GB2589511A - Vegetable oil polyol and preparation method and application thereof - Google Patents

Vegetable oil polyol and preparation method and application thereof Download PDF

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GB2589511A
GB2589511A GB2101198.6A GB202101198A GB2589511A GB 2589511 A GB2589511 A GB 2589511A GB 202101198 A GB202101198 A GB 202101198A GB 2589511 A GB2589511 A GB 2589511A
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vegetable oil
reaction
preparation
reactor
epoxidized
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Guo Kai
Fang Zheng
He Wei
Liu Fujian
Huang Yiping
Zhu Ning
Yang Man
Chen Changzhu
Ma Ren
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Nanjing Tech University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/28—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
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    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation
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    • C08G2101/00—Manufacture of cellular products
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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  • General Chemical & Material Sciences (AREA)
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  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Compounds (AREA)

Abstract

A preparation method of a vegetable oil polyol comprising [i] adding a metal catalyst and an organic solvent system dissolved with secondary amine into a reactor, introducing hydrogen into the reactor, and then adding a glucose solution into the reactor to carry out a reductive ammonolysis reaction to obtain a mixed solution containing polyhydroxy compounds of formula III and formula IV;

Description

VEGETABLE OIL POLYOL AND PREPARATION METHOD AND APPLICATION THEREOF
TECHNICAL FIELD
The present invention belongs to the field of chemical materials arid production technologies, and particularly relates to a vegetable oil polyol and a preparation method and an application thereof
BACKGROUND
Polyurethane is a repeat unit structure with a carbamate chain segment, which is made by a reaction between an isocyanate arid a polyol, and is widely used in foam plastics, surface coatings, adhesives, sealants, complexing agent materials, and other fields. Polyurethane materials have excellent performances, wide application, and can be manufactured into multiple products, wherein polyurethane foaming plastics are most widely used. At present, consumption of petrochemical fuel resources and increasing concern about environmental problems force global researchers to use vegetable oil to prepare the polyurethane.
A vegetable oil polyol is mainly applied to the field of polyurethane preparation, and vegetable oil-based polyurethane materials prepared with the vegetable oil polyol fully meets requirements of environmental protection. Moreover, due to a hydrophobicity of fatty glyceride, which is a main ingredient of the vegetable oil, the vegetable oil-based polyurethane materials have good physical and chemical properties, especially have better hydrophobicity and thermal stability. Therefore, the vegetable oil polyol and the polyurethane materials thereof have been developed rapidly.
The vegetable oil polyol is an important renewable resource, which can react with isocyanate compounds to form the polyurethane, and is a good substitute for a petroleum-based polyol. In recent years, major methods for synthesizing the vegetable oil polyol are as follows: 1) an alcoholysis reaction is carried out on the vegetable oil and the polyol to generate a polyhydroxy compound; 2) unsaturated double bonds in the vegetable oil are oxidized with ozone to generate a polyhydroxy compound with terminated hydroxyl; and 3) the vegetable oil is oxidized into epoxidized vegetable oil, and then the polyhydroxy compound is generated by hydrolysis, hydrogenation, methyl esterification, or halogenation.
The method 1) and the method 3) in the above methods for synthesizing the vegetable oil polyol are often used. In CN1837180A and CN101139252A, the vegetable oil polyol is prepared by a three-step reaction of a1coholysis/epoxidation/ring opening with rapeseed oil and jatropha oil as raw materials respectively. In CN1837181A and CN10118803A, the vegetable oil polyol is prepared by a three-step reaction of epoxidation/ring opening/alcoholysis with rapeseed oil and jatropha oil as raw materials. In CN101906016A, the vegetable oil polyol is prepared by a two-step reaction of epoxidation/ring opening with rubber seed oil as a raw material. In CN101659627A, the vegetable oil polyol is prepared by a ring-opening reaction and an ester amidation reaction between the epoxidized vegetable oil and diol amine. In CN101747184A and CN101230020A, the vegetable oil polyol is prepared by a one-step method through an epoxidation reaction and a ring opening reaction under acidic conditions.
In the above patents, the vegetable oil polyol is synthesized on the basis of double-bond epoxy and then ring-opening, and small molecule alcohol, alcohol amine, or carboxylic acid is mainly used as a ring-opening reagent. However, there are some problems such as a low product quality, complicated post-treatment, an easy cross-linking side reaction in reaction, and the like, and a certain proportion of petrochemical polyol still needs to be compounded when applied to polyurethane materials.
SUMMARY
Objective of the present invention: in order to solve the problems that the vegetable oil polyol prepared by the existing preparation method is low in quality, complicated in post-treatment, and prone to cross-linking side reactions in reaction, a first aspect of the present invention provides a preparation method of a vegetable oil polyol; a second aspect of the present invention provides a vegetable oil polyol prepared by the above method, and the prepared vegetable oil polyol has high hydroxyl value, low viscosity and simple process, and the product does not need further refining treatment; a third aspect of the present invention provides an application of the vegetable oil polyol in preparing a polyurethane rigid foam, which can completely replace a traditional petrochemical polyol.
Technical solutions: the preparation method of the vegetable oil polyol according to the first aspect of the present invention comprises the following steps of (1) adding a metal catalyst and an organic solvent system dissolved with secondary amine into a reactor, introducing hydrogen into the reactor, and then adding a glucose solution into the reactor to carry out a reductive ammonolysis reaction to obtain a mixed solution containing polyhydroxy compounds of formula III and formula IV, wherein R is CH1 or CH2CH3; and (2) dissolving epoxidized vegetable oil and a basic catalyst into an organic solvent to obtain a mixed solution containing the epoxidized vegetable oil, and respectively and simultaneously pumping the mixed solution containing the epoxidized vegetable oil and the mixed solution containing the polyhydroxy compounds of formula In and formula IV obtained in step (1) into a microstructure reactor of a microchannel modular reaction device for reaction to obtain the vegetable oil polyol, wherein the epoxidized vegetable oil has an iodine value of 10 to 15 and an epoxy value of 6.0% to 6.7%. Preferably, the epoxy value of the obtained vegetable oil polyol is 0.25% to 1.00%.
In step (1), the glucose (I) and the secondary amine (II) are synthesized into polyhydroxy compounds (III, IV) according to a synthetic route shown in the figure: OH OH 0 OH OH OH HOH)Y HN,-R OH OH HOJ_NR,R
R
OH OH OH
I ii III wherein R is CH3 or CH2CH3; and A reaction formula of the bio-based polyol (vegetable oil polyol) of the present invention is as follows: OH OH 0 OH OH OH o
--
g+.able oil 1 HO + R HO I
OH OH
wherein R is C113 or CH2CH3.
In step (1), the metal catalyst is any one or a combination of several of Ni/Si02-A1203 (65vvt.%), Pt/C (lvvt.%), Pd/C (5wt.%) or Ru/C (5wt.%), preferably Ni/Si02-A1203 (65wt.%).
The metal catalysts are commercially available, and activated metal catalysts are preferred, and a preferred activation method of the metal catalyst is to put the metal catalyst into a reaction tube, introduce a certain flow of hydrogen, and calcine at 120°C to 350°C for two hours. The secondary amine is any one or a combination of dimethylamine and diethylamine, and preferably dimethylamine; the solvent in the organic solution is any one or a combination of several of tetrahydrofuran, methanol, ethanol, and ethyl acetate, and preferably tetrahydrofuran; and the organic solution dissolved with the secondary amine in step (1) has a concentration of 55wt..% to 75wt.%, and preferably 60wt.%. The glucose solution has a concentration of 20wt.% to 35wt9/10, and preferably 33wt.%; and a ratio of a mass of the metal catalyst to a molar weight of the glucose is 9 g to 31 g: 1 mol, and preferably 12 g: 1 mol. A reaction temperature is 110°C to 125°C, a reaction pressure is 6.0 Mpa to 7.5 Mpa, a reaction time lasts for 2 hours to 2.5 hours, a feeding speed of the glucose aqueous solution is 8.1 ml/min to 15 ml/min; preferably, the reaction temperature is 120°C, the reaction pressure is 7.0 Mpa, the reaction time lasts for 2 hours, and the feeding rate is 10 mL/min. Preferably, the reactor is a tank reactor.
In step (2), the epoxidized vegetable oil is any one or a combination of several of epoxidized peanut oil, epoxidized rapeseed oil, epoxidized cottonseed oil, and epoxidized soybean oil, and preferably an epoxidized vegetable oil prepared according to a preparation method of Chinese patent 2014104412890. The basic catalyst is any one or a combination of several of sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate, and preferably sodium carbonate, and the organic solvent is any one or a combination of several of tetrahydrofuran, methanol, ethanol, and ethyl acetate, and preferably tetrahydrofuran, wherein the solvent in the organic solution in step (1) is the same (:)+1 CH OH as the organic solvent in step (2). A mass percentage of the basic catalyst to the epoxidized vegetable oil is 0.02% to 0.1%, and preferably 0.08%; a mass ratio of the organic solvent to the epoxidized vegetable oil is 2 to 6: 1, and preferably 4.3: 1. A flow rate of the mixed solution containing polyhydroxy compounds of formula III and formula IV pumped into the microchannel modular reaction device is 1.0 ml/min to 3.0 ml/min, and a flow rate of the mixed solution containing epoxidized vegetable oil pumped into the microchannel modular reaction device is 2.0 ml/min to 4.0 ml/min. A reaction temperature in the microstructure reactor is 60°C to 100°C, and preferably 80°C; a reaction residence time is 10 minutes to 15 minutes, and preferably 12 minutes; and a volume of the microstnicture reactor is 40 mL to 120 mL.
A molar ratio of the basic catalyst to the secondary amine and the glucose in step (1) to an epoxy group of the epoxidized vegetable oil in step (2) is 1 to 1.05: 0.5 to 1.0, and preferably 1: 1: 0.8.
The microchannel modular reaction device comprises a micromixer, a microstructure heat exchanger, a tubular temperature control module and a microstructure reactor which are sequentially connected in series through a connecting pipe, wherein two accurate and low-arterial feed pumps are connected to the micromixer through a pipeline, one pump is responsible for pumping the mixed solution containing polyhydroxy compounds of formula III and formula IV, and the other pump is responsible for pumping the mixed solution obtained by dissolving the epoxidized vegetable oil and the basic catalyst into the organic solvent.
A model of the micromixer is preferably slit plate mixer LH25, a model of the microstructure heat exchanger is preferably coaxial heat exchanger, and a model of the microstructure reactor is Vapotech.
An effluent of the reaction solution of the microstructure reactor in step (2) is separated, an oil phase is washed with water to neutrality and then subjected to liquid separation again, and the solvent is evaporated from the oil phase to obtain the vegetable oil polyol.
The second aspect of the present invention provides the vegetable oil polyol prepared by the above method.
The third aspect of the present invention provides the application of the vegetable oil polyol in preparing polyurethane rigid foam.
Beneficial effects: (1) The biggest problem in ring-opening of the polyhydroxy compounds is the problem of high viscosity due to crosslinking caused by polyhydroxy. In the present invention, the epoxidized vegetable oil (an iodine value of 10 to 15 and an epoxy value of 6.0% to 6.7%) prepared according to Chinese patent 2014104412890 is employed, and the vegetable oil polyol which retains the epoxy value and the iodine value is obtained through cooperative control of a microreaction structurer, wherein the structure of the vegetable oil polyol obtained is quite different from that of the existing vegetable oil polyol, and the viscosity of the vegetable oil polyol obtained is greatly reduced and a fluidity thereof is increased, which is beneficial to foam making. (2) In the present invention, the polyhydroxy compounds of formula III and formula IV are used as novel ring-opening reagents, basic groups are introduced into the structure, a plurality of hydroxyl groups exist in the structure, which have high functional groups, so that the vegetable oil polyol product prepared by ring-opening can be guaranteed to have higher hydroxyl values, cross-linking side reactions can be reduced, and the product viscosity can be reduced. (3) The hydroxyl position of the vegetable oil polyol is uniform, which can completely replace the traditional petrochemical polyol applied to polyurethane rigid foam. The vegetable oil polyol can foam independently without adding a basic catalyst during foaming. In theory, the less small molecules are introduced, the more uniform the foam pore size is, the better the thermal insulation performance is, the better the stability is, and the better the performance is. (4) In addition, the catalyst used in the present invention is very small, and a trace residue thereof does not affect the use of the polyol, the product does not need further refining treatment, and the process is simple.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG 1 is a schematic diagram of a microchannel modular reaction device
DETAILED DESCRIPTION
The present invention can be better understood according to the following embodiments. However, those skilled in the art will easily understand that the contents described in the embodiments are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.
Related determination methods of the present invention on the prepared vegetable oil polyol and polyurethane foam material are as follows: (1) determine a hydroxyl value according to GB/T 12008.3-2009; (2) determine a viscosity according to GB/T 12008.7-2010; (3) determine an iodine value according to GB/T 5532-2008; (4) determine an apparent density of a foam plastic according to GB/T 6343-2009; (5) determine a compressive strength of a rigid foam plastic, take a vertical section of foam as a compression plane, wherein a compression rate is S mm/min, and take a test value when the sample is 10% deformed as the compressive strength of the material; and (6) determine a thermal conductivity of a rigid polyurethane foam plastic material according to GB/T 10294-2008.
In the following embodiments, a microchannel modular reaction device used, as shown in FIG. 1, comprises a micromixer, a microstructure heat exchanger, a tubular temperature control module, and a microstructure reactor which are sequentially connected in series through a connecting pipe. A temperature is controlled by oil bath heating. Two accurate and low-arterial feed pumps are connected to the micromixer through a pipeline, one pump is responsible for pumping a mixed solution containing polyhydroxy compounds of formula III and formula W and the other pump is responsible for pumping a mixed solution obtained by dissolving an epoxidized vegetable oil and a basic catalyst into an organic solvent. Embodiment 1 18.5 g of Ni/Si02-A1203 (65wt.%) and 78.90 g of tetrahydrofuran solution (60wt.%, about 1.05 mol of dimethylamine) of dimethylamine were added into a kettle reactor and stirred, and a temperature was raised to 120°C. 1-12 was introduced into the reactor to keep a pressure in the reactor at 7.0 Mpa. After the reaction conditions were stable, 545 g of glucose solution (33wt.%, 1 mol of glucose) were added into the reactor at a feeding rate of 10 mL/min, and reacted for 2 hours. After a catalytic reductive ammonolysis reaction of the glucose was completed, an obtained mixed solution containing polyhydroxy compounds of formula III and formula IV was placed in a liquid storage tank A. 191 g of epoxidized soybean oil (an epoxy group quantity of 0.8 mol, and an iodine value of 10) prepared according to a preparation method of Chinese Patent 2014104412890 and 0.153 g of sodium carbonate were dissolved in 1,000 mL of tetrahydrofuran solution, and placed in a liquid storage tank B. A temperature of an oil bath pan was adjusted to 80°C, and reaction was continued in a continuous flow system of a microchannel modular reaction device. An injection rate of A was 1.2 mL/min, an injection rate of B was 25 mL/min, and a reaction residence time was kept for 12 minutes. The reaction product was left to stand for liquid separation, an oil phase was collected, washed to neutrality with water, and then subjected to liquid separation and rotary evaporation to obtain a vegetable oil polyol with a hydroxyl value of 426 mgKOH/g, a viscosity of 6,230 mPa.s, an iodine value of 5.72, and an epoxy value of 0.29%.
Embodiment 2 15.5 g of Ni/Si02-A1203 (65wt.%) and 70.74 g of tetrahydrofuran solution (65wt.%, about 1.02 mol of dimethylamine) of dimethylamine were added into a kettle reactor and stirred, and a temperature was raised to 120°C. H2 was introduced into the reactor to keep a pressure in the reactor at 6.5 Mpa. After the reaction conditions were stable, 600 g of glucose solution (30wt.%, 1 mol of glucose) were added into the reactor at a feeding rate of 10 mL/min, and reacted for 2 hours. After a catalytic reductive ammonolysis reaction of the glucose was completed, an obtained mixed solution containing polyhydroxy compounds of formula 111 and formula IV was placed in a liquid storage tank A. 232 g of epoxidized peanut oil (an epoxy group quantity of 0.9 mol, and an iodine value of 13) prepared according to a preparation method of Chinese Patent 2014104412890 and 0.186 g of sodium bicarbonate were dissolved in 1,250 mL of tetrahydrofuran solution, and placed in a liquid storage tank B. A temperature of an oil bath pan was adjusted to 80°C, and reaction was continued in a continuous flow system of a microchannel modular reaction device. An injection rate of A was 1.6 mL/min, an injection rate of B was 3.2 mL/min, and a reaction residence time was kept for 10 minutes. The reaction product was left to stand for liquid separation, an oil phase was collected, washed to neutrality with water, and then subjected to liquid separation and rotary evaporation to obtain a vegetable oil polyol with a hydroxyl value of 417 mgKOH/g, a viscosity of 6,590 mPa.s, an iodine value of 8.18, and an epoxy value of 0.53%.
Embodiment 3 23.0 g of Ni/Si02-A1203 (65wt.%) and 64.40 g of tetrahydrofuran solution (70wt1110, about 1 mol of dimethylamine) of dimethylamine were added into a kettle reactor and stirred, and a temperature was raised to 110°C. 112 was introduced into the reactor to keep a pressure in the reactor at 7.0 N/Ipa. After the reaction conditions were stable, 720 g of glucose solution (25wt.%, 1 mol of glucose) were added into the reactor at a feeding rate of 8.5 mL/min, and reacted for 2.5 hours. After a catalytic reductive ammonolysis reaction of the glucose was completed, an obtained mixed solution containing polyhydroxy compounds of formula In and formula IV was placed in a liquid storage tank A. 190 g of epoxidized rapeseed oil (an epoxy group quantity of 0.75 mol, and an iodine value of 15) prepared according to a preparation method of Chinese Patent 2014104412890 and 0.152 g of sodium hydroxide were dissolved in 1,000 mL of tetrahydrofuran solution, and placed in a liquid storage tank B. A temperature of an oil bath pan was adjusted to 90°C, and reaction was continued in a continuous flow system of a microchannel modular reaction device. An injection rate of A was 2.0 mL/min, an injection rate of B was 3 2 mL/min, and a reaction residence time was kept for 15 minutes. The reaction product was left to stand for liquid separation, an oil phase was collected, washed to neutrality with water, and then subjected to liquid separation and rotary evaporation to obtain a vegetable oil polyol with a hydroxyl value of 396 mgKOH/g, a viscosity of 6,020 mPa-s, an iodine value of 9.36, and an epoxy value of 0.37%.
Embodiment 4 18.5 g of Ni/Si02-A1203 (65wt.%) and 75.13 g of tetrahydrofuran solution (60wt.%, about 1 mol of dimethylamine) of dimethylamine were added into a kettle reactor and stirred, and a temperature was raised to 120°C. FL was introduced into the reactor to keep a pressure in the reactor at 7.2 Mpa. After the reaction conditions were stable, 545 g of glucose solution (33wt.%, 1 mol of glucose) were added into the reactor at a feeding rate of 10 mL/min, and reacted for 2 hours. After a catalytic reductive ammonolysis reaction of the glucose was completed, an obtained mixed solution containing polyhydroxy compounds of formula In and formula IV was placed in a liquid storage tank A. 214 g of epoxidized cottonseed oil (an epoxy group quantity of 0.8 mol, and an iodine value of 14) prepared according to a preparation method of Chinese Patent 2014104412890 and 0.173 g of sodium carbonate were dissolved in 1,200 mL of tetrahydrofuran solution, and placed in a liquid storage tank B. A temperature of an oil bath pan was adjusted to 70°C, and reaction was continued in a continuous flow system of a microchannel modular reaction device. An injection rate of A was 1.4 mL/min, an injection rate of B was 3.5 mL/min, and a reaction residence time was kept for 12 minutes. The reaction product was left to stand for liquid separation, an oil phase was collected, washed to neutrality with water, and then subjected to liquid separation and rotary evaporation to obtain a vegetable oil polyol with a hydroxyl value of 393 mgKOH/g, a viscosity of 5,920 mPa.s, an iodine value of 9.04, and an epoxy value of 0.61%.
Embodiment 5 g of Pd/C (5wt.%) and 78.89 g of tetrahydrofuran solution (60wt.%, about 1.05 mol of dimethylamine) of dimethylamine were added into a kettle reactor and stirred, and a temperature was raised to 110°C. H2 was introduced into the reactor to keep a pressure in the reactor at 7.0 Mpa. After the reaction conditions were stable, 545 g of glucose solution (33wt.%, 1 mol of glucose) were added into the reactor at a feeding rate of 10 mL/min, and reacted for 2.5 hours. After a catalytic reductive ammonolysis reaction of the glucose was completed, an obtained mixed solution containing polyhydroxy compounds of formula III and formula IV was placed in a liquid storage tank A. 240 g of epoxidized soybean oil (an epoxy group quantity of 1 mol, and an iodine value of 11) prepared according to a preparation method of Chinese Patent 2014104412890 and 0.192 g of sodium carbonate were dissolved in 1,500 mL of tetrahydrofuran solution, and placed in a liquid storage tank B A temperature of an oil bath pan was adjusted to 90°C, and reaction was continued in a continuous flow system of a microchannel modular reaction device. An injection rate of A was 1.8 mL/min, an injection rate of B was 4.0 mL/min, and a reaction residence time was kept for 10 minutes. The reaction product was left to stand for liquid separation, an oil phase was collected, washed to neutrality with water, and then subjected to liquid separation and rotary evaporation to obtain a vegetable oil polyol with a hydroxyl value of 387 mgKOH/g, a viscosity of 6,310 mPa.s, an iodine value of 7.05, and an epoxy value of 0.85%.
Embodiment 6 Performance test of polyurethane rigid foam prepared by vegetable oil polyol The soybean oil polyol prepared in Embodiment 1 was foamed and reacted with a foam stabilizer AK8803 (Nanjing MAYSTA), a cyclohexylamine (Jiangdu Dajiang Chemical), an isocyanate WANNATE PM-200 (Yantai Wanhua), and a foaming agent cyclopentane (Foshan Meilong) by one-step free foaming process, thus preparing a rigid polyurethane foam with an apparent density of 39.3kg/m3 and a vertical compressive strength of 229, and a thermal conductivity of 20.37 W/m*K.
Comparative Example 1 47.0 g of Ni/Si02-A1203 (65wt. AO and 60 g of tetrahydrofuran solution (75wt.%, about 1 mol of dimethylamine) of dimethylamine were added into a kettle reactor and stirred, and a temperature was raised to 125°C. 112 was introduced into the reactor to keep a pressure in the reactor at 7.5 Mpa. After the reaction conditions were stable, 900 g of glucose solution (20wt.%, 1 mol of glucose) were added into the reactor at a feeding rate of 15 mL/min, and reacted for 2 hours. After a catalytic reductive ammonolysis reaction of the glucose was completed, an obtained mixed solution containing polyhydroxy compounds of formula III and formula IV was placed in a liquid storage tank A. 215 g of epoxidized soybean oil (an epoxy group quantity of 0.9 mol, and an iodine value of 11) prepared according to a preparation method of Chinese Patent 2014104412890 and 0.1_72 g of sodium carbonate were dissolved in 1,200 mL of tetrahydrofuran solution, and placed in a liquid storage tank B. The mixed solution in the liquid storage tank A and the raw materials in the liquid storage tank B were added into a kettle reactor and stirred, and the temperature was raised to 125°C, wherein an injection rate of A was 25 mL/min, an injection rate of B was 35 mL/min, and the reaction lasted for 2.5 hours. After the reaction was completed, the reaction product was left to stand for liquid separation, an oil phase was collected, washed to neutrality with water, and then subjected to liquid separation and rotary evaporation to obtain a vegetable oil polyol with a hydroxyl value of 255 mgKOH/g, a viscosity of 16,160 mPa.s, an iodine value of 7.30, and an epoxy value of 1.11%.
Comparative Example 2 g of glucose (1 mol of glucose) were dissolved in 1,000 mL of tetrahydrofuran solution, and placed in a liquid storage tank A. 191 g of epoxidized soybean oil (an epoxy group quantity of 0.8 mol, and an iodine value of 10) prepared according to a preparation method of Chinese Patent 2014104412890 and 0.153 g of sodium carbonate were dissolved in 1,000 mL of tetrahydrofuran solution, and placed in a liquid storage tank B. A temperature of an oil bath pan was adjusted to 80°C, and reaction was continued in a continuous flow system of a microchannel modular reaction device. An injection rate of A was 3 6 mL/min, an injection rate of B was 2.7 mL/min, and a reaction residence time was kept for 12 minutes.
The reaction product was left to stand for liquid separation, an oil phase was collected, washed to neutrality with water, and then subjected to liquid separation and rotary evaporation to obtain a vegetable oil polyol with a hydroxyl value of 238 mgKOH/g, a viscosity of 14,310 mPa.s, an iodine value of 7.41, and an epoxy value of 1.83%.
Comparative Example 3 22.14 g of Ni/Si02-A1203 (65wt9zb) and 92.414 g of tetrahydrofuran solution (60wt. about 1.23 mol of dimethylamine) of dimethylamine were added into a kettle reactor and stirred, and a temperature was raised to 120°C. H2 was introduced into the reactor to keep a pressure in the reactor at 7.0 Mpa. After the reaction conditions were stable, 654 g of glucose solution (33wt.%, 1.2 mol of glucose) were added into the reactor at a feeding rate of 15 mL/min, and reacted for 2.5 hours. After a catalytic reductive ammonolysis reaction of the glucose was completed, an obtained mixed solution containing polyhydroxy compounds of formula III and formula IV was placed in a liquid storage tank A. g of epoxidized soybean oil (an epoxy value of 6.40%, and an iodine value of 4.4) and 0.160 g of sodium carbonate were dissolved in 1,150 mL of tetrahydrofuran solution, and placed in a liquid storage tank B. A temperature of an oil bath pan was adjusted to 80°C, and reaction was continued in a continuous flow system of a microchannel modular reaction device. An injection rate of A was 1.5 mL/min, an injection rate of B was 3 4 mL/min, and a reaction residence time was kept for 12 minutes. The reaction product was left to stand for liquid separation, an oil phase was collected, washed to neutrality with water, and then subjected to liquid separation and rotary evaporation to obtain a vegetable oil polyol with a hydroxyl value of 185 mgKOH/g, a viscosity of 11,230 mPa.s, an iodine value of 2.44, and an epoxy value of 0.
Comparative Example 4 18.5 g of Ni/Si02-A1203 (65wt.%) and 75.13 g of tetrahydrofuran solution (60wt.°70, about I mol of dimethylamine) of dimethylamine were added into a kettle reactor and stirred, and a temperature was raised to 120°C. H2 was introduced into the reactor to keep a pressure in the reactor at 7.0 Mpa. After the reaction conditions were stable, 545 g of glucose solution (33wt.%, 1 mol of glucose) were added into the reactor at a feeding rate of 10 mL/min, and reacted for 2 hours. After a catalytic reductive ammonolysis reaction of the glucose was completed, an obtained mixed solution containing polyhydroxy compounds of formula In and formula IV was placed in a liquid storage tank A. g of epoxidized soybean oil (an epoxy value of 6.40%, and an iodine value of 4.2) and 0.162 g of sodium carbonate were dissolved in 1,100 mL of tetrahydrofuran solution, and placed in a liquid storage tank B. A temperature of an oil bath pan was adjusted to 80°C, and reaction was continued in a continuous flow system of a microchannel modular reaction device. An injection rate of A was 1.5 mL/min, an injection rate of B was 3 6 mL/min, and a reaction residence time was kept for 12 minutes. The reaction product was left to stand for liquid separation, an oil phase was collected, washed to neutrality with water, and then subjected to liquid separation and rotary evaporation to obtain a vegetable oil polyol with a hydroxyl value of 244 mgKOH/g, a viscosity of 10,880 mPa.s, an iodine value of 2.65, and an epoxy value of 0.64%.
Comparative Example 5 25.54 g of Ni/Si02-A1203 (65wt.%) and 130.73 g of tetrahydrofuran solution (60wt.%, about L74 mol of dimethylamine) of dimethylamine were added into a kettle reactor and stirred, and a temperature was raised to 120°C. I-12 was introduced into the reactor to keep a pressure in the reactor at 7.0 Mpa. After the reaction conditions were stable, 905 g of glucose solution (33wt.%, 1.66 mol of glucose) were added into the reactor at a feeding rate of 15 mL/min, and reacted for 2.5 hours. After a catalytic reductive ammonolysis reaction of the glucose was completed, an obtained mixed solution containing polyhydroxy compounds of formula III and formula IV was placed in a liquid storage tank A. 262 g of epoxidized soybean oil (an epoxy value of 6.10%, and an iodine value of 63.5) and 0.212 g of sodium carbonate were dissolved in 1,400 mL of tetrahydrofuran solution, and placed in a liquid storage tank B. A temperature of an oil bath pan was adjusted to 80°C, and reaction was continued in a continuous flow system of a microchannel modular reaction device. An injection rate of A was 1.8 mL/min, an injection rate of B was 3 6 mL/min, and a reaction residence time was kept for 12 minutes. The reaction product was left to stand for liquid separation, an oil phase was collected, washed to neutrality with water, and then subjected to liquid separation and rotary evaporation to obtain a vegetable oil polyol with a hydroxyl value of 140 mgKOH/g, a viscosity of 17,450 mPa.s, an iodine value of 36.43, and an epoxy value of 0.
The present invention provides an idea and a method for a vegetable oil polyol and a preparation method and an application thereof There are many methods and ways to realize the technical solutions specifically. Those described above are merely the preferred embodiments of the present invention. It should 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 should also be regarded as the scope of protection of the present invention. All unspecified components in the
embodiments can be implemented in the prior art.

Claims (10)

  1. CLAIMS1. A preparation method of a vegetable oil polyol, comprising the following steps of: (1) adding a metal catalyst and an organic solvent system dissolved with secondary amine into a reactor, introducing hydrogen into the reactor, and then adding a glucose solution into the reactor to carry out a reductive ammonolysis reaction to obtain a mixed solution containing polyhydroxy compounds of formula HI and formula IV; wherein R is CH3 or CH2CH3; and (2) dissolving epoxidized vegetable oil and a basic catalyst into an organic solvent to obtain a mixed solution containing the epoxidized vegetable oil, and respectively and simultaneously pumping the mixed solution containing the epoxidized vegetable oil and the mixed solution containing the polyhydroxy compounds of formula III and formula IV obtained in step (1) into a microstructure reactor of a microchannel modular reaction device for reaction to obtain the vegetable oil polyol, wherein the epoxidized vegetable oil has an iodine value of 10 to 15 and an epoxy value of 6.0% to 6.7%.
  2. 2. The preparation method according to claim 1, wherein the metal catalyst in step (1) is any one or a combination of several of Ni/Si02-A1203, Pt/C, Pd/C, and Ru/C; the secondary amine is any one or a combination of dimethylamine and diethylamine, and the solvent in the organic solution is any one or a combination of several of tetrahydrofuran, methanol, ethanol, and ethyl acetate.
  3. 3. The preparation method according to claim t, wherein the organic solution dissolved with the secondary amine in step (1) has a concentration of 55wt.% to 75wt.%; the glucose solution has a concentration of 20wt.% to 35wt.%; and a ratio of a mass of the metal catalyst to a molar weight of the glucose is 9 g to 31 g: 1 mol.
  4. 4. The preparation method according to claim 1, wherein a reaction temperature in step (1) is 110°C to 125°C, a reaction pressure is 6.0 Mpa to 7.5 Mpa, arid a reaction time lasts for 2 hours to 2.5 hours; and a feeding speed of the glucose solution is 8.1 ml/min to 15m1/min.
  5. The preparation method according to claim 1, wherein the epoxidized vegetable oil in step (2) is any one or a combination of several of epoxidized peanut oil, epoxidized rapeseed oil, epoxidized cottonseed oil, and epoxidized soybean oil; the basic catalyst is any one or a combination of several of sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate; and the organic solvent is any one or a combination of several of tetra.hydrofuran, methanol, ethanol, and ethyl acetate.
  6. 6. The preparation method according to claim 1, wherein a mass percentage of the basic catalyst to the epoxidized vegetable oil in step (2) is 0.02% to 0.1%, and a mass ratio of the organic solvent to the epoxidized vegetable oil is 2 to 6: 1
  7. 7. The preparation method according to claim 1, wherein a molar ratio of the basic catalyst to the secondary amine and the glucose in step (1) to an epoxy group of the epoxidized vegetable oil in step (2) is Ito 1.05: 0.5 to 1.0.
  8. 8. The preparation method according to claim 1_, wherein the reaction in the microstructure reactor in step (2) has a temperature of 60°C to 100°C, and has a residence time of 10 minutes to 15 minutes.
  9. 9. A vegetable oil polyol prepared by the preparation method according to any one of claims 1 to 8
  10. 10. An application of the vegetable oil polyol according to claim 9 in preparing a polyurethane rigid foam.
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