CN107151211B - Tung oil polyol with high hydroxyl value and preparation method thereof - Google Patents

Tung oil polyol with high hydroxyl value and preparation method thereof Download PDF

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CN107151211B
CN107151211B CN201610119887.5A CN201610119887A CN107151211B CN 107151211 B CN107151211 B CN 107151211B CN 201610119887 A CN201610119887 A CN 201610119887A CN 107151211 B CN107151211 B CN 107151211B
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tung oil
acid
reaction
oil polyol
hydroxyl value
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CN107151211A (en
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李澜鹏
白富栋
李政
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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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid

Abstract

The invention discloses a preparation method of tung oil polyol with a high hydroxyl value, which comprises the following steps of (1) mixing tung oil, carboxylic acid, an acid catalyst and a hydroxylation reagent in proportion, and heating to 35-45 ℃; dropwise adding hydrogen peroxide solution under vigorous stirring, controlling the dropwise adding speed to maintain the reaction temperature at 40-65 ℃, and maintaining the reaction temperature for 3-5h after the dropwise adding is finished; standing and layering after the reaction is finished, separating out a water phase, and then neutralizing, washing and drying under reduced pressure to obtain tung oil polyol; (2) mixing the tung oil polyol obtained in the step (1) and an aminolysis agent in proportion, and carrying out aminolysis reaction under the action of an alkali catalyst to obtain the tung oil polyol with a high hydroxyl value. According to the invention, by utilizing the characteristic that the conjugated double bond of the tung oil can improve the reaction activity of an epoxy group, a hydroxylation reagent is added during epoxidation to synthesize tung oil polyol; then the tung oil polyol with high hydroxyl value is prepared through aminolysis reaction. The hydroxyl value of the prepared tung oil polyol is 250-450mgKOH/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

Tung oil polyol with high hydroxyl value and preparation method thereof
Technical Field
The invention belongs to the field of polyurethane materials, and particularly relates to a tung oil polyol with a high hydroxyl value and a preparation method thereof.
Background
With the gradual depletion of petroleum fossil resources worldwide, the development and utilization of biomass resources are receiving much attention. Vegetable oils are triglycerides of long carbon chain acids containing double bonds, which are widely distributed in nature and are in a wide variety of forms, among which common ones include tung oil, soybean oil, linseed oil, corn oil, rapeseed oil, peanut oil, olive oil, palm oil, castor oil, and the like. Due to the special structure and degradability of the vegetable oil, the polymer obtained from the vegetable oil is low in cost, environment-friendly and widely applied to multiple fields of polyurethane, biodiesel, paint, biomedical use and the like.
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 is reacted with organic acid and hydrogen peroxide to form epoxidized vegetable oil, and then the epoxidized vegetable oil is subjected to ring-opening reaction with a mixed solution of methanol and water to generate vegetable oil polyol.
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-.
Tung oil polyol can also be prepared from tung oil by ester bond alcoholysis method. CN103360246A discloses a method for preparing eleostearic acid monoglyceride from tung oil, which is to hydrolyze the tung oil under alkaline condition and then acidify and separate to obtain eleostearic acid; reacting glycerol and acetone under the catalysis of solid acid to obtain isopropylidene glycerol; finally, eleostearic acid and isopropylidene glycerol are subjected to esterification reaction under the catalysis of solid acid, and hydrolysis deprotection is carried out to obtain eleostearic acid monoglyceride. However, in the method, the carbon-carbon conjugated triene bond of the tung oil is not effectively converted and utilized, so that the stability of the product is poor, and side reactions such as crosslinking and curing are easy to occur in the storage process. In addition, the ester bond alcoholysis method has the defects of low conversion rate, overhigh reaction temperature (220-.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a tung oil polyol with a high hydroxyl value and a preparation method thereof. According to the invention, by utilizing the characteristic that the conjugated double bond of the tung oil can improve the reaction activity of an epoxy group, a hydroxylation reagent is added during epoxidation, so that the occurrence of a cross-linking side reaction can be effectively avoided, and the tung oil polyol is synthesized; and then, through aminolysis reaction, the hydroxyl value of the tung oil polyol is improved, and the tung oil polyol product with high hydroxyl value is prepared.
The preparation method of the tung oil polyol with the high hydroxyl value comprises the following steps:
(1) mixing tung oil, carboxylic acid, acid catalyst and hydroxylation reagent in proportion, and heating to 35-45 ℃; dropwise adding hydrogen peroxide solution under vigorous stirring, controlling the dropwise adding speed to maintain the reaction temperature at 40-65 ℃, and maintaining the reaction temperature for 3-5h after the dropwise adding is finished; standing and layering after the reaction is finished, separating out a water phase, and then neutralizing, washing and drying under reduced pressure to obtain tung oil polyol;
(2) mixing the tung oil polyol prepared in the step (1) and an aminolysis agent in proportion, and carrying out aminolysis reaction under the action of an alkali catalyst to prepare the tung oil polyol with a high hydroxyl value.
The carboxylic acid in step (1) of the present invention may be formic acid or acetic acid, preferably formic acid. The carboxylic acid can react with the hydrogen peroxide solution to generate peroxycarboxylic acid, the peroxycarboxylic acid converts conjugated double bonds in the tung oil into epoxy bonds and releases the carboxylic acid, so that the carboxylic acid is not consumed while the epoxy bonds are generated, but the reaction rate of the system is slowed down due to too small content of the carboxylic acid, and the mass ratio of the carboxylic acid to the tung oil is controlled to be 0.05:1-0.3: 1.
The acid catalyst in the step (1) of the invention can be one or more of sulfuric acid, phosphoric acid, hydrochloric acid or sulfonic acid type ion exchange resin, and the like, and is preferably sulfuric acid; the dosage of the acid catalyst is 0.01-1.0 percent of the mass of the tung oil.
The hydroxylation reagent in the step (1) of the invention 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. 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 fatty acid is easier to ionize, and the reaction activity is obviously higher than that of the alcoholic hydroxyl group formed by the adjacent vegetable oil molecular chain, so that the 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, and has wider reaction temperature window; (2) the selected fatty acid can be dissolved in the oil phase in the reaction system, so that the problem of reaction rate reduction caused by migration between oil and water phases is avoided, and the reaction selectivity is improved; (3) the oil-soluble fatty acid and the formic acid as the oxygen-carrying agent do not have chemical reaction in the system, so that the concentration of a reaction substrate is reduced, and the epoxidation and in-situ ring-opening reaction effects are influenced; (4) the use amounts of hydroxylation reagent, formic acid and hydrogen peroxide are reduced, and deionized water is not added in the initial stage of the reaction system, so that the production raw material cost and the treatment capacity of industrial wastewater are reduced.
The hydrogen peroxide solution in step (1) of the present invention functions as an oxidizing agent to oxidize carboxylic acids to peroxy acids. The higher the concentration of the hydrogen peroxide solution is, the more violent the reaction is, the serious the heat release of the system is, and side reaction is easy to occur, so the concentration of the hydrogen peroxide solution is selected to be 20-60 wt%, and the dosage of the hydrogen peroxide solution is 0.4-0.8 times of the quality of the tung oil.
The neutralization reaction in step (1) of the present invention may be carried out by using aqueous ammonia, sodium carbonate or sodium bicarbonate, preferably an aqueous solution of sodium bicarbonate having a concentration of 5wt% to 20 wt%. The washing temperature 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 aminolysis reaction in the step (2) of the invention comprises the following specific processes: mixing the tung oil polyol prepared in the step (1) and an aminolysis agent in proportion, gradually heating to 80-100 ℃ under the protection of nitrogen, and adding an alkali catalyst; then heating to 110-150 ℃ under vigorous stirring, maintaining the reaction temperature for 4-8h, and finishing the reaction to obtain the tung oil polyol with the high hydroxyl value. Compared with alcoholysis reaction, the vegetable oil has lower aminolysis reaction temperature and less side reaction, and is a method more suitable for preparing tung oil polyol.
The aminolysis agent in the step (2) is an organic alcohol amine compound with a-NH structure, preferably diethanolamine, and the dosage of the aminolysis agent is 0.05-0.2 times of the mass of the tung oil polyol prepared in the step (1).
In the step (2), the alkali catalyst is one or more of sodium methoxide, sodium ethoxide, sodium hydroxide, lithium hydroxide and the like, and the dosage of the alkali catalyst is 0.05-0.5% of the mass of the tung oil polyol prepared in the step (1).
The tung oil polyol with high hydroxyl value is prepared by the method. The hydroxyl value of the prepared tung oil polyol with the high hydroxyl value is 250-450mgKOH/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.
The application of the tung oil polyol with the high hydroxyl value prepared by the invention is that tung oil polyol and polyether polyol are taken as basic raw materials, auxiliary agents are added to prepare a combined material, the auxiliary agents comprise but are not limited to catalysts, foam stabilizers, water and flame retardants, the combined material and a foaming agent are uniformly mixed, and then the mixture reacts with isocyanate to foam, so that rigid polyurethane foam plastic and the like can be prepared.
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. According to the invention, by utilizing the characteristic that the conjugated double bond of the tung oil can improve the reaction activity of an epoxy group, a hydroxylation reagent is added during epoxidation, so that the occurrence of a cross-linking side reaction can be effectively avoided; the prepared tung oil polyol and an aminolysis agent are subjected to aminolysis reaction, so that a tung oil polyol product with a high hydroxyl value is prepared. Compared with petroleum-based polyol, the prepared tung oil polyol product with high hydroxyl value has the advantages of high hydroxyl value, good stability, renewable raw materials, nontoxicity and good biodegradability, 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 the tung oil polyol 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 problems by increasing the feeding amount of the small molecular alcohol reagent, formic acid and hydrogen peroxide, 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 under the condition of an acid catalyst, and the defects of reduction of hydroxyl value, increase of viscosity and the like of a product easily occur when the reaction temperature is high, the reaction temperature must be strictly controlled, and the construction cost of a production device is increased. According to the invention, the oil-soluble fatty acid is used as a hydroxylation reagent instead of micromolecule alcohol, so that the epoxy bond in-situ ring-opening reaction has higher selectivity and wider reaction temperature window, the problems that the concentration of the micromolecule alcohol reagent and formic acid is obviously reduced, the epoxidation and in-situ ring-opening reaction rate is slow, the cross-linking side reaction effect is not good and the like caused by the fact that the micromolecule alcohol reagent and the formic acid are easy to perform esterification reaction in the epoxidation reaction process are solved, the feeding amount of the hydroxylation reagent, the formic acid and hydrogen peroxide is effectively reduced, and the production cost is saved.
Drawings
FIG. 1 is an infrared spectrum of a high hydroxyl number tung oil polyol prepared in accordance with the present invention.
Detailed Description
The process of the present invention is further illustrated by 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, and the viscosity is measured according to a rotational viscometer method in GB/T12008.7-2010.
Example 1
500g of tung oil, 80g of formic acid (85 wt% solution), 0.5g of concentrated sulfuric acid and 150g of n-hexanoic acid are added into a 2000m L three-neck flask, the temperature is raised to 40 ℃, the mixture is stirred uniformly, 325g of 30wt% hydrogen peroxide solution is slowly dripped under the condition of vigorous stirring, the dripping speed is controlled to keep the reaction temperature at about 50 ℃, after the dripping is finished, the temperature is kept at 50 ℃ for 4 hours, the reaction is finished, the reaction system is kept still for layering, the water phase is removed, the oil phase is washed to be neutral by 10wt% sodium bicarbonate solution, the product is washed by 70 ℃ hot water for 3 times, and the washed product is distilled for 2 hours under the conditions of 2000Pa and 80 ℃ to prepare the tung oil polyol.
Uniformly mixing 80g of the prepared tung oil polyol with 11g of diethanolamine, gradually heating to 90 ℃ under the protection of nitrogen, adding 0.16g of catalyst sodium methoxide, heating to 130 ℃ under the condition of vigorous stirring, reacting at constant temperature for 6h, and finishing the reaction to obtain the tung oil polyol with high hydroxyl value. The hydroxyl value is 427mgKOH/g, the viscosity is 9100 mPa.s, the water content is lower than 0.1wt%, the yield is 92.8%, and the polyurethane rigid foam can be prepared.
Example 2
500g of tung oil, 55g of formic acid (85 wt% solution), 4g of concentrated sulfuric acid and 130g of hexanoic acid are added into a 2000m L three-neck flask, the temperature is raised to 45 ℃ and stirred uniformly, then 285g of 30wt% hydrogen peroxide solution is slowly dripped under the condition of vigorous stirring, the dripping speed is controlled to keep the reaction temperature at about 65 ℃, after the dripping is finished, the temperature is kept for 3 hours at 65 ℃, the reaction is finished, after the reaction system is kept standing and the reaction system is layered, the water phase is removed, the oil phase is washed to be neutral by 10wt% sodium bicarbonate solution, then the product is washed by 70 ℃ hot water for 3 times, and the washed product is distilled for 2 hours under the conditions of 2000Pa and 80 ℃ to prepare the tung oil polyol.
Uniformly mixing 80g of the prepared tung oil polyol with 11g of diethanolamine, gradually heating to 100 ℃ under the protection of nitrogen, adding 0.16g of catalyst sodium methoxide, heating to 150 ℃ under the condition of vigorous stirring, reacting at constant temperature for 4 hours, and finishing the reaction to obtain the tung oil polyol with high hydroxyl value. The hydroxyl value is 282mgKOH/g, the viscosity is 8800mPa & s, the water content is lower than 0.1wt%, the yield is 92.1% by detection, and the polyurethane rigid foam can be prepared.
Example 3
500g of tung oil, 100g of formic acid (85 wt% solution), 0.25g of concentrated sulfuric acid and 250g of n-hexanoic acid are added into a 2000m L three-neck flask, the temperature is raised to 35 ℃ and the mixture is stirred uniformly, then 380g of 30wt% hydrogen peroxide solution is slowly dripped under the condition of vigorous stirring, the dripping speed is controlled to keep the reaction temperature at about 40 ℃, after the dripping is finished, the temperature is kept for 5 hours at 40 ℃, after the reaction system is layered, the water phase is removed, the oil phase is washed to be neutral by 10wt% sodium bicarbonate solution, then the product is washed by 70 ℃ hot water for 3 times, and the washed product is distilled for 2 hours under the conditions of 2000Pa and 80 ℃ to prepare the tung oil polyol.
Uniformly mixing 80g of the prepared tung oil polyol with 11g of diethanolamine, gradually heating to 80 ℃ under the protection of nitrogen, adding 0.16g of catalyst sodium methoxide, heating to 110 ℃ under the condition of vigorous stirring, reacting at constant temperature for 8h, and finishing the reaction to obtain the tung oil polyol with high hydroxyl value. The detection proves that the hydroxyl value is 447mgKOH/g, the viscosity is 9050mPa & s, the water content is lower than 0.1wt%, the yield is 93.1%, and the polyurethane rigid foam can be used for preparing polyurethane rigid foam products.
Example 4
The same treatment and operating conditions as in example 1 were used, except that the carboxylic acid added was acetic acid. The obtained tung oil polyol with high hydroxyl value has the hydroxyl value of 288mgKOH/g, the viscosity of 4200mPa & s, the moisture content of less than 0.1wt percent and the yield of 92.0 percent and can be used for preparing polyurethane hard foam products.
Example 5
The same treatment and operating conditions as in example 1 were used except that the acid catalyst added was phosphoric acid. The prepared tung oil polyol with high hydroxyl value has the hydroxyl value of 408mgKOH/g, the viscosity of 8600mPa & s, the moisture content of less than 0.1wt percent and the yield of 92.5 percent, and can be used for preparing polyurethane hard foam products.
Example 6
The same treatment and operating conditions were used as in example 1, except that the hydroxylating agent added was n-heptanoic acid. The prepared tung oil polyol with high hydroxyl value has the hydroxyl value of 420mgKOH/g, the viscosity of 9140mPa & s, the water content of less than 0.1wt percent and the yield of 92.4 percent, and can be used for preparing polyurethane hard foam products.
Example 7
The same treatment and operating conditions were used as in example 1, except that the hydroxylating agent added was n-octanoic acid. The prepared tung oil polyol with high hydroxyl value has the hydroxyl value of 416mgKOH/g, the viscosity of 9210mPa & s, the moisture content of less than 0.1wt percent and the yield of 92.3 percent, and can be used for preparing polyurethane hard foam products.
Example 8
The same treatment and operating conditions were used as in example 1, except that isooctanoic acid was used as the hydroxylating agent. The prepared tung oil polyol with high hydroxyl value has the hydroxyl value of 405mgKOH/g, the viscosity of 9420mPa & s, the water content of less than 0.1wt percent and the yield of 92.2 percent, and can be used for preparing polyurethane hard foam products.
Example 9
The same treatment and operating conditions were used as in example 1, except that the base catalyst added was sodium hydroxide. The prepared tung oil polyol with high hydroxyl value has the hydroxyl value of 422mgKOH/g, the viscosity of 9050mPa & s, the water content of less than 0.1wt percent and the yield of 92.7 percent, and can be used for preparing polyurethane hard foam products.
Comparative example 1
The same treatment and operating conditions were used as in example 1, except that no hydroxylating agent was added. The viscosity of the product was 470000 mPas, and the product was too high to be dissolved and further aminolysis reaction could not be performed, so that it could not be used for the production of rigid polyurethane foam.
Comparative example 2
The same treatment and operating conditions were used as in example 1, except that the soybean oil was used to prepare the polyol. The product had a hydroxyl value of 138mgKOH/g and a viscosity of 3400 mPas. Because the soybean oil does not undergo hydroxylation reaction in situ in the first step of reaction, the unsaturated double bond utilization efficiency is low, the hydroxyl value of the product is low, and the product cannot be used for preparing polyurethane hard foam products.
Comparative example 3
The same treatment and operating conditions were used as in example 1, except that methanol was used as the hydroxylating agent. The hydroxyl value of the prepared tung oil polyol is 245.5mgKOH/g, the viscosity is 83200 mPa.s, and the actual concentration of methanol in a reaction system is low because the methanol is easy to generate esterification reaction with formic acid in the reaction system, so that the cross-linking of tung oil in the epoxidation reaction cannot be completely avoided, and the viscosity is too high, so that the tung oil polyol cannot be used for preparing polyether polyol products.
Comparative example 4
The same treatment and operating conditions were used as in example 1, except that tung oil was used directly to react with the aminolysis agent and the base catalyst. The hydroxyl value of the prepared tung oil polyol is 182mgKOH/g, and the carbon-carbon conjugated double bonds of the tung oil are not effectively utilized, so that the hydroxyl value of the product is lower. In addition, the carbon-carbon conjugated double bond has high reactivity, is easy to generate polymerization or diene synthesis and the like, and is unstable in the process of storage or use, so that the product cannot be used for synthesizing polyurethane products.

Claims (11)

1. The preparation method of the tung oil polyol with the high hydroxyl value is characterized by comprising the following steps:
(1) tung oil, carboxylic acid, acid catalyst and hydroxylation reagentMixing in proportion, wherein the hydroxylating agent is an oil-soluble fatty acid selected from C6-C12The carboxylic acid is formic acid or acetic acid, the acid catalyst is one or more of sulfuric acid, phosphoric acid, hydrochloric acid and sulfonic acid type ion exchange resin, and the temperature is raised to 35-45 ℃; dropwise adding hydrogen peroxide solution under vigorous stirring, controlling the dropwise adding speed to maintain the reaction temperature at 40-65 ℃, and maintaining the reaction temperature for 3-5h after the dropwise adding is finished; standing and layering after the reaction is finished, separating out a water phase, and then neutralizing, washing and drying under reduced pressure to obtain tung oil polyol; (2) mixing the tung oil polyol prepared in the step (1) and an aminolysis agent in proportion, and carrying out aminolysis reaction under the action of an alkali catalyst to prepare the tung oil polyol with a high hydroxyl value.
2. The method of claim 1, wherein: in the step (1), the mass ratio of the carboxylic acid to the tung oil is controlled to be 0.05:1-0.3: 1.
3. The method of claim 1, wherein: the dosage of the acid catalyst in the step (1) is 0.01-1.0 percent of the mass of the tung oil.
4. The method of claim 1, wherein: the dosage of the hydroxylation reagent in the step (1) is 0.1-0.5 time of the mass of the tung oil.
5. The method of claim 1 or 4, wherein: the oil-soluble fatty acid is n-hexanoic acid, n-heptanoic acid, n-octanoic acid, isocaproic acid, isoheptanoic acid or isooctanoic acid.
6. The method of claim 1, wherein: the concentration of the hydrogen peroxide solution in the step (1) is 20-60 wt%, and the dosage is 0.4-0.8 time of the mass of the tung oil.
7. The method of claim 1, wherein: neutralizing the neutralization reaction in the step (1) by using a sodium bicarbonate water solution with the concentration of 5-20 wt%; 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 pressure of 1000-3000Pa and temperature of 60-120 ℃ so as to ensure that the moisture content of the product is less than 0.1 wt%.
8. The method of claim 1, wherein: the aminolysis reaction in the step (2) comprises the following specific processes: mixing the tung oil polyol prepared in the step (1) and an aminolysis agent in proportion, gradually heating to 80-100 ℃ under the protection of nitrogen, and adding an alkali catalyst; then heating to 110-150 ℃ under vigorous stirring, maintaining the reaction temperature for 4-8h, and finishing the reaction to obtain the tung oil polyol with the high hydroxyl value.
9. The method of claim 1 or 8, wherein: the aminolysis agent in the step (2) is an organic alcohol amine compound with a-NH structure, and the dosage of the aminolysis agent is 0.05-0.2 times of the mass of the tung oil polyol in the step (1).
10. The method of claim 9, wherein: and (3) the aminolysis agent in the step (2) is diethanolamine.
11. The method of claim 1 or 8, wherein: the alkali catalyst in the step (2) is one of sodium methoxide, sodium ethoxide, sodium hydroxide and lithium hydroxide, and the dosage of the alkali catalyst is 0.05-0.5% of the mass of the tung oil polyalcohol in the step (1).
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103274930A (en) * 2013-06-20 2013-09-04 南京工业大学 Vegetable oil polyol preparation method by using continuous method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103274930A (en) * 2013-06-20 2013-09-04 南京工业大学 Vegetable oil polyol preparation method by using continuous method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Chemically modified biolubricant basestocks from epoxidized oleic acid: Improved low temperature properties and oxidative stability;Jumat Salimon，et al.;《Journal of Saudi Chemical Society》;20110906(第15期);195-201 *
Polyurethanes From Tung Oil: Polymer Characterization and Composites;M.A.Mosiewicki等;《Polymer Engineering and Science》;20090430;第49卷(第4期);685-692 *

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