CN107151304B - Preparation method of tung oil polyol - Google Patents

Preparation method of tung oil polyol Download PDF

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CN107151304B
CN107151304B CN201610119881.8A CN201610119881A CN107151304B CN 107151304 B CN107151304 B CN 107151304B CN 201610119881 A CN201610119881 A CN 201610119881A CN 107151304 B CN107151304 B CN 107151304B
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tung oil
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autoclave
acid
oil
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CN107151304A (en
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李风华
李澜鹏
白富栋
乔凯
王领民
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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
    • C08G18/28—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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
    • C07D301/16—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof formed in situ, e.g. from carboxylic acids and hydrogen peroxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid

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Abstract

The invention relates to a preparation method of tung oil polyalcohol, which comprises the steps of adding tung oil, a hydroxylation reagent, deionized water, an auxiliary oxidant aldehyde compound and a free radical initiator into an autoclave in proportion, introducing nitrogen into the autoclave, replacing air in the autoclave, and filling oxygen/nitrogen mixed gas into the autoclave until the pressure in the autoclave reaches 6.0-8.5 MPa; starting stirring, controlling the reaction temperature to be 65-80 ℃, reacting for 2.5-4.5h, and finishing the reaction; and (3) reducing the pressure of the reaction system to normal pressure, reducing the temperature to normal temperature, and then washing with water and carrying out reduced pressure distillation to obtain the tung oil polyol. The method utilizes the characteristic that the conjugated double bond of the tung oil can improve the reaction activity of an epoxy group, utilizes a molecular oxygen/aldehyde system to catalyze epoxidation reaction, and adds a hydroxylation reagent during epoxidation, so that the generation of a cross-linking side reaction can be effectively avoided, and a tung oil polyalcohol product is synthesized. The hydroxyl value of the prepared tung oil polyol is 120-270mgKOH/g, the acid value is lower than 1.0mgKOH/g, the water content is lower than 0.1wt%, the yield is higher than 92%, and the tung oil polyol is suitable for preparing polyurethane materials.

Description

Preparation method of tung oil polyol
Technical Field
The invention belongs to the field of polyurethane materials, and particularly relates to a preparation method of tung oil polyol.
Background
Polyurethane materials have been widely used in industry and in people's daily life due to their good mechanical properties and easy moldability. The main raw materials for producing polyurethane comprise isocyanate, polyol and other additives, wherein the proportion of the polyol accounts for more than 50%. In the industrial production process, the polyol is mainly applied to the polyurethane field, so the influencing factors of the polyurethane industry are also the main influencing factors of the polyol market. The polyols can be classified into polyether polyols and polyester polyols according to their molecular structures, with polyether polyols dominating the market and occupying more than 70% of the total polyol demand.
Generally, polyols are prepared by extraction from petroleum. The scarcity of petroleum as an unrenewable resource causes the price to continuously rise, and the price of the main raw materials for producing the downstream products of polyhydric alcohols such as propylene oxide and ethylene oxide continuously rises, and the petroleum resource is consumed at all times according to the current consumption rate. Therefore, from the perspective of sustainable development and enterprise competitiveness, it is a strategic development task to find new materials and new processes that can replace petroleum-based polyethers.
The united states is the major world-wide soybean oil producing country, and in addition to food, research institutes in the united states are actively engaged in developing various chemical products using soybean oil as a raw material to replace petroleum-based chemicals. Recently, the method focuses on preparing soybean oil polyol by modifying double bonds through unsaturated bonds in soybean oil molecular chains to perform epoxidation and hydroxylation on vegetable oil. The method has the advantages of low reaction temperature (40-70 ℃), good product quality and color and luster, so the method is widely concerned.
Reacting peroxide acid with soybean oil to prepare epoxidized soybean oil, wherein double bonds are converted into epoxy groups; then the epoxidized soybean oil and water and alcohol generate ring-opening reaction under the catalysis of a high-efficiency catalyst tetrafluoroboric acid to prepare the vegetable oil polyol containing hydroxyl, wherein the hydroxyl value of the polyol is 110-213mgKOH/g, the viscosity is 1000-7000 mPa.s, and the conversion rate can reach 85-95%.
US20070123725 provides a process for preparing a soybean oil polyol, comprising the epoxidation and hydroxylation process of an unsaturated vegetable oil to form a vegetable oil based polyether polyol. Firstly, unsaturated vegetable oil such as soybean oil or rapeseed oil reacts with organic acid and hydrogen peroxide solution to form epoxy vegetable oil, and then the epoxy vegetable oil is subjected to ring-opening reaction with mixed solution of methanol and water to generate vegetable oil polyalcohol.
US20060041157 describes a process for making a soy oil polyol comprising reacting a partially epoxidized vegetable oil under catalyst conditions with a ring-opening reagent comprising a small molecule polyol, vegetable oil polyol or other polyol to form an oligomeric vegetable oil-based polyol. The functionality of the oligomeric vegetable oil polyol is 1 to 6 and the hydroxyl value is 20 to 300 mgKOH/g.
Tung oil is an important industrial raw material and a traditional export commodity. At present, the annual output of China tung oil reaches more than 10 ten thousand tons, which accounts for about 35 percent of the world tung oil output. Therefore, it is of particular importance to study tung oil and industrialize more products related to tung oil. However, the tung oil is used for preparing the high-quality vegetable oil polyol, because the tung oil has high unsaturation degree and is the only unsaturated vegetable oil with conjugated double bonds in nature, the iodine value reaches more than 170, wherein more than 85% of unsaturated bonds are carbon-carbon conjugated triene bonds, epoxy groups have high reaction activity and poor selectivity and are easy to generate side reactions due to the existence of the conjugated double bonds in the epoxidation process of the tung oil for preparing the polyol, so that a macromolecular cross-linked product is generated, the viscosity is increased sharply, and the tung oil is usually solid at room temperature and cannot be used for further synthesizing polyurethane materials. Research literature (such as Epoxidation of natural triglyceridees with ethylene oxidation, Journal of the American oil chemists' Society, 1996, 73: 461-.
The preparation of epoxy vegetable oil by catalytic oxidation of vegetable oil with a molecular oxygen/aldehyde system is always a research hotspot in the field of deep processing of vegetable oil, because the traditional vegetable oil epoxidation process needs to use a large amount of carboxylic acid and hydrogen peroxide solution, and the hydrogen peroxide solution is easy to decompose and generate explosion danger when being used as an oxidant in industrial production, and needs to use a large amount of carboxylic acid, thereby putting strict requirements on the material selection of a reaction kettle. Molecular oxygen is the best oxidant from both economic and environmental aspects. Blumenstein et al (Blumenstein M. oxidation of Methyl Oleate With molecular oxygen in Presence of Aldehydes, European great of lipid science and technology, Vol.110, No. 6, p. 581. 586) adopt molecular oxygen/aldehyde system for catalytic oxidation to synthesize Methyl epoxyoleate, the conversion rate of double bonds reaches over 95%, good effect is obtained, and a large amount of hydrogen peroxide solution and formic acid are not needed in the reaction, so that the production process is safer and more environment-friendly.
However, the reaction temperature for achieving a better epoxidation effect of the vegetable oil is usually above 65 ℃ by adopting a molecular oxygen/aldehyde catalytic oxidation system, and under the condition that a small molecular alcohol reagent is used as a hydroxylation reagent, a cross-linking side reaction is easy to occur due to low reaction selectivity at a high temperature, so that the hydroxyl value of a product is reduced, the viscosity is increased, and the molecular oxygen/aldehyde catalytic oxidation system is difficult to be used for catalytically oxidizing and synthesizing the tung oil polyol.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of tung oil polyol. The method utilizes the characteristic that the conjugated double bond of the tung oil can improve the reaction activity of an epoxy group, utilizes the molecular oxygen/aldehyde system to catalyze the epoxidation reaction, and adds the oil-soluble fatty acid during the epoxidation reaction, thereby effectively avoiding the occurrence of cross-linking side reaction and efficiently synthesizing the tung oil polyol product.
The preparation method of the tung oil polyol comprises the following steps: adding tung oil, a hydroxylation reagent, deionized water, an auxiliary oxidant aldehyde compound and a free radical initiator into an autoclave according to a proportion, introducing nitrogen into the autoclave, replacing air in the autoclave, and filling oxygen/nitrogen mixed gas into the autoclave after replacement is finished until the pressure in the autoclave reaches 6.0-8.5 MPa; starting stirring, controlling the reaction temperature to be 65-80 ℃, reacting for 2.5-4.5h, and finishing the reaction; and (3) reducing the pressure of the reaction system to normal pressure, reducing the temperature to normal temperature, and then washing with water and carrying out reduced pressure distillation to obtain the tung oil polyol.
The hydroxylation reagent is oil-soluble fatty acid, and the dosage of the hydroxylation reagent is 0.1-0.5 time of the mass of the tung oil. The oil-soluble fatty acid may be selected from C6-C12One or more of straight chain or branched chain saturated fatty acids, such as n-hexanoic acid, n-heptanoic acid, n-octanoic acid, isocaproic acid, isoheptanoic acid, isocaprylic acid, etc. Compared with a small molecular alcohol reagent, the oil-soluble fatty acid has the following advantages: (1) the hydrogen of the oil-soluble fatty acid is easier to ionize, the reaction activity is obviously higher than that of the alcoholic hydroxyl group formed by the adjacent vegetable oil molecular chain, so that the oil-soluble fatty acid still has good reaction selectivity at higher reaction temperature, avoids the cross-linking side reaction among the vegetable oil molecular chains, forms the alcoholic hydroxyl group, has wider reaction temperature window, and is suitable for the characteristic that a molecular oxygen/aldehyde compound system can achieve better epoxidation effect at higher temperature; (2) the oil-soluble fatty acid can be dissolved in the oil phase in the reaction system, so that the problem of reduced hydroxylation ring-opening reaction rate caused by migration between oil and water phases is avoided, and the reaction selectivity is improved; (3) the oil-soluble fatty acid and the carboxylic acid generated by the reaction can not generate chemical reaction in a system, so that the concentration of a reaction substrate is reduced, the epoxidation and in-situ ring-opening reaction effects are influenced, the dosage of a hydroxylation reagent is obviously reduced, and the production raw material cost is reduced.
The dosage of the deionized water is 0.01 to 0.2 times of the quality of the tung oil, and the deionized water is a green solvent for reaction.
The pro-oxidant aldehyde compound is one or more of acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, benzaldehyde, phenylacetaldehyde and the like, preferably acetaldehyde, and the dosage of the pro-oxidant aldehyde compound is 0.05 to 0.3 times of the mass of the tung oil. Pro-oxidant aldehydes (RCHO) first form acyl Radicals (RCO) under the induction of a radical initiator (initiator), and then the acyl radicals are in oxygen (O)2) Under the action of the oxygen, peroxy Radicals (RCOOO) are generated, which transfer free radicals to aldehyde compounds to form peroxy acids (RCOOOH) and acyl free Radicals (RCO), and the reaction is carried out repeatedly. Wherein peroxygen is generatedThe acid can convert conjugated double bonds in the tung oil into epoxy bonds, and the epoxy bonds are further reacted with a hydroxylation reagent to form the tung oil polyol.
Figure 234326DEST_PATH_IMAGE001
The free radical initiator is selected from azo initiators such as azobisisobutyronitrile, azobisisoheptonitrile and the like, or is selected from organic peroxides such as cyclohexanone peroxide, dibenzoyl peroxide and the like, and the dosage of the free radical initiator is 0.001-0.01 time of the mass of the tung oil.
The invention introduces nitrogen into the autoclave to replace air, and fills oxygen/nitrogen mixed gas with the volume ratio of 1/99-10/90 into the autoclave after replacement is finished, so that the pressure in the autoclave reaches 6.0-8.5 MPa.
The washing temperature of the invention is 50-80 ℃ to prevent the system from emulsifying. The reduced pressure distillation is to remove the hydroxylation reagent and residual moisture in the system under the conditions of the pressure of 1000-3000Pa and the temperature of 60-120 ℃ so as to ensure that the moisture content of the product is less than 0.1 wt%.
The tung oil polyol of the present invention is prepared by the above-described process of the present invention. The hydroxyl value of the prepared tung oil polyol is 120-270mgKOH/g, the acid value is lower than 1.0mgKOH/g, the water content is lower than 0.1wt%, the yield is higher than 92%, and the tung oil polyol is suitable for preparing polyurethane materials.
More than 85% of unsaturated bonds in tung oil molecules are carbon-carbon conjugated triene bonds, so that epoxy groups have high reaction activity, poor selectivity and easy side reaction in the process of preparing the polyol, and consequently, macromolecular cross-linked products are generated, the viscosity is increased sharply, and the polyurethane material cannot be further synthesized. The method utilizes the characteristic that the conjugated double bond of the tung oil can improve the reaction activity of an epoxy group, adopts a molecular oxygen/aldehyde system to catalyze epoxidation reaction, and adds oil-soluble fatty acid during epoxidation, so that the occurrence of a cross-linking side reaction can be effectively prevented, and a tung oil polyalcohol product is efficiently synthesized. Compared with petroleum-based polyol, the prepared tung oil polyol has the advantages of renewable raw materials, no toxicity, good biodegradability and the like, and belongs to environment-friendly bio-based polyol.
The micromolecular alcohol reagent is added in the epoxidation reaction process of the tung oil, so that the cross-linking side reaction among tung oil molecular chains can be avoided under certain conditions, and a tung oil polyalcohol product is synthesized. However, in the epoxidation reaction process, the small molecular alcohol reagent is easy to perform esterification reaction with formic acid serving as an oxygen-carrying agent, so that the concentration of the small molecular alcohol reagent and the formic acid in a reaction system is obviously reduced, the epoxidation and in-situ ring-opening reaction rate is slow, and the problems of poor crosslinking side reaction effect and the like are solved. Therefore, the reaction system must avoid the above problems by increasing the feeding amount of small molecular alcohol reagent, formic acid, hydrogen peroxide solution, etc., and the production raw material cost and the treatment amount of industrial wastewater are greatly increased. In addition, since the small molecular alcohol reagent has a problem of poor high-temperature reaction selectivity, and is liable to cause disadvantages such as a decrease in hydroxyl value and an increase in viscosity of the product at a high reaction temperature, the reaction temperature must be strictly controlled, which increases the construction cost of the production apparatus. The invention adopts oil-soluble fatty acid as a hydroxylation reagent, so that the epoxy bond in-situ ring-opening reaction has higher selectivity and wider reaction temperature window, and can meet the use requirement of a molecular oxygen/aldehyde oxidation system. And the problems that the concentration of the small molecular alcohol reagent in a reaction system is obviously reduced, the cross-linking side reaction effect is not good and the like because the small molecular alcohol reagent is easy to perform esterification reaction with formic acid generated by the reaction in the epoxidation reaction process are solved, the using amount of the hydroxylation reagent is effectively reduced, and the production raw material cost is reduced.
In addition, a molecular oxygen/aldehyde catalytic oxidation system is adopted, the danger that a large amount of hydrogen peroxide solution is easily decomposed and exploded in the traditional plant oil epoxidation process is avoided, and compared with the traditional process that a large amount of carboxylic acid is used as an oxygen carrying agent and the requirement on material selection of a reaction kettle is strict, the equipment construction cost is obviously reduced.
Detailed Description
The present invention will be further described with reference to the following examples. In the present invention, wt% means mass fraction.
The hydroxyl value of the tung oil polyol prepared by the invention is measured according to a phthalic anhydride esterification method in GB/T12008.3-2009, the acid value is measured according to a GB/T12008.5-2010 method, and the viscosity is measured according to a rotary viscometer method in GB/T12008.7-2010.
Example 1
500g of tung oil, 70g of acetaldehyde, 2.5g of azobisisobutyronitrile, 150g of n-hexanoic acid and 50g of deionized water are added into an autoclave and stirred uniformly. Then introducing nitrogen into the autoclave to replace the air in the autoclave for 3 times, and filling an oxygen/nitrogen mixed gas with a volume ratio of 5/95 into the autoclave until the pressure in the autoclave reaches 7.5 MPa. Starting stirring, controlling the reaction temperature at 70 ℃, reacting for 3.5h, and finishing the reaction. Opening air release valve to reduce system pressure to normal pressure, cooling to normal temperature, removing water phase after reaction system layering, washing oil phase with 10wt% sodium bicarbonate water solution to neutrality, and washing product with 70 deg.C hot water for 3 times. Distilling the washed product for 2h under the conditions of 2000Pa and 80 ℃ to prepare the tung oil polyol. The hydroxyl value is 246mgKOH/g, the viscosity is 7350 mPa.s, the acid value is 0.71mgKOH/g, the water content is lower than 0.1wt%, the yield is 93.4%, and the polyurethane rigid foam can be prepared.
Example 2
500g of tung oil, 90g of propionaldehyde, 2.5g of azobisisobutyronitrile, 100g of n-hexanoic acid and 50g of deionized water are added into an autoclave and stirred uniformly. Then introducing nitrogen into the autoclave to replace the air in the autoclave for 3 times, and filling an oxygen/nitrogen mixed gas with a volume ratio of 5/95 into the autoclave until the pressure in the autoclave reaches 6.5 MPa. Starting stirring, controlling the reaction temperature at 80 ℃, reacting for 2.5h, and finishing the reaction. The pressure of the system is reduced to normal pressure by opening a deflation valve, the temperature is reduced to normal temperature, and then the reaction system washes the product for 3 times by using hot water with the temperature of 70 ℃. Distilling the washed product for 2h under the conditions of 2000Pa and 80 ℃ to obtain the tung oil polyol. The hydroxyl value is 234mgKOH/g, the viscosity is 7210 mPa.s, the acid value is 0.70mgKOH/g, the water content is lower than 0.1wt%, the yield is 93.2%, and the polyurethane rigid foam can be prepared.
Example 3
500g of tung oil, 115g of n-butyraldehyde, 3.8g of azobisisoheptonitrile, 200g of n-hexanoic acid and 50g of deionized water are added into an autoclave and stirred uniformly. Then introducing nitrogen into the autoclave to replace the air in the autoclave for 3 times, and filling an oxygen/nitrogen mixed gas with a volume ratio of 5/95 into the autoclave until the pressure in the autoclave reaches 8.5 MPa. Starting stirring, controlling the reaction temperature to be 65 ℃, reacting for 4h, and finishing the reaction. The pressure of the system is reduced to normal pressure by opening a deflation valve, the temperature is reduced to normal temperature, and then the reaction system washes the product for 3 times by using hot water with the temperature of 70 ℃. Distilling the washed product for 2h under the conditions of 2000Pa and 80 ℃ to obtain the tung oil polyol. The hydroxyl value is 208mgKOH/g, the viscosity is 7040 mPa.s, the acid value is 0.68mgKOH/g, the water content is lower than 0.1wt%, the yield is 92.9%, and the polyurethane rigid foam can be prepared.
Example 4
The same treatment conditions as in example 1 were used except that the pro-oxidant aldehyde added was isobutyraldehyde. The hydroxyl value of the prepared tung oil polyol is 174mgKOH/g, the viscosity is 6200mPa · s, the acid value is 0.63mgKOH/g, the water content is lower than 0.1wt%, the yield is 92.5%, and the tung oil polyol can be used for preparing polyurethane rigid foam products.
Example 5
The same treatment conditions as in example 1 were used except that the pro-oxidant aldehyde added was n-valeraldehyde. The prepared tung oil polyol has a hydroxyl value of 228mgKOH/g, viscosity of 7290mPa & s, an acid value of 0.68mgKOH/g, water content of less than 0.1wt%, and yield of 93.1%, and can be used for preparing polyurethane rigid foam products.
Example 6
The same treatment conditions as in example 1 were used except that benzaldehyde was used as the pro-oxidant. The hydroxyl value of the prepared tung oil polyol is 166mgKOH/g, the viscosity is 5600mPa · s, the acid value is 0.55mgKOH/g, the water content is lower than 0.1wt%, the yield is 92.3%, and the tung oil polyol can be used for preparing polyurethane products.
Example 7
The same processing conditions as in example 1 were used except that azobisisoheptonitrile was used as the radical initiator. The hydroxyl value of the prepared tung oil polyol is 232mgKOH/g, the viscosity is 7140mPa & s, the acid value is 0.69mgKOH/g, the water content is lower than 0.1wt%, the yield is higher than 93.3%, and the tung oil polyol can be used for preparing polyurethane rigid foam products.
Example 8
The same process conditions as in example 1 were used except that the free radical initiator added was cyclohexanone peroxide. The prepared tung oil polyol has a hydroxyl value of 228mgKOH/g, a viscosity of 7050mPa & s, an acid value of 0.67mgKOH/g, a water content of less than 0.1wt%, and a yield of more than 93.2%, and can be used for preparing polyurethane rigid foam products.
Example 9
The same process conditions as in example 1 were used except that the free radical initiator added was dibenzoyl peroxide. The hydroxyl value of the prepared tung oil polyol is 230mgKOH/g, the viscosity is 7110mPa & s, the acid value is 0.68mgKOH/g, the water content is lower than 0.1wt%, the yield is higher than 93.3%, and the tung oil polyol can be used for preparing polyurethane rigid foam products.
Example 10
The same process conditions as in example 1 were used except that the hydroxylating agent added was n-heptanoic acid. The hydroxyl value of the prepared tung oil polyol is 238mgKOH/g, the viscosity is 7640mPa & s, the acid value is 0.73mgKOH/g, the water content is lower than 0.1wt%, the yield is higher than 93.2%, and the tung oil polyol can be used for preparing polyurethane rigid foam products.
Example 11
The same process conditions as in example 1 were used except that the hydroxylating agent added was isoheptanoic acid. The hydroxyl value of the prepared tung oil polyol is 211mgKOH/g, the viscosity is 8450 mPa.s, the acid value is 0.78mgKOH/g, the water content is lower than 0.1wt%, the yield is higher than 92.9%, and the tung oil polyol can be used for preparing polyurethane rigid foam products.
Example 12
The same process conditions as in example 1 were used except that the hydroxylating agent added was n-octanoic acid. The hydroxyl value of the prepared tung oil polyol is 224mgKOH/g, the viscosity is 8030 mPa.s, the acid value is 0.75mgKOH/g, the water content is lower than 0.1wt%, the yield is higher than 93.1%, and the tung oil polyol can be used for preparing polyurethane rigid foam products.
Example 13
The same process conditions as in example 1 were used except that the hydroxylating agent added was isooctanoic acid. The hydroxyl value of the prepared tung oil polyol is 202mgKOH/g, the viscosity is 8820mPa & s, the acid value is 0.81mgKOH/g, the water content is lower than 0.1wt%, the yield is higher than 92.7%, and the tung oil polyol can be used for preparing polyurethane rigid foam products.
Comparative example 1
The same process conditions as in example 1 were used except that no hydroxylating agent was added. The viscosity of the product was 383000 mPas, and the product was too high to be dissolved and could not be further hydroxylated, so that it could not be used for the production of polyurethane products.
Comparative example 2
The same process conditions as in example 1 were used except that methanol was used as the hydroxylating agent. The hydroxyl value of the product is 125mgKOH/g, the viscosity is 69600 mPa.s, the actual concentration of methanol in the reaction system is low due to the fact that the methanol is easy to perform esterification reaction with generated formic acid in the reaction system, the reaction selectivity of the methanol serving as a hydroxylation reagent at a high temperature is poor, the alcohol reagents such as the methanol cannot avoid the cross-linking side reaction of tung oil epoxidation due to the above factors, the viscosity of the product is increased rapidly, and the polyurethane product cannot be further synthesized.
Comparative example 3
The same processing conditions as in example 1 were used except that soybean oil was used to prepare the polyol. The hydroxyl value of the product is 4.1mgKOH/g, and the product cannot be used for preparing polyurethane products because the product does not undergo hydroxylation reaction and has too low hydroxyl value.

Claims (9)

1. The preparation method of the tung oil polyol is characterized by comprising the following steps: adding tung oil, a hydroxylation reagent, deionized water, an auxiliary oxidant aldehyde compound and a free radical initiator into an autoclave according to a proportion, introducing nitrogen into the autoclave, replacing air in the autoclave, and filling oxygen/nitrogen mixed gas into the autoclave after replacement is finished until the pressure in the autoclave reaches 6.0-8.5 MPa; starting stirring, controlling the reaction temperature to be 65-80 ℃, reacting for 2.5-4.5h, and finishing the reaction; reducing the pressure of a reaction system to normal pressure, reducing the temperature to normal temperature, and then washing with water and carrying out reduced pressure distillation to obtain tung oil polyol; the hydroxylating agent is an oil-soluble fatty acid selected from C6-C12Linear or branched saturated esters of (2)One or more of fatty acids.
2. The method of claim 1, wherein: the dosage of the oil-soluble fatty acid is 0.1-0.5 times of the mass of the tung oil.
3. The method according to claim 1 or 2, characterized in that: the oil-soluble fatty acid is n-hexanoic acid, n-heptanoic acid, n-octanoic acid, isocaproic acid, isoheptanoic acid or isooctanoic acid.
4. The method of claim 1, wherein: the dosage of the deionized water is 0.01 to 0.2 times of the mass of the tung oil.
5. The method of claim 1, wherein: the pro-oxidant aldehyde compound is one or more of acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, benzaldehyde and phenylacetaldehyde, and the dosage of the pro-oxidant aldehyde compound is 0.05 to 0.3 times of the mass of the tung oil.
6. The method of claim 1, wherein: the free radical initiator is selected from azo initiators or organic peroxides, and the dosage of the free radical initiator is 0.001-0.01 time of the mass of the tung oil.
7. The method of claim 6, wherein: the azo initiator is azobisisobutyronitrile or azobisisoheptonitrile; the organic peroxide is cyclohexanone peroxide or dibenzoyl peroxide.
8. The method of claim 1, wherein: the volume ratio of the oxygen/nitrogen mixed gas filled into the autoclave is 1/99-10/90.
9. The method of claim 1, wherein: the washing temperature is 50-80 ℃; the reduced pressure distillation is to remove the hydroxylation reagent and residual moisture in the system under the conditions of the pressure of 1000-3000Pa and the temperature of 60-120 ℃ so as to ensure that the moisture content of the product is less than 0.1 wt%.
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