CN107151212B - Tung oil polyol with low hydroxyl value and preparation method thereof - Google Patents

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

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CN107151212B
CN107151212B CN201610119888.XA CN201610119888A CN107151212B CN 107151212 B CN107151212 B CN 107151212B CN 201610119888 A CN201610119888 A CN 201610119888A CN 107151212 B CN107151212 B CN 107151212B
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tung oil
acid
catalyst
reaction
oil polyol
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CN107151212A (en
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李澜鹏
李志瑞
白富栋
乔凯
王领民
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
China Petrochemical Corp
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
China Petrochemical Corp
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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
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a preparation method of tung oil polyol with a low hydroxyl value, which comprises the following steps of (1) mixing tung oil, carboxylic acid, a catalyst and a hydroxylation reagent in proportion, and heating to 35-45 ℃; dropping hydrogen peroxide solution under the condition of violent stirring to maintain the reaction temperature at 40-65 ℃, and maintaining the reaction temperature for 3-5 hours after dropping; standing and layering after the reaction is finished, separating out a water phase, and then neutralizing, washing and distilling under reduced pressure to obtain tung oil polyol; (2) mixing the tung oil polyol prepared in the step (1) with an alkaline catalyst in proportion, heating to 90-140 ℃, adding an epoxide for polymerization, and performing acid neutralization, water washing and reduced pressure distillation after the reaction is finished to obtain the tung oil polyol with the low hydroxyl value. The hydroxyl value of the low-hydroxyl value tung oil polyol prepared by the invention is 30-100mgKOH/g, the acid value is lower than 1.0mgKOH/g, the water content is lower than 0.1wt%, the yield is higher than 90%, and the low-hydroxyl value tung oil polyol is suitable for preparing polyurethane soft foam materials, polyurethane elastomers and the like.

Description

Tung oil polyol with low hydroxyl value and preparation method thereof
Technical Field
The invention belongs to the field of polyurethane materials, and particularly relates to a low-hydroxyl-value tung oil polyol and a preparation method thereof.
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 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-.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a tung oil polyol with a low 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 efficiently synthesized; and then polymerizing the prepared tung oil polyol with an epoxide to obtain a low hydroxyl value tung oil polyol product.
The preparation method of the low hydroxyl value tung oil polyol comprises the following steps: (1) mixing tung oil, carboxylic acid, a catalyst and a hydroxylation reagent in proportion, and heating to 35-45 ℃; dropwise adding a hydrogen peroxide solution under the condition of violent stirring, controlling the dropwise adding speed to keep the reaction temperature at 40-65 ℃, and maintaining the reaction temperature for 3-5 hours after the dropwise adding is finished; standing and layering after the reaction is finished, separating out a water phase, and then neutralizing, washing and distilling under reduced pressure to obtain tung oil polyol; (2) mixing the tung oil polyol prepared in the step (1) with an alkaline catalyst in proportion, heating to 90-140 ℃, adding an epoxide for polymerization, and performing acid neutralization, water washing and reduced pressure distillation after the reaction is finished to obtain the tung oil polyol with the low 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 catalyst in the step (1) of the invention is inorganic acid, urea or metal ion loaded cation exchange resin catalyst and the like. The inorganic acid catalyst can be one or more of sulfuric acid, phosphoric acid, hydrochloric acid and the like, and is preferably sulfuric acid; the dosage of the inorganic acid catalyst is 0.01-1.0 percent of the mass of the tung oil. When the urea catalyst is adopted, the dosage is 0.1-2.0% of the tung oil by mass. In the adopted metal ion supported cation exchange resin catalyst, the matrix cation exchange resin is macroporous strong-acid styrene cation exchange resin, and the supported metal ion is selected from Al3+、Fe3+、Fe2+、Cu2+、Zn2+、Sn4+、Ni2+、Co3+Etc., preferably Al3+The metal ion load accounts for 0.5 to 3 percent of the mass of the catalyst; the dosage of the catalyst is 5 to 15 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. 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 small molecule alcoholsThe 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 neutralized with aqueous ammonia, sodium carbonate or sodium bicarbonate, preferably with a sodium bicarbonate solution 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 reaction process in the step (2) of the invention is specifically that tung oil polyol and an alkaline catalyst are mixed according to a proportion, after the temperature is gradually raised to 90-140 ℃ under the protection of nitrogen, epoxide is added within 5-10h, and the reaction is finished after the reaction is carried out for 2-6h at constant temperature.
In step (2), the alkaline catalyst is an oxide or hydroxide of an alkali metal (such as lithium, sodium, potassium, rubidium, cesium, francium, and the like), such as one or more of lithium oxide, sodium oxide, potassium oxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like; the dosage of the catalyst is 0.1-1.0% of the mass of the tung oil polyalcohol.
The epoxide in the step (2) is one or more of epoxides such as propylene oxide, ethylene oxide, butylene oxide and the like; the dosage of the epoxide is 2.0 to 5.0 times of the mass of the tung oil polyalcohol.
The acid neutralization reaction in step (2) of the present invention is carried out by using an aqueous phosphoric acid solution having a concentration of 5 to 20% by weight. The washing temperature is 50-80 ℃, the reduced pressure distillation is to remove the residual moisture in the system under the conditions of the pressure of 1000-3000Pa and the temperature of 60-120 ℃ to ensure that the moisture content of the product is less than 0.1 wt%.
The low hydroxyl value tung oil polyol of the invention is prepared by the method of the invention. The hydroxyl value of the prepared tung oil polyol is 30-100mgKOH/g, the acid value is lower than 1.0mgKOH/g, the water content is lower than 0.1wt%, the yield is higher than 90%, and the tung oil polyol is suitable for preparing polyurethane flexible foam materials, polyurethane elastomers and the like.
The application of the tung oil polyol prepared by the invention is that tung oil polyol and polyether polyol are used as basic raw materials, auxiliary agents are used for preparing 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 mixed material reacts with isocyanate for foaming, so that polyurethane soft foam materials, polyurethane elastomers and the like can be prepared.
More than 85% of unsaturated bonds in tung oil molecules are carbon-carbon conjugated triene bonds, and in the process of preparing the polyol, due to the existence of the conjugated double bonds, epoxy groups have higher reactivity and poor selectivity and are easy to generate side reactions, so that macromolecular cross-linked products are generated, the viscosity is increased rapidly, 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 obtained tung oil polyol is further polymerized with epoxide to obtain a high-quality tung oil polyol product with a low hydroxyl value, and the product can be used for preparing polyurethane soft foam materials and polyurethane elastomers. Compared with petroleum-based polyol, the low-hydroxyl-value tung oil polyol prepared by the invention has the advantages of renewable raw materials, no toxicity 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 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 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, because the small molecular alcohol reagent has the 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 higher, 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 a small molecular alcohol reagent, so that the epoxy bond in-situ ring-opening reaction has higher selectivity and a wider reaction temperature window, and the problems that the small molecular alcohol reagent and an oxygen-carrying agent formic acid are easy to perform esterification reaction in the epoxidation reaction process, 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, the cross-linking side reaction effect is not good and the like 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 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 product 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, 80g of formic acid (85 wt% solution), 0.5g of concentrated sulfuric acid and 150g of n-hexanoic acid are added into a 2000mL three-neck flask, and the mixture is heated to 40 ℃ and stirred uniformly. Then, 325g of 30wt% hydrogen peroxide solution is slowly dropped into the solution under the condition of vigorous stirring, the dropping speed is controlled to keep the reaction temperature at about 50 ℃, and after the dropping is finished, the temperature is kept constant at 50 ℃ for 4 hours, and the reaction is finished. After the reaction system was layered, the aqueous phase was removed, the oil phase was washed with 10wt% aqueous sodium bicarbonate solution to neutrality, and the product was then washed with hot water at 70 ℃ 3 times. Distilling the washed product for 2h under the conditions of 2000Pa and 80 ℃ to prepare the tung oil polyol.
Adding 250g of the prepared tung oil polyol and 1.25g of sodium hydroxide into a reaction kettle, uniformly mixing, gradually heating to 120 ℃ under the protection of nitrogen, adding 760g of propylene oxide within 7.5h, continuously reacting for 4h, and finishing the reaction. The reaction system was washed to neutrality with a 10wt% phosphoric acid aqueous solution, and then the product was washed 3 times with hot water at 70 ℃. Distilling the washed product for 2h under the conditions of 2000Pa and 80 ℃ to obtain the tung oil polyol with the low hydroxyl value. The detection proves that the hydroxyl value is 68.3mgKOH/g, the viscosity is 7300 mPa.s, the acid value is 0.42mgKOH/g, the water content is lower than 0.1wt%, the yield is 92.4%, and the polyurethane can be used for preparing products such as polyurethane soft foam materials, polyurethane elastomers and the like.
Example 2
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 2000mL three-neck flask, and the mixture is heated to 45 ℃ and stirred uniformly. Then slowly dripping 380g of 30wt% hydrogen peroxide solution under the condition of violent stirring, controlling the dripping speed to keep the reaction temperature at about 65 ℃, keeping the temperature at 65 ℃ for 3 hours after finishing dripping, and finishing the reaction. After the reaction system was layered, the aqueous phase was removed, the oil phase was washed with 10wt% aqueous sodium bicarbonate solution to neutrality, and the product was then washed with hot water at 70 ℃ 3 times. Distilling the washed product for 2h under the conditions of 2000Pa and 80 ℃ to obtain the tung oil polyol.
Adding 250g of the prepared tung oil polyol and 1.25g of potassium hydroxide into a reaction kettle, uniformly mixing, gradually heating to 140 ℃ under the protection of nitrogen, adding 760g of ethylene oxide within 7.5h, continuing to react for 3h, and finishing the reaction. The reaction system was washed to neutrality with a 10wt% phosphoric acid aqueous solution, and then the product was washed 3 times with hot water at 70 ℃. Distilling the washed product for 2h under the conditions of 2000Pa and 80 ℃ to obtain the tung oil polyol with the low hydroxyl value. The hydroxyl value is 72.4mgKOH/g, the viscosity is 7220 mPa.s, the acid value is 0.42mgKOH/g, the water content is lower than 0.1wt%, the yield is 92.5%, and the polyurethane can be used for preparing products such as polyurethane flexible foam materials, polyurethane elastomers and the like.
Example 3
500g of tung oil, 55g of formic acid (85 wt% solution), 4g of concentrated sulfuric acid and 100g of n-hexanoic acid are added into a 2000mL three-neck flask, and the mixture is heated to 35 ℃ 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 40 ℃, and after the dripping is finished, the temperature is kept constant at 40 ℃ for 5 hours, and the reaction is finished. After the reaction system was layered, the aqueous phase was removed, the oil phase was washed with 10wt% aqueous sodium bicarbonate solution to neutrality, and the product was then washed with hot water at 70 ℃ 3 times. Distilling the washed product for 2h under the conditions of 1000-3000Pa and 80 ℃ to obtain the tung oil polyalcohol.
Adding 250g of the prepared tung oil polyol and 1.25g of lithium hydroxide into a reaction kettle, uniformly mixing, gradually heating to 90 ℃ under the protection of nitrogen, adding 510g of butylene oxide within 5h, continuing to react for 6h, and finishing the reaction. The reaction system was washed to neutrality with a 10wt% phosphoric acid aqueous solution, and then the product was washed 3 times with hot water at 70 ℃. Distilling the washed product for 2h under the conditions of 2000Pa and 80 ℃ to obtain the tung oil polyol with the low hydroxyl value. The hydroxyl value is 95.6mgKOH/g, the viscosity is 7750 mPa.s, the acid value is 0.46mgKOH/g, the water content is lower than 0.1wt%, the yield is 92.9%, and the polyurethane can be used for preparing products such as polyurethane soft foam materials, polyurethane elastomers and the like.
Example 4
The same treatment and operating conditions as in example 1 were used, except that 5g of urea was used as the catalyst in step (1). The prepared tung oil polyol has a hydroxyl value of 72.2mgKOH/g, viscosity of 7250mPa & s, an acid value of 0.41mgKOH/g, water content of less than 0.1wt% and yield of 92.6%, and can be used for preparing products such as polyurethane flexible foam materials, polyurethane elastomers and the like.
Example 5
The same treatment and operating conditions as in example 1 were used, except that 50g of Al was used as the catalyst in step (1)3+Supported cation exchange resin catalyst of Al3+The loading amount of (A) was 1.0% by mass of the catalyst. The hydroxyl value of the prepared tung oil polyol is 75.4mgKOH/g, the viscosity is 7180mPa & s, the acid value is 0.40mgKOH/g, the water content is lower than 0.1wt%, the yield is 92.8%, and the tung oil polyol can be used for preparing products such as polyurethane flexible foam materials, polyurethane elastomers and the like.
Example 6
The same treatment and operating conditions as in example 1 were used except that acetic acid was used as the carboxylic acid in step (1). The prepared tung oil polyol has a hydroxyl value of 46.4mgKOH/g, a viscosity of 7080mPa & s, an acid value of 0.40mgKOH/g, water content of less than 0.1wt% and a yield of 92.2%, and can be used for preparing products such as polyurethane flexible foam materials, polyurethane elastomers and the like.
Example 7
The same treatment and operating conditions as in example 1 were used except that n-heptanoic acid was used as the hydroxylating agent in step (1). The hydroxyl value of the prepared tung oil polyol is 56.3mgKOH/g, the viscosity is 8800 mPa.s, the acid value is 0.44mgKOH/g, the water content is lower than 0.1wt%, the yield is 92.3%, and the tung oil polyol can be used for preparing products such as polyurethane flexible foam materials, polyurethane elastomers and the like.
Example 8
The same treatment and operating conditions as in example 1 were used, except that isooctanoic acid was used as the hydroxylating agent in step (1). The hydroxyl value of the prepared tung oil polyol is 52.4mgKOH/g, the viscosity is 9400 mPa.s, the acid value is 0.47mgKOH/g, the water content is lower than 0.1wt%, the yield is 91.9%, and the tung oil polyol can be used for preparing products such as polyurethane flexible foam materials, polyurethane elastomers and the like.
Example 9
The same treatment and operating conditions as in example 1 were used except that sodium oxide was used as the basic catalyst in step (2). The hydroxyl value of the prepared tung oil polyol is 73.6mgKOH/g, the viscosity is 6940 mPa.s, the acid value is 0.40mgKOH/g, the water content is lower than 0.1wt%, the yield is 92.7%, and the tung oil polyol can be used for preparing products such as polyurethane flexible foam materials, polyurethane elastomers and the like.
Comparative example 1
The same treatment and operating conditions as in example 1 were used, except that no hydroxylating agent was added in step (1). The product viscosity was 470000 mPas, and the product viscosity was too high to be dissolved and further hydroxylation reaction could not be carried out, so that it could not be used for the production of polyurethane products.
Comparative example 2
The same treatment and operating conditions as in example 1 were used, except that butanol was used as the hydroxylating agent. The hydroxyl value of the prepared tung oil polyol is 42.5mgKOH/g, the viscosity is 57200 mPa.s, and the actual concentration of butanol in a reaction system is lower due to the fact that butanol is easy to perform esterification reaction with formic acid in the reaction system, and the cross-linking of tung oil in epoxidation reaction cannot be completely avoided, so that the viscosity is too high, and the tung oil polyol cannot be used for preparing polyether polyol products.
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 6.2mgKOH/g, and the product cannot be subjected to polymerization reaction with epoxide because the product does not undergo hydroxylation reaction in the first step of reaction and has too low hydroxyl value, so that the product cannot be used for preparing polyether polyol products.
Comparative example 4
The same treatment conditions as in example 1 were used except that tung oil was directly reacted with an alkaline catalyst. As the tung oil is not subjected to epoxidation and hydroxylation, the product has no reactive hydroxyl group and cannot be used for preparing polyether polyol products.

Claims (13)

1. The preparation method of the low hydroxyl value tung oil polyol is characterized by comprising the following steps: (1) mixing tung oil, carboxylic acid, a catalyst and a hydroxylation reagent in proportion, and heating to 35-45 ℃; the carboxylic acid is formic acidOr acetic acid; the hydroxylating agent is an oil-soluble fatty acid selected from C6-C12One or more of the straight chain or branched chain saturated fatty acids of (1); dropwise adding a hydrogen peroxide solution under the condition of violent stirring, controlling the dropwise adding speed to keep the reaction temperature at 40-65 ℃, and maintaining the reaction temperature for 3-5 hours after the dropwise adding is finished; standing and layering after the reaction is finished, separating out a water phase, and then neutralizing, washing and distilling under reduced pressure to obtain tung oil polyol; (2) mixing the tung oil polyol prepared in the step (1) with an alkaline catalyst in proportion, heating to 90-140 ℃, adding an epoxide for polymerization, and performing acid neutralization, water washing and reduced pressure distillation after the reaction is finished to obtain the tung oil polyol with the low 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 catalyst in the step (1) is inorganic acid, urea or metal ion loaded cation exchange resin catalyst.
4. A method according to claim 3, characterized by: the inorganic acid catalyst is one or more of sulfuric acid, phosphoric acid or hydrochloric acid, and the using amount of the inorganic acid catalyst is 0.01-1.0% of the mass of the tung oil; when the urea catalyst is adopted, the dosage is 0.1-2.0% of the tung oil by mass; in the catalyst of metal ion supported cation exchange resin, the matrix cation exchange resin is macroporous strong acid styrene cation exchange resin, and the supported metal ion is Al3+、Fe3+、Fe2+、Cu2+、Zn2+、Sn4+、Ni2+、Co3+The metal ion load accounts for 0.5-3% of the mass of the catalyst, and the dosage of the catalyst is 5-15% of the mass of the tung oil.
5. The method of claim 1, wherein: the dosage of the oil-soluble fatty acid in the step (1) is 0.1 to 0.5 time of the mass of the tung oil.
6. The method of claim 1 or 5, wherein: the oil-soluble fatty acid is n-hexanoic acid, n-heptanoic acid, n-octanoic acid, isocaproic acid, isoheptanoic acid or isooctanoic acid.
7. 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.
8. The method of claim 1, wherein: sodium bicarbonate solution with the concentration of 5wt% -20wt% is used in the neutralization reaction in the step (1); 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%.
9. The method of claim 1, wherein: and (3) in the reaction process of the step (2), gradually heating to 90-140 ℃ under the protection of nitrogen, adding epoxide in 5-10h, reacting for 2-6h at constant temperature, and finishing the reaction.
10. A method according to claim 1 or 9, characterized by: and (3) in the step (2), the alkaline catalyst is oxide or hydroxide of alkali metal, and the alkali metal is lithium, sodium, potassium, rubidium, cesium or francium.
11. The method of claim 10, wherein: the alkaline catalyst is one or more of lithium oxide, sodium oxide, potassium oxide, sodium hydroxide, potassium hydroxide and lithium hydroxide, and the dosage of the catalyst is 0.1-1.0% of the mass of the tung oil polyalcohol.
12. A method according to claim 1 or 9, characterized by: the epoxide in the step (2) is one or more of propylene oxide, ethylene oxide and butylene oxide, and the dosage of the epoxide is 2.0 to 5.0 times of the mass of the tung oil polyol.
13. A method according to claim 1 or 9, characterized by: neutralizing the acid in the step (2) by using a phosphoric acid aqueous solution with the concentration of 5-20 wt%; the washing temperature is 50-80 ℃; the reduced pressure distillation is to remove the 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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WO2006012344A1 (en) * 2004-06-25 2006-02-02 Pittsburg State University Modified vegetable oil-based polyols
WO2008130646A1 (en) * 2007-04-18 2008-10-30 Biobased Technologies, Llc A process for the manufacture of natural oil hydroxylates
CN101386563A (en) * 2008-10-24 2009-03-18 江苏钟山化工有限公司 Method for preparing plant oil-based polyol
CN102206154A (en) * 2011-03-11 2011-10-05 清华大学 Vegetable oil polyol and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006012344A1 (en) * 2004-06-25 2006-02-02 Pittsburg State University Modified vegetable oil-based polyols
WO2008130646A1 (en) * 2007-04-18 2008-10-30 Biobased Technologies, Llc A process for the manufacture of natural oil hydroxylates
CN101386563A (en) * 2008-10-24 2009-03-18 江苏钟山化工有限公司 Method for preparing plant oil-based polyol
CN102206154A (en) * 2011-03-11 2011-10-05 清华大学 Vegetable oil polyol and preparation method thereof

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