I and the ingredient II were simultaneously pumped into a first micromixer 1 at an introduction rate of 1.0 mL/min and an introduction rate of 4.0 mL/min respectively, and pumped into a first microreactor 2 (20 mL) after mixing, and the reaction remained for 4 minutes. Epoxidized vegetable oil was obtained by the reaction under a normal pressure at 190 °C. The epoxidized vegetable oil and a mixture of 138 g of ethanol (3.0 mol) and 7.04 g of fluoroboric acid (0.08 mol) with an introduction rate of 7 3 mL/min were simultaneously pumped into a second micromixer 3, and pumped into a second microreactor 4 (86.1 mL) after mixing, the reaction remained for 7 minutes, and the reaction was carried out under a normal pressure at 100°C. An obtained product was reacted with 42.4 g of Pd/C (0.4 mol) under a condition of continuously introducing hydrogen for 9 hours, and then washed with water to obtain a corn oil polyol (with a hydroxyl value of 148 mgKOH/g).

(2) Preparation of polyurethane structural adhesive A preparation method of the ingredient I was as follows: 100 parts of corn oil polyol and 10 parts of trimethylolpropane were added into a reaction kettle, heated to I 10°C, stirred and dehydrated at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 MPa for 2 hours, then cooled to less than 60°C, and transferred to a stirrer at a rotating speed of 1,200 r/min. Then, 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KH-550, 4 parts of organotin ii immobilized on silicon dioxide, and 2 parts of molecular sieve were added, stirred under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient I. A preparation method of the ingredient 11 was as follows: toluene diisocyanate (TDI) and polyaryl polymethylene isocyanate (PAPI) were added into a stirrer according to a ratio of 7: 3, stirred at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient II. Sizing for use was carried out: the ingredient I and the ingredient II were mixed according to a mass ratio of 1: 0.8 to obtain the polyurethane structural adhesive.

(3) Preparation of polyurethane coating parts of corn oil polyol and 60 parts of isophorone diisocyanate (IPDI) were mixed in 5 parts of acetone, and 2 parts of dibutyltin dilaurate was added to react at 50°C for 2 hours to obtain a prepolymer mixed solution. 15 parts of epoxy resin iii, 18 parts of casein protein as flame retardant, and 9 parts of dihydroxy half-ester as hydrophilic chain-extending agent were added into the prepolymer mixed solution, and reacted at 50°C for 3 hours to obtain a polymer mixed solution. After cooling the polymer mixed solution to 30°C, 25 parts of triethylamine as neutralizer was added to neutralize the polymer mixed solution to be neutral, and 30 parts of deionized water was added for high-speed shearing and emulsification to form a polyurethane emulsion. The polyurethane emulsion was distilled under a reduced pressure to remove the acetone to obtain a waterborne polyurethane coating.

Embodiment 4 (1) Preparation of vegetable oil polyol 303 g of castor oil (containing 1 mol of double bonds), 50.4 g of ethylene (1.8 mol), and 169.8 g of Grubbs Catalyst rd Generation (0.2 mol) were reacted in a reaction kettle at 70°C for 4 hours to obtain vegetable oil with a suspension chain removed, which was used as an ingredient I. 188 g of 7-azabicyclo[4,1,0]-2,4-heptadiene (2 mol) was used as an ingredient II. The ingredient I and the ingredient II were simultaneously pumped into a first micromixer 1 at an introduction rate of 1.2 mL/min and an introduction rate of 5.0 mL/min respectively, and pumped into a first microreactor 2 (31 mL) after mixing, and the reaction remained for 5 minutes. Epoxidized vegetable oil was obtained by the reaction under a normal pressure at 200°C. The epoxidized vegetable oil and a mixture of 180 g of n-propanol (3.0 mol) and 10.56 g of fluoroboric acid (0.12 mol) with an introduction rate of 10.0 mL/min were simultaneously pumped into a second micromixer 3, and pumped into a second microreactor 4 (129 6 mL) after mixing, the reaction remained for 8 minutes, and the reaction was carried out under a normal pressure at 130°C. An obtained product was reacted with 53 g of Pd/C (0.5 mol) under a condition of continuously introducing hydrogen for 12 hours, and then washed with water to obtain a castor oil polyol (with a hydroxyl value of 153 mgKOH/g).

(2) Preparation of polyurethane structural adhesive A preparation method of the ingredient I was as follows: 100 parts of castor oil polyol and 10 parts of trimethylolpropane were added into a reaction kettle, heated to 110°C, stirred and dehydrated at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 MPa for 2 hours, then cooled to less than 60°C, and transferred to a stirrer at a rotating speed of 1,200 r/min. Then, 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KH-550, 4 parts of organotin ii immobilized on silicon dioxide, and 2 parts of molecular sieve were added, stirred under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient I. A preparation method of the ingredient II was as follows: toluene diisocyanate (TM) and polyaryl polymethylene isocyanate (PAPI) were added into a stirrer according to a ratio of 7: 3, stirred at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient II. Sizing for use was carried out: the ingredient I and the ingredient II were mixed according to a mass ratio of 1: 0.8 to obtain the polyurethane structural adhesive.

(3) Preparation of polyurethane coating parts of castor oil polyol and 60 parts of isophorone diisocyanate (WDI) were mixed in 5 parts of acetone, and 2 parts of dibutyltin dilaurate was added to react at 50°C for 2 hours to obtain a prepolymer mixed solution. 15 parts of epoxy resin iii, 18 parts of casein protein as flame retardant, and 9 parts of dihydroxy half-ester as hydrophilic chain-extending agent were added into the prepolymer mixed solution, and reacted at 50°C for 3 hours to obtain a polymer mixed solution. After cooling the polymer mixed solution to 30°C, 25 parts of triethylamine as neutralizer was added to neutralize the polymer mixed solution to be neutral, and 30 parts of deionized water was added for high-speed shearing and emulsification to form a polyurethane emulsion. The polyurethane emulsion was distilled under a reduced pressure to remove the acetone to obtain a waterborne polyurethane coating Embodiment 5 (1) Preparation of vegetable oil polyol 265 g of peanut oil (containing 1 mol of double bonds), 56 g of ethylene (2 mol), and 42.45 g of Grubbs Catalyst 2"d Generation (0.05 mol) were reacted in a reaction kettle at 60°C for 3 hours to obtain vegetable oil with a suspension chain removed, which was used as an ingredient I. 188 g of 7-azabicyclo[4,1,0]-2,4-heptadiene (2 mol) was used as an ingredient II. The ingredient I and the ingredient H were simultaneously pumped into a first micromixer 1 at an introduction rate of 1.0 mL/min and an introduction rate of 4.0 mL/min respectively, and pumped into a first microreactor 2 (20 mL) after mixing, and the reaction remained for 4 minutes. Epoxidized vegetable oil was obtained by the reaction under a normal pressure at 190°C. The epoxidized vegetable oil and a mixture of 138 g of ethanol (3 mol) and 7.04 g of fluoroboric acid (0.08 mol) with an introduction rate of 7 3 mL/min were simultaneously pumped into a second micromixer 3, and pumped into a second microreactor 4 (86 1 mL) after mixing, the reaction remained for 6 minutes, and the reaction was carried out under a normal pressure at 100°C. An obtained product was reacted with 42.4 g of Pd/C (0.4 mol) under a condition of continuously introducing hydrogen for 9 hours, and then washed with water to obtain a peanut oil polyol (with a hydroxyl value of 132 mgKOH/g).

(2) Preparation of polyurethane structural adhesive A preparation method of the ingredient I was as follows: 100 parts of peanut oil polyol and 10 parts of trimethylolpropane were added into a reaction kettle, heated to 110°C, stirred and dehydrated at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 MiPa for 2 hours, then cooled to less than 60°C, and transferred to a stirrer at a rotating speed of 1,200 r/min. Then, 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KH-550, 4 parts of organotin ii immobilized on silicon dioxide, and 2 parts of molecular sieve were added, stirred under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient I. A preparation method of the ingredient II was as follows: toluene diisocyanate (TDI) and polyaryl polymethylene isocyanate (PAPI) were added into a stirrer according to a ratio of 7: 3, stirred at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient II. Sizing for use was carried out: the ingredient I and the ingredient II were mixed according to a mass ratio of 1: 0.8 to obtain the polyurethane structural adhesive.

(3) Preparation of polyurethane coating parts of peanut oil polyol and 60 parts of isophorone diisocyanate (IPDI) were mixed in 5 parts of acetone, and 2 parts of dibutyltin dilaurate was added to react at 50°C for 2 hours to obtain a prepolymer mixed solution. 15 parts of epoxy resin iii, 18 parts of casein protein as flame retardant, and 9 parts of dihydroxy half-ester as hydrophilic chain-extending agent were added into the prepolymer mixed solution, and reacted at 50°C for 3 hours to obtain a polymer mixed solution. After cooling the polymer mixed solution to 30°C, 25 parts of triethylamine as neutralizer was added to neutralize the polymer mixed solution to be neutral, and 30 parts of deionized water was added for high-speed shearing and emulsification to form a polyurethane emulsion. The polyurethane emulsion was distilled under a reduced pressure to remove the acetone to obtain a waterborne polyurethane coating.

Comparative Example

(1) Preparation of vegetable oil polyol 265 g of peanut oil (containing 1 mol of double bonds) was used as an ingredient I. 188 g of 7-azabicyclo[4,1,0]-2,4-heptadiene (2 mol) was used as an ingredient II. The ingredient I and the ingredient II were simultaneously pumped into a first micromixer I at an introduction rate of 0.8 mL/min and an introduction rate of 4.5 mL/min respectively, and pumped into a first microreactor 2 (15 9 mL) after mixing, and the reaction remained for 3 minutes. Epoxidized vegetable oil was obtained by the reaction under a normal pressure at 180°C. The epoxidized vegetable oil and a mixture of 185 g of 2-butanol (2.5 mol) and 8.8 g of fluoroboric acid (0.1 mol) with an introduction rate of 8 6 mL/min were simultaneously pumped into a second micromixer 3, and pumped into a second microreactor 4 (83 4 mL) after mixing, the reaction remained for 6 minutes, and the reaction was carried out under a normal pressure at 120°C. An obtained product was reacted with 48.76 g of Pd/C (0.46 mol) under a condition of continuously introducing hydrogen for 10 hours, and then washed with water to obtain a peanut oil polyol (with a hydroxyl value of 195 mgKOH/g).

(2) Preparation of polyurethane structural adhesive A preparation method of the ingredient I was as follows: 100 parts of peanut oil polyol and 10 parts of trimethylolpropane were added into a reaction kettle, heated to 110°C, stirred and dehydrated at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 MIPa for 2 hours, then cooled to less than 60°C, and transferred to a stirrer at a rotating speed of 1,200 r/min. Then, 15 parts of plasticizer i, 3 parts of KH-560, 3 parts of KH-550, 4 parts of organotin ii immobilized on silicon dioxide, and 2 parts of molecular sieve were added, stirred under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient I. A preparation method of the ingredient 11 was as follows: toluene diisocyanate (TDI) and polyaryl polymethylene isocyanate (PAPI) were added into a stirrer according to a ratio of 7: 3, stirred at a rotating speed of 1,200 r/min under a vacuum degree less than or equal to -0.09 Mpa for 30 minutes, and discharged to obtain the ingredient II. Sizing for use was carried out: the ingredient I and the ingredient II were mixed according to a mass ratio of 1: 0.8 to obtain the polyurethane structural adhesive.

(3) Preparation of polyurethane coating parts of peanut oil polyol and 60 parts of isophorone diisocyanate (WDI) were mixed in 5 parts of acetone, and 2 parts of dibutyltin dilaurate was added to react at 50°C for 2 hours to obtain a prepolymer mixed solution. 15 parts of epoxy resin iii, 18 parts of casein protein as flame retardant, and 9 parts of dihydroxy half-ester as hydrophilic chain-extending agent were added into the prepolymer mixed solution, and reacted at 50°C for 3 hours to obtain a polymer mixed solution. After cooling the polymer mixed solution to 30°C, 25 parts of triethylamine as neutralizer was added to neutralize the polymer mixed solution to be neutral, and 30 parts of deionized water was added for high-speed shearing and emulsification to form a polyurethane emulsion. The polyurethane emulsion was distilled under a reduced pressure to remove the acetone to obtain a waterborne polyurethane coating.

Related determination methods of the present invention on the prepared vegetable oil polyol, polyurethane structural adhesive and polyurethane coating in each embodiment are as follows: (1) determine a hydroxyl value of the vegetable oil polyol according to GB/T 12008.3-2009; (2) determine a shore hardness of the polyurethane structural adhesive according to GB/T 531.1-2008; (3) determine a right-angle tear strength of the polyurethane structural adhesive according to GB/T 529-2008; (4) determine a shear strength of the polyurethane structural adhesive according to GB/T 7124-2008; (5) determine a tensile strength of the polyurethane structural adhesive according to GB/T 528-2009; 6) determine a hard drying time of the coating according to GB/T 1728-19790989); (7) determine a 60°gloss of the coating according to GB/T 9754-1988; (8) determine a pendulum hardness of the coating according to GB/T 1730-1993; (9) determine an impact resistance of the coating according to GB/T 1732-1993; and (10) determine a water resistance of the coating according to GB/T 1733-1993.

Property indexes of the vegetable oil-based polyurethane structural adhesives prepared in Embodiments 1 to 5, and Comparative Example are shown in Table 1, and property indexes of the vegetable oil-based polyurethane coatings prepared in Embodiments 1 to 5, and Comparative Example are shown in Table 2.

Table 1

Test item Embodiment Comparative Example 1 2 3 4 5 1 Curing speed 3.6 3.1 3.2 3.3 2.8 1.2 (mm/24h) Shore hardness A 70 53 56 61 55 43 Right-angled tear 15.3 142 13.8 13.2 13.5 11.4 strength (N/m) Shear strength (MPa) 5.1 4.5 4.6 4.2 3.8 2.7 Tensile strength (M Pa) 8.6 7.8 7.5 8.1 7.9 6.3 It can be seen from Table 1 that the step of removing the suspension chain in the vegetable oil in the reaction step is eliminated in Comparative Example, and other steps are the same as those in Embodiment 1. It can be known from Embodiments 1 to 5, and Comparative Example that, after the suspension chain in the vegetable oil is removed, the curing speed, the shore hardness, the right-angle tear strength, the shear strength, and the tensile strength of the polyurethane structural adhesive can be significantly improved. Embodiment 1 is an optimal embodiment, and the polyurethane structural adhesive has optimal properties: fastest curing speed as well as maximum shore hardness, right-angle tear strength, shear strength, and tensile strength.

Table 2

Test item Embodiment Comparative

Example

1 2 3 4 5 1 Hard drying time (h) 4 5 5.5 4.5 5.5 7 60° gloss 93 85 87 86 91 74 Pendulum hardness (s) 178.5 153.5 160.1 169.8 150.7 137.8 Impact resistance (cm) 50 45 40 45 50 35 Water resistance (h) 96, pass 96, pass 96, pass 96, pass 96, pass 48, not pass It can be seen from Table 2 that the step of removing the suspension chain in the vegetable oil in the reaction step is eliminated in Comparative Example, and other steps are the same as those in Embodiment 1. It can be known from Embodiments 1 to 5, and Comparative Example that, after the suspension chain in the vegetable oil is removed, the hard drying time, the 60° gloss, the pendulum hardness, the impact resistance, and the water resistance of the polyurethane coating can be significantly improved. Embodiment I is an optimal embodiment, and the polyurethane coating has optimal properties: shortest hard drying time, best gloss, highest hardness, best impact resistance, and good water resistance.

The present invention provides an idea and a method for a vegetable oil polyol and a preparation method and an application thereof in a polyurethane material, with many methods and ways to realize the technical solution specifically. Those described above are merely the preferred embodiments of the present invention, and it shall be pointed out that those of ordinary skills in the art may further make improvements and decorations without departing from the principle of the present invention, and these improvements and decorations shall also be regarded as falling within the scope of protection of the present invention. All unspecified components in the embodiments can be implemented in the prior art

Claims

CLAIMS1. A preparation method of a vegetable oil polyol, comprising the following steps of: (1) reacting vegetable oil with ethylene and a Grubbs Catalyst 2"d Generation in a reaction kettle to obtain vegetable oil with a suspension chain removed; (2) respectively and simultaneously pumping the vegetable oil with the suspension chain removed obtained in step (1) and 7-azabicyclo[4,1,0]-2,4-heptadiene into a first micromixer of a micro channel modular reaction device for mixing, and pumping the mixture into a first microreactor for reaction after mixing to obtain epoxidized vegetable oil; (3) respectively and simultaneously pumping the epoxidized vegetable oil obtained in step (2) and a mixed solution made of a ring-opening reagent and a catalyst into a second micromixer of the micro channel modular reaction device for mixing, and pumping the mixture into a second microreactor for a ring-opening reaction after mixing to obtain a ring-opening product; and (4) carrying out a hydrogenation reaction on the ring-opening product obtained in step (3) with a Pd/C catalyst and hydrogen in the reaction kettle to obtain the vegetable oil polyol.
2. The preparation method of the vegetable oil polyol according to claim 1, wherein in step (1), the vegetable oil is any one of soybean oil, corn oil, peanut oil, and castor oil; and a molar ratio of a double bond in the vegetable oil to the ethylene and the Grubbs Catalyst 2nd Generation is 1: (1 to 2): (0:05 to 0.2), a reaction temperature is 50°C to 70°C, and the reaction lasts for 2 hours to 4 hours.
3. The preparation method of the vegetable oil polyol according to claim 1, wherein in step (2), the 7-azabicyclo[4,1,0]-2,4-heptadiene is synthes zed from 3,4-dibromo-7-oxabicyclo[4,1,0]heptane, 1,8-diazabicyclo[5.4.0]undec-7-ene, and diethyl ether; and a reaction molar ratio of the vegetable oil with the suspension chain removed obtained in step (1) to the 7-azabicyclo[4,1,0]-2,4-heptadiene is 1:2.
4. The preparation method of the vegetable oil polyol according to claim 1, wherein in step (2), a flow rate of the vegetable oil with the suspension chain removed obtained in step (1) pumped into the micro channel modular reaction device is 0.6 mL/min to 1.2 mL/min; a flow rate of the 7-azabicyclo[4,1,0]-2,4-heptadiene pumped into the micro channel modular reaction device is 3 mL/min to 5 mL/min; and a volume of the first microreactor is 7.2 mL to 31 mL, a reaction temperature is controlled to be 170°C to 200°C, and the reaction remains for 2 minutes to 5 minutes.
5. The preparation method of the vegetable oil polyol according to claim 1, wherein in step (3), the ring-opening reagent is any one of methanol, ethanol, n-propanol, and 2-butanol; the catalyst is a fluoroboric acid; and a reaction molar ratio of the epoxidized vegetable oil obtained in step (2) to the ring-opening reagent and the catalyst is 1: (2 to 3): (0.05 to 0.12).
6. The preparation method of the vegetable oil polyol according to claim I, wherein in step (3), a flow rate of the mixed solution made of the ring-opening reagent and the catalyst pumped into the micro channel modular reaction device is 5.5 mL/min to 10 0 mL/min; and a volume of the second microreactor is 45.5 mL to 129.6 mL, a reaction temperature of the ring-opening reaction is controlled to be 80°C to 130°C, and the reaction remains for 5 minutes to 8 minutes.
7. The preparation method of the vegetable oil polyol according to claim I, wherein in step (4), a reaction molar ratio of the ring-opening product obtained in step (3) to the Pd/C catalyst is 1: (0.3 to 0.5), the hydrogen is introduced to keep a pressure of the reaction kettle at 1 MiPa, and the reaction lasts for 8 hours to 12 hours.
8. A vegetable oil polyol prepared by the preparation method according to any one of claims 1 to 7.
9. An application of the vegetable oil polyol according to claim 8 in preparing a polyurethane structural adhesive.
10. An application of the vegetable oil polyol according to claim 8 in preparing a polyurethane coating.