[go: up one dir, main page]

CN107151303B - Tung oil-based hard polyurethane foam plastic and preparation method thereof - Google Patents

Tung oil-based hard polyurethane foam plastic and preparation method thereof Download PDF

Info

Publication number
CN107151303B
CN107151303B CN201610119877.1A CN201610119877A CN107151303B CN 107151303 B CN107151303 B CN 107151303B CN 201610119877 A CN201610119877 A CN 201610119877A CN 107151303 B CN107151303 B CN 107151303B
Authority
CN
China
Prior art keywords
tung oil
acid
reaction
catalyst
polyol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610119877.1A
Other languages
Chinese (zh)
Other versions
CN107151303A (en
Inventor
李澜鹏
白富栋
李政
薛冬
乔凯
王领民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Original Assignee
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Fushun Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201610119877.1A priority Critical patent/CN107151303B/en
Publication of CN107151303A publication Critical patent/CN107151303A/en
Application granted granted Critical
Publication of CN107151303B publication Critical patent/CN107151303B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C07C67/30—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • 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
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a tung oil-based rigid polyurethane foam plastic and a preparation method thereof, which comprises the steps of firstly mixing tung oil, carboxylic acid, an acid catalyst and a hydroxylation reagent in proportion, and heating to 35-45 ℃; dropwise adding a hydrogen peroxide solution to maintain the reaction at 40-65 ℃, and after dropwise adding, maintaining the reaction for 3-5 h; 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; mixing the tung oil polyol and an aminolysis agent, and carrying out aminolysis reaction under the action of an alkali catalyst to prepare the tung oil polyol with a high hydroxyl value; and (2) uniformly mixing the tung oil polyol with the high hydroxyl value, a foam stabilizer, a catalyst and a foaming agent in proportion to prepare a component A, adding isocyanate of the component B, stirring and mixing at a high speed, and pouring into a mould for foaming to prepare the tung oil-based rigid polyurethane foam plastic. The tung oil-based rigid polyurethane foam plastic prepared by the invention has the advantages of renewable raw materials, no toxicity, good biodegradability and the like, and belongs to environment-friendly bio-based polyurethane.

Description

Tung oil-based hard polyurethane foam plastic and preparation method thereof
Technical Field
The invention belongs to the field of polyurethane materials, and particularly relates to tung oil-based rigid polyurethane foam plastic 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 various types, and common among them are tung oil, soybean oil, linseed oil, corn oil, rapeseed oil, peanut oil, olive oil, palm oil, castor oil, and the like. The vegetable oil has special structure and degradability, so that the obtained polymer is low in cost, environment-friendly and widely applied to the fields of polyurethane, biodiesel, paint, biomedicine 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 higher 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 percent of unsaturated bonds are carbon-carbon conjugated triene bonds, the epoxy groups have higher reaction activity and poor selectivity in the process of preparing the polyol, and side reactions are easy to occur, so that macromolecular cross-linked products are generated, the viscosity is increased rapidly, and the high-quality vegetable oil polyol is usually solid at room temperature and cannot be used for further synthesizing polyurethane materials. Research literature (such as Epoxidation of Natural Triglycerides with ethylene oxidation, Journal of the American Oil Chemists' Society, 1996, 73: 461-.
CN103360246A discloses a method for preparing eleostearic acid monoglyceride, which comprises the steps of hydrolyzing eleostearic oil into eleostearic acid under an alkaline condition, reacting with glycerol and acetone under the catalysis of solid acid to obtain isopropylidene glycerol, and hydrolyzing and deprotecting 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 tung oil-based rigid polyurethane foam plastic and a preparation method thereof. The tung oil-based rigid polyurethane foam plastic prepared by the invention has the advantages of renewable raw materials, no toxicity, good biodegradability and the like, belongs to environment-friendly bio-based polyurethane, and has wide application prospect.
The preparation method of the tung oil-based rigid polyurethane foam plastic 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 at 40-65 ℃, and maintaining the reaction for 3-5h after the dropwise adding is finished; standing and layering after the reaction is finished, separating out a water phase, and neutralizing, washing and distilling an oil phase under reduced pressure to obtain tung oil polyol;
(2) mixing the tung oil polyol prepared in the step (1) with an aminolysis agent, and carrying out aminolysis reaction under the action of an alkali catalyst to prepare tung oil polyol with a high hydroxyl value;
(3) and (3) uniformly mixing the tung oil polyol with the high hydroxyl value prepared in the step (2), a foam stabilizer, a catalyst and a foaming agent in proportion to prepare a component A, adding isocyanate of the component B, stirring and mixing at a high speed, and pouring into a mould for foaming to prepare the tung oil-based rigid polyurethane foam plastic.
The carboxylic acid in step (1) of the present invention is 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 is an inorganic acid catalyst, such as one or more of sulfuric acid, phosphoric acid, hydrochloric acid and the like, and 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. The oil-soluble fatty acid may be selected from C6-C12The one or more of the straight chain or branched chain saturated fatty acids can be 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 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 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 that 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 mass 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%.
In the ammonolysis reaction in the step (2), tung oil polyalcohol and an ammonolysis agent are mixed in proportion, the temperature is gradually increased to 80-100 ℃ under the protection of nitrogen, and an alkali catalyst is added; then heating to 110-150 ℃ under the condition of vigorous stirring, and maintaining the reaction temperature for 4-8h to prepare the tung oil polyol with high hydroxyl value. Compared with alcoholysis reaction, the vegetable oil has lower aminolysis reaction temperature, less side reaction and reaction conversion rate of over 90 percent, and is a method 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 tung oil polyol.
The alkali catalyst in the step (2) 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 percent of the mass of the tung oil polyalcohol.
In the component A in the step (3), 100 parts of high hydroxyl value tung oil polyol, 2-3 parts of foam stabilizer, 0.5-5 parts of catalyst and 10-20 parts of foaming agent are calculated by weight. Wherein the foam stabilizer is an organic silicon foam stabilizer. The catalyst is amine catalyst, and can be one or more selected from N, N-dimethylcyclohexylamine, triethylene diamine, triethanolamine, diethylenetriamine and the like. The foaming agent is cyclopentane. The cyclopentane foaming agent has the advantages of zero ODP (ozone depletion potential) and GWP (global warming potential) less than 10, and meets the requirement of environmental protection. In addition, the high hydroxyl value tung oil polyol prepared by the invention and cyclopentane have excellent compatibility and can meet the use requirement of cyclopentane as a foaming agent.
The component B isocyanate in the step (3) of the invention is selected from one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), polymethylene polyphenyl polyisocyanate (PAPI) and the like, and the using amount of the component B isocyanate is 0.75-1.6 times of the mass of the component A.
The tung oil-based rigid polyurethane foam plastic is prepared by the method. The prepared tung oil-based hard polyurethane foam plastic has the heat conductivity coefficient of less than or equal to 0.021W/m.k, the compression strength of more than or equal to 130kPa, the dimensional stability (70 ℃, 48 h) of less than or equal to 1.5 percent, the water absorption of less than or equal to 2.0 percent and the apparent core density of less than or equal to 38kg/cm3The performance index reaches the use requirement of the polyurethane rigid foam plastic.
As more than 85% of unsaturated bonds in molecules of the tung oil are carbon-carbon conjugated triene bonds, epoxy groups have higher reactivity, poor selectivity and easy side reaction in the process of preparing the polyol, so that macromolecular cross-linked products are generated, the viscosity is increased sharply, and the tung oil cannot be used for further synthesizing polyurethane materials. 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, the tung oil polyol is prepared by adding the oil-soluble fatty acid while epoxidizing, so that the occurrence of a cross-linking side reaction can be effectively avoided; then, preparing the tung oil polyol with high hydroxyl value through aminolysis reaction; and then the tung oil polyol with the high hydroxyl value is used as a polyether raw material, and cyclopentane is used as a foaming agent to prepare the tung oil-based hard polyurethane foam plastic. The prepared tung oil-based rigid polyurethane foam plastic has the advantages of renewable raw materials, no toxicity, good biodegradability and the like, belongs to environment-friendly bio-based polyurethane, and has wide application prospect.
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 small molecular alcohol reagents, formic acid and hydrogen peroxide and adding deionized water, and the production raw material cost and the treatment amount of industrial wastewater are greatly increased. According to the invention, 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 in the epoxidation reaction process, the micromolecule alcohol reagent is easy to perform esterification reaction with an oxygen-carrying agent formic acid, the concentration of the micromolecule 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, deionized water is not required to be added in the initial stage of the reaction system, and the production raw material cost and the treatment amount of industrial.
In the preparation process of rigid polyurethane foam, the used foaming agents F11 and HCFC-141b have good compatibility with polyether polyol commonly used at present, but the foaming agents have destructive effect on atmospheric ozone layers, and are eliminated according to the provisions of Montreal protocol. Cyclopentane serving as a foaming agent has no destructive effect on an ozone layer, but has poor compatibility with common polyether polyol, and cannot achieve a good foaming effect. According to the invention, the tung oil polyol is prepared by adding the oil-soluble fatty acid and adopting a one-step method, and then the tung oil polyol with high hydroxyl value and excellent compatibility with the environment-friendly foaming agent cyclopentane is prepared through aminolysis reaction, so that the foaming effect is good, and the compatibility of the foaming agent and the polyol is obviously improved. The prepared rigid polyurethane foam plastic is an environment-friendly bio-based polyurethane material.
Detailed Description
The process of the present invention is further illustrated by the following examples. In the present invention, wt% means mass fraction.
The heat conductivity coefficient of the tung oil-based rigid polyurethane foam plastic prepared by the invention is determined according to a method specified in GB/T10294-. The hydroxyl value of the prepared tung oil polyol 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 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. Standing until the reaction system is layered, removing the water phase, washing the oil phase to be neutral by using 10wt% of sodium bicarbonate water solution, and then washing the product for 3 times by using hot water at 70 ℃. Distilling the washed product for 2h under the conditions of 2000Pa and 80 ℃ to prepare the tung oil polyol.
Uniformly mixing 80g of the prepared tung oil polyol with 14g 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.
100g of tung oil polyol with high hydroxyl value, 2.5g of organosilicon foam stabilizer, 2g of N, N-dimethylcyclohexylamine and 14g of cyclopentane are uniformly mixed, 115g of diphenylmethane diisocyanate is added, and the mixture is poured into a mould to be foamed after being fully and uniformly stirred, so that the tung oil-based rigid polyurethane foam plastic is prepared. The product properties are shown in Table 1.
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 4 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 prepare the tung oil polyol.
Uniformly mixing 80g of the prepared tung oil polyol with 16g of diethanolamine, gradually heating to 100 ℃ under the protection of nitrogen, adding 0.16g of catalyst sodium hydroxide, heating to 150 ℃ under vigorous stirring, reacting at constant temperature for 4 hours, and finishing the reaction to obtain the tung oil polyol with high hydroxyl value.
100g of tung oil polyol with high hydroxyl value, 2.5g of organosilicon foam stabilizer, 2.5g of triethylene diamine and 14g of cyclopentane are uniformly mixed, 90g of toluene diisocyanate is added, and the mixture is poured into a mould to be foamed after being fully and uniformly stirred, so that the tung oil-based rigid polyurethane foam plastic is prepared. The product properties are shown in Table 1.
Example 3
500g of tung oil, 60g of formic acid (85 wt% solution), 4g of concentrated sulfuric acid and 120g of n-hexanoic acid are added into a 2000mL three-neck flask, and the mixture is heated to 35 ℃ and stirred uniformly. Then slowly adding 280g of 30wt% hydrogen peroxide solution dropwise under the condition of vigorous stirring, controlling the dropping speed to keep the reaction temperature at about 45 ℃, keeping the temperature at 45 ℃ for 5 hours after the dropwise addition is finished, 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 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 0.12g of catalyst sodium ethoxide, heating to 120 ℃ under vigorous stirring, reacting at constant temperature for 6 hours, and finishing the reaction to obtain the tung oil polyol with high hydroxyl value.
100g of the prepared tung oil polyol with the high hydroxyl value, 2.5g of an organosilicon foam stabilizer, 3.0g of diethylenetriamine and 14g of cyclopentane are uniformly mixed, 75g of isophorone diisocyanate is added, and the mixture is poured into a mould to be foamed after being fully and uniformly stirred, so that the tung oil-based rigid polyurethane foam plastic is prepared. The product properties are shown in Table 1.
Example 4
The same treatment and operating conditions were used as in example 1, except that the hydroxylating agent added was n-heptanoic acid. The product characteristics of the obtained tung oil-based rigid polyurethane foam are shown in Table 1.
Example 5
The same treatment and operating conditions were used as in example 2, except that the hydroxylating agent added was n-octanoic acid. The product characteristics of the obtained tung oil-based rigid polyurethane foam are shown in Table 1.
Example 6
The same treatment and operating conditions were used as in example 3, except that isoheptanoic acid was the hydroxylating agent added. The product characteristics of the obtained tung oil-based rigid polyurethane foam are shown in Table 1.
Example 7
The same treatment and operating conditions were used as in example 1, except that isooctanoic acid was used as the hydroxylating agent. The product characteristics of the obtained tung oil-based rigid polyurethane foam are shown in Table 1.
Example 8
The same treatment and operating conditions as in example 1 were used except that the acid catalyst added was phosphoric acid. The product characteristics of the obtained tung oil-based rigid polyurethane foam are shown in Table 1.
Example 9
The same treatment and operating conditions as in example 1 were used, except that the carboxylic acid added was acetic acid. The product characteristics of the obtained tung oil-based rigid polyurethane foam are shown in Table 1.
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, 470000 mPas, is too high to be dissolved, so that aminolysis reaction cannot be carried out, and the product cannot be used for preparing polyurethane rigid foam products.
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. After aminolysis, the hydroxyl value of the product is 207 mgKOH/g. Because soybean oil does not undergo hydroxylation reaction in situ in the first step of reaction, the utilization efficiency of unsaturated double bonds is low, the hydroxyl value of the product is lower than that of tung oil polyol with high hydroxyl value prepared in the embodiment, and hydroxyl functional groups mainly exist at the tail ends of molecular chains of vegetable oil, so that the crosslinking degree in the reaction for synthesizing polyurethane rigid foam is insufficient, and the mechanical property of the product is greatly lower than that of the polyurethane rigid foam product prepared by the method in the embodiment of the invention. The product properties are shown in Table 1.
Comparative example 3
The same treatment and operating conditions were used as in example 1, except that methanol was used as the hydroxylating agent. After aminolysis, the hydroxyl value of the product is 268mgKOH/g, the viscosity is 34000 mPa.s, the actual concentration of formic acid and methanol in a reaction system is lower due to the fact that the methanol is easy to have esterification reaction with the formic acid in the reaction system, the cross-linking of tung oil in epoxidation reaction cannot be completely avoided, and the epoxidation efficiency is low, so that the hydroxyl value of the product is lower than that of the tung oil polyol with a high hydroxyl value prepared in the embodiment, the viscosity is higher, the polyol component and the isocyanate component are difficult to be uniformly mixed in the reaction of synthesizing the rigid polyurethane foam, and the heat insulation performance and the mechanical property of the product are lower than those of the rigid polyurethane foam prepared by the method in the embodiment of the invention. The product properties are shown in Table 1.
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. After the amination, the hydroxyl value of the prepared tung oil polyol is 212mgKOH/g, and the carbon-carbon conjugated double bond of the tung oil is not effectively utilized, so that the hydroxyl value of the product is lower than that of the tung oil polyol with high hydroxyl value prepared in the embodiment. In addition, since the carbon-carbon conjugated double bond has high reactivity, and is liable to undergo polymerization or diene synthesis, and is unstable during storage or use, it cannot be used for synthesizing polyurethane products.
Comparative example 5
The same treatment process and operation conditions as in example 1 were used, except that the prepared tung oil polyol was not subjected to an aminolysis reaction, and was directly used for preparing tung oil-based rigid polyurethane foam. Because the aminolysis reaction is not carried out, the hydroxyl value of the prepared tung oil polyol is 244mgKOH/g, the hydroxyl value of the product is lower than that of the tung oil polyol with high hydroxyl value prepared in the embodiment, the crosslinking degree in the reaction of synthesizing the rigid polyurethane foam is insufficient, and the mechanical property of the product is greatly lower than that of the rigid polyurethane foam product prepared by the method in the embodiment of the invention. The product properties are shown in Table 1.
Table 1 shows the product characteristics of the tung oil-based rigid polyurethane foams prepared in examples 1 to 9 and comparative examples 2, 3 and 5. The dimensional stability was determined at 70 ℃ for 24 h.
TABLE 1 Properties of polyurethane rigid foam products prepared in various examples and comparative examples
Figure DEST_PATH_IMAGE001
As can be seen from Table 1, compared with the tung oil-based rigid polyurethane foam prepared in the comparative example, the product prepared by the method has lower heat conductivity coefficient, better mechanical strength and dimensional stability, and can better meet the use requirement of the rigid polyurethane foam.

Claims (13)

1. A preparation method of tung oil-based rigid polyurethane foam plastic is characterized by comprising 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 at 40-65 ℃, and maintaining the reaction for 3-5h after the dropwise adding is finished; standing and layering after the reaction is finished, separating out a water phase, and neutralizing, washing and distilling an oil phase under reduced pressure to obtain tung oil polyol; 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); the carboxylic acid isFormic acid or acetic acid;
(2) mixing the tung oil polyol prepared in the step (1) with an aminolysis agent, and carrying out aminolysis reaction under the action of an alkali catalyst to prepare tung oil polyol with a high hydroxyl value;
(3) and (3) uniformly mixing the tung oil polyol with the high hydroxyl value prepared in the step (2), a foam stabilizer, a catalyst and a foaming agent in proportion to prepare a component A, adding isocyanate of the component B, stirring and mixing at a high speed, and pouring into a mould for foaming to prepare the tung oil-based rigid polyurethane foam plastic.
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 acid catalyst in the step (1) is one or more of sulfuric acid, phosphoric acid or hydrochloric acid, and the dosage of the acid catalyst is 0.01-1.0% of the mass of the tung oil.
4. 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.
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) is to mix tung oil polyalcohol and aminolysis agent in proportion, gradually raise the temperature to 80-100 ℃ under the protection of nitrogen, and add alkali catalyst; then heating to 110-150 ℃ under the condition of 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.
10. 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 percent of the mass of the tung oil polyalcohol.
11. The method of claim 1, wherein: in the component A in the step (3), by weight, 100 parts of high hydroxyl value tung oil polyol, 2-3 parts of foam stabilizer, 0.5-5 parts of catalyst and 10-20 parts of foaming agent.
12. A method according to claim 1 or 11, characterized by: the foam stabilizer in the step (3) is an organic silicon foam stabilizer; the catalyst is an amine catalyst, and the foaming agent is cyclopentane.
13. The method of claim 1, wherein: the isocyanate in the step (3) is selected from one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) and polymethylene polyphenyl polyisocyanate (PAPI), and the using amount of the isocyanate is 0.75-1.6 times of the mass of the component A.
CN201610119877.1A 2016-03-03 2016-03-03 Tung oil-based hard polyurethane foam plastic and preparation method thereof Active CN107151303B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610119877.1A CN107151303B (en) 2016-03-03 2016-03-03 Tung oil-based hard polyurethane foam plastic and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610119877.1A CN107151303B (en) 2016-03-03 2016-03-03 Tung oil-based hard polyurethane foam plastic and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107151303A CN107151303A (en) 2017-09-12
CN107151303B true CN107151303B (en) 2020-08-11

Family

ID=59792033

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610119877.1A Active CN107151303B (en) 2016-03-03 2016-03-03 Tung oil-based hard polyurethane foam plastic and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107151303B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110387027A (en) * 2018-04-18 2019-10-29 山东顺皓聚氨酯保温材料有限公司 Renewable raw materials and the method for preparing spray coating type polyurethane foamed plastics using it
CN108948067B (en) * 2018-06-26 2021-02-02 中国林业科学研究院林产化学工业研究所 Silicon-containing flame-retardant tung oil-based polyol and preparation method and application thereof
CN109111561A (en) * 2018-08-24 2019-01-01 吉林大学 A kind of eleostearic acid based polyurethanes sound-absorbing material and preparation method thereof
CN115304816B (en) * 2022-09-14 2023-08-22 张家界湘汉仿真花有限公司 Polyurethane foaming sheet for simulated printing and preparation method thereof
CN116218607B (en) * 2022-12-23 2024-11-12 中国林业科学研究院林产化学工业研究所 A plant oil-based polyphenol and a method for preparing recyclable polyurethane foam using the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1844183A (en) * 2006-04-27 2006-10-11 南京红宝丽股份有限公司 Rigid polyurethane foam prepared by using rape seed oil
CN101125912A (en) * 2007-08-13 2008-02-20 南京红宝丽股份有限公司 Polyurethane foam plastic prepared from barbadosnut oil
CN103274930A (en) * 2013-06-20 2013-09-04 南京工业大学 Method for preparing vegetable oil polyalcohol by adopting continuous method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1844183A (en) * 2006-04-27 2006-10-11 南京红宝丽股份有限公司 Rigid polyurethane foam prepared by using rape seed oil
CN101125912A (en) * 2007-08-13 2008-02-20 南京红宝丽股份有限公司 Polyurethane foam plastic prepared from barbadosnut oil
CN103274930A (en) * 2013-06-20 2013-09-04 南京工业大学 Method for preparing vegetable oil polyalcohol by adopting continuous method

Also Published As

Publication number Publication date
CN107151303A (en) 2017-09-12

Similar Documents

Publication Publication Date Title
CN107151302B (en) Vegetable oil-based soft polyurethane foam plastic and preparation method thereof
CN107151303B (en) Tung oil-based hard polyurethane foam plastic and preparation method thereof
CN102199272A (en) Soybean oil-based polyurethane acrylate and preparation method thereof
WO2010020903A1 (en) Process for the production of liquid poliols of renewable origin by the liquefaction of agro-forestry and agro-food biomass
KR20140143374A (en) Composition of matter polyols for polyurethane applications
CN106748767B (en) Low-hydroxyl-value vegetable oil-based polyol and preparation method thereof
WO2016094859A1 (en) Polyols from protein biomass
RU2510798C2 (en) Method of obtaining polyols basing on renewable initial raw material
WO2009048927A1 (en) Vernonia oil polyols
CN107151213B (en) Halogen-free flame-retardant tung oil polyol and preparation method and application thereof
EP1765901B1 (en) Process for preparing polyurethane polyol and rigid foams therefrom from cardanol
CN107151520A (en) A kind of tung oil base water polyurethane coating and preparation method thereof
CN107151680B (en) Tung oil-based polyol and preparation method thereof
CN107151209B (en) Method for synthesizing tung oil polyol by using ionic liquid
CN107151211B (en) Tung oil polyol with high hydroxyl value and preparation method thereof
CN107151215B (en) Tung oil polyol and preparation method thereof
CN106957229B (en) Tung oil polyol and preparation method thereof
CN107151210B (en) Method for preparing tung oil polyol under ultrasonic condition
CN107151212B (en) Tung oil polyol with low hydroxyl value and preparation method thereof
RU2513019C2 (en) Method of obtaining polyols based on renewable initial raw material
CN107151214B (en) Method and device for preparing tung oil polyol under hypergravity condition
US8828269B1 (en) Method for increasing miscibility of natural oil polyol with petroleum-based polyol
CN106957228B (en) Tung oil-based polyol and preparation method thereof
CN107151217B (en) Tung oil-based polyol and synthesis method thereof
CN106957227B (en) Method for producing tung oil polyalcohol and byproduct glycerol

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant