CN107857871A - A kind of preparation method of malic acid polyalcohol and its application in polyurethane foam - Google Patents
A kind of preparation method of malic acid polyalcohol and its application in polyurethane foam Download PDFInfo
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- CN107857871A CN107857871A CN201711112990.8A CN201711112990A CN107857871A CN 107857871 A CN107857871 A CN 107857871A CN 201711112990 A CN201711112990 A CN 201711112990A CN 107857871 A CN107857871 A CN 107857871A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4286—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones prepared from a combination of hydroxycarboxylic acids and/or lactones with polycarboxylic acids or ester forming derivatives thereof and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- 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
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- 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
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/10—Rigid foams
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a kind of preparation method and application of malic acid polyalcohol, has obtained the renewable environment-friendly materials malic acid polyalcohol of bio-based source, and for preparing hard polyurethane foam material.Using malic acid and a variety of dihydric alcohols as raw material, in the presence of catalyst, polyhydroxy polylol is made in esterification under condition of heating and stirring.Malic acid polyalcohol raw material sources obtained by the present invention are extensive, can be extracted from animals and plants and microorganism, have it is renewable, it is nontoxic, the advantages of being easy to get extensively.With method provided by the invention, reaction is thorough, and the malic acid polyalcohol that can be obtained performance by adjusting proportioning and differ.Its obtained hard polyurethane foam, has that density is low, high mechanical properties, the advantages of good heat insulating.
Description
Technical field
The present invention relates to a kind of synthesis of bio-based source malic acid polyalcohol and its application in polyurethane foam, category
In can biological source polymeric material field.
Background technology
Polyurethane foam is a kind of important material, and because it has a porous, thus obtained product has that density is small,
The characteristics of specific strength is high.In addition, polyurethane foam also has an excellent physical and mechanical properties, acoustical behavior, electric property and resistance to
Chemical property, the polyurethane foam plastics of different performance can be obtained by changing the component of formula, disclosure satisfy that all trades and professions
The various technical requirements proposed.Therefore application is quite varied, almost penetrates into each department of national economy, particularly household and produces
Product, transport, refrigeration, the department such as building, thermal insulation, have become one of indispensable material.
In polyurethane foam plastics, RPUF (RPUF) is highly important one kind, with poly- ammonia
In the extensive use of every field, its yield increases ester hard bubble year by year.Polyurethane foam is existed through polyalcohol and polyisocyanates
Porous material made from reaction under the effects such as foaming agent, catalyst, foam stabiliser.So far, the important original of polyalcohol
Material oxirane, expoxy propane, epoxy butane etc. are more to be extracted from oil, and oil makes in global wide excess
With and it is non-renewable, cause oil to exhaust in the near future, seek renewable resource substitute petroleum-based polyols turn into
The heat subject of numerous material scholars researchs.
Compared with conventional petroleum polylol, vegetable based polyol can reduce the use of non-renewable resources, reduce resource
Nervous pressure, while the discharge of greenhouse gases can also be reduced.In addition, the wide material sources of plant polyatomic alcohol, cost is cheap, because
This, the development and application of plant polyatomic alcohol is of great importance to social progress.Malic acid also known as 2- hydroxysuccinic acids are a kind of wide
The general binary acid being present in animals and plants and microorganism, contain two carboxyls and a hydroxyl in molecular structure, can enter with alcohol
Row esterifying polycondensation reacts, meanwhile, itself can improve the degree of functionality and hydroxyl value of PEPA with monohydroxy, be advantageous to gather
The raising of urethane hard bubble mechanical property.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the bio-based source malic acid polyalcohol of different hydroxyls, this
The synthesis of kind malic acid polyalcohol, can substitute use of the petroleum-based polyols in polyurethane foam, so as to reach protection ring
Border, reduce pollution, and the purpose of sustainable development.
To achieve these goals, the technical scheme is that:
The preparation of malic acid polyalcohol follows the steps below:
(1) weigh malic acid and dihydric alcohol is poured into 250ml four-hole boiling flasks, and add the catalysis of 0.5% malic acid quality
Agent.
(2) nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in four-hole boiling flask side, oil bath pan is heated
To 135 DEG C, stirring is reacted and monitors acid number, stops reaction when acid number is reduced to below 1mg KOH/g, and it is more that malic acid is made
First alcohol, vacuum drying oven measure hydroxyl value after drying.
Species by adjusting acid-alcohol ratio and dihydric alcohol can obtain the malic acid polyalcohol of different hydroxyl values, present invention system
The malic acid polyalcohol acid number obtained is less than 1mg KOH/g, and hydroxyl value scope is 250-600mg KOH/g.
Wherein, the molar ratio of malic acid and dihydric alcohol is 1:2-2:3.
The species of dihydric alcohol is butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol, decanediol, hendecane
Any one in alcohol, dodecanol.
Catalyst can be butyl titanate, dibutyl tin laurate, and any one in zinc acetate, dosage is malic acid
The 0.5% of quality.
Malic acid polyalcohol produced by the present invention is used to prepare rigid polyurethane foam.
The method for preparing rigid polyurethane foam is as follows:
Sequentially add 100 parts of malic acid polyalcohol in container, 1 part of catalyst, 2 parts of silicone oil, 1 part of water, 20 parts of foaming agent,
3min is stirred under 1000r/min rotating speeds;Then add a certain proportion of polyisocyanates according to isocyanate index 1.2, i.e., it is more
The ratio of hydroxyl is 1.2 in isocyanates and polyalcohol in isocyanates:1,8s is stirred under 2500r/min rotating speeds, rapidly
Free foaming in mould is poured into, hard polyurethane foams are made after curing 24h, cuts out sample test.
Wherein, foaming agent is:One fluorine dichloroethanes (HCFC-141b);Catalyst is:N, N- dimethyl cyclohexyl amine (PC-
8);Silicone oil is AK8805, a kind of non-hydrolytic type polysiloxane-polyether copolymer of silicon-carbon bond;
Wherein, as a kind of CBA, the carbon-to-nitrogen double bon in active hydrogen and isocyanates in hydrone occurs water
Addition reaction, generates carbamic acid, and unstable carbamic acid easily generates amine and carbon dioxide, caused atmospheric carbon dioxide
Foaming agent can be served as;Polyisocyanates is polymethylene multi-phenenyl isocyanate, model PM-200.
The hard polyurethane foam of malic acid polyols preparation, isocyanate index remain 1.2.
The present invention has the advantages of following:
(1) malic acid is a kind of important organic acid in the present invention, wide material sources, is distributed in animals and plants and microbial cell
In.
(2) conventional urethane derives from oil with polyalcohol, due to excessive use of the oil in worldwide, and
Oil is non-renewable resources, result in the worsening shortages of oil, and the malic acid polyalcohol prepared from biological source belongs to can be again
Production-goods source, the dependence to oil can be reduced, realizes sustainable development.
(3) present invention can prepare different hydroxyl values by adjusting the ratio of dihydric alcohol and malic acid and the species of dihydric alcohol
Malic acid polyalcohol, to prepare the hard polyurethane foam of different performance.
(4) in the embodiment cited by the present invention, can obtain it is anticipated that obtain the malic acid polyalcohol of different performance
The malic acid polyol reaction arrived is thorough, and because malic acid has extra hydroxyl in side chain, the polyalcohol of preparation is with higher
Hydroxyl value and degree of functionality, be advantageous to form cross-linked structure in polyurethane foam, thus prepare foam there is good mechanics
Performance, thermal and insulating performance protrude.
Embodiment
Some concrete numerical value parameter that the present embodiment only wins in specification in listed scope is illustrated, as long as saying
Within the scope of listed by bright book, the specific steps of invention can be completed.
The properties of the present invention are carried out according to following testing standard:
Acid number:ATSM D4662.08;
Hydroxyl value:ATSM D4274-05;
Density:GB/T6343-2009;
Compressive strength:GB/T8813-2008;
Thermal conductivity factor:GB 3399-1982.
Embodiment 1:
26.8g malic acid and 27.0g butanediols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 2
26.8g malic acid and 32.4g butanediols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 3
26.8g malic acid and 36g butanediols are added in 250ml four-hole boiling flasks, 0.13g tin dilaurate is then added dropwise
Dibutyl tin, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan is heated to 135 DEG C, stirred
Mix and monitor acid number, stop reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 4
26.8g malic acid and 31.2g pentanediols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 5
26.8g malic acid and 37.4g pentanediols are added in 250ml four-hole boiling flasks, 0.13g acetic acid is then added dropwise
Zinc, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan is heated to 135 DEG C, stirs and supervises
Acid number is surveyed, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 6
26.8g malic acid and 41.6g pentanediols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 7
26.8g malic acid and 35.4g hexylene glycols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 8
26.8g malic acid and 42.5g hexylene glycols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 9
26.8g malic acid and 47.2g hexylene glycols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 10
26.8g malic acid and 39.6g heptandiols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 11
26.8g malic acid and 47.5g heptandiols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 12
26.8g malic acid and 52.8g heptandiols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 13
26.8g malic acid and 43.8g ethohexadiols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 14
26.8g malic acid and 52.6g ethohexadiols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 15
26.8g malic acid and 58.4g ethohexadiols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 16
26.8g malic acid and 48.0g nonanediols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 17
26.8g malic acid and 57.6g nonanediols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 18
26.8g malic acid and 64.0g nonanediols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 19
26.8g malic acid and 52.2g decanediols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 20
26.8g malic acid and 62.6g decanediols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 21
26.8g malic acid and 69.6g decanediols are added in 250ml four-hole boiling flasks, 0.13g metatitanic acid four is then added dropwise
Butyl ester, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan are heated into 135 DEG C, stirring is simultaneously
Acid number is monitored, stops reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 22
26.8g malic acid and 56.4g undecanes are added in 250ml four-hole boiling flasks, 0.13g titanium is then added dropwise
Sour four butyl esters, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan is heated to 135 DEG C, stirred
Mix and monitor acid number, stop reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 23
26.8g malic acid and 67.7g undecanes are added in 250ml four-hole boiling flasks, 0.13g titanium is then added dropwise
Sour four butyl esters, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan is heated to 135 DEG C, stirred
Mix and monitor acid number, stop reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 24
26.8g malic acid and 75.2g undecanes are added in 250ml four-hole boiling flasks, 0.13g titanium is then added dropwise
Sour four butyl esters, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan is heated to 135 DEG C, stirred
Mix and monitor acid number, stop reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 25
26.8g malic acid and 60.6g dodecanediols are added in 250ml four-hole boiling flasks, 0.13g titanium is then added dropwise
Sour four butyl esters, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan is heated to 135 DEG C, stirred
Mix and monitor acid number, stop reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 26
26.8g malic acid and 75.7g dodecanediols are added in 250ml four-hole boiling flasks, 0.13g titanium is then added dropwise
Sour four butyl esters, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan is heated to 135 DEG C, stirred
Mix and monitor acid number, stop reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Embodiment 27
26.8g malic acid and 80.8g dodecanediols are added in 250ml four-hole boiling flasks, 0.13g titanium is then added dropwise
Sour four butyl esters, nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in side, oil bath pan is heated to 135 DEG C, stirred
Mix and monitor acid number, stop reaction when acid number is reduced to below 1mg KOH/g, vacuum drying oven measures hydroxyl value after drying.
The malic acid polyalcohol of the above-mentioned preparations of 30g is weighed in 250ml plastic cup, then adds 0.60g silicone oil, 0.3g
Catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanate index
1.2 add polyisocyanates (PM-200), stir 8s under 2500r/min, pour the mixture into mould, are cut out after 24h is cured
Sample is tested, test result such as table 1.
Comparative example 1
30g commercial polyols GR4110 (Shanghai Gaoqiao petrochemical industry) is weighed in 250ml plastic cup, then adds 0.60g
Silicone oil, 0.3g catalyst (PC-8), 0.30g water, 6.00g 141b, the mechanical agitation 3min under 1000r/min, then with isocyanide
Acid esters index 1.2 adds polyisocyanates (PM-200), stirs 8s under 2500r/min, pours the mixture into mould, waits to cure
Sample test, test result such as table 1 are cut out after 24h.
The performance of malic acid polyalcohol and the performance of polyurethane foam in 1. each embodiment of table
As can be seen from the above table, by different ratio and the dihydric alcohol of species can be made low acid number, high hydroxyl value apple
Sour polyalcohol, and commercially available polyalcohol is contrasted using the hard polyurethane foam of the biopolyol preparation of the present invention, have good
Mechanical property and excellent thermal and insulating performance, and the polyalcohol and rigid polyurethane of different performance can be prepared according to demand
Bubble.The malic acid polyalcohol of the present invention can reduce resource anxiety as commercially available polyester and polyether petroleum-based polyols are substituted
Pressure, realize the purpose of sustainable development and environmental protection.
Claims (9)
- A kind of 1. preparation method of malic acid polyalcohol, it is characterised in that:The preparation method is:(1) weigh malic acid and dihydric alcohol is poured into 250ml four-hole boiling flasks, and add the catalyst of 0.5% malic acid quality;(2) nitrogen, opposite side access water knockout drum and condensation reflux unit are passed through in four-hole boiling flask side, oil bath pan is heated to 135 DEG C, stirring is reacted and monitors acid number, stops reaction when acid number is reduced to below 1mg KOH/g, and it is polynary that malic acid is made Alcohol, vacuum drying oven measure hydroxyl value after drying.
- 2. the preparation method of malic acid polyalcohol as claimed in claim 1, it is characterised in that:The malic acid and dihydric alcohol Mol ratio is:1:2-2:3.
- 3. the preparation method of malic acid polyalcohol as claimed in claim 1, it is characterised in that:The dihydric alcohol is:Butanediol, One kind in pentanediol, hexylene glycol, heptandiol, ethohexadiol, nonanediol, decanediol, tip-nip, dodecanol.
- 4. the preparation method of malic acid polyalcohol as claimed in claim 1, it is characterised in that:The catalyst is the fourth of metatitanic acid four Ester, dibutyl tin laurate, one kind in zinc acetate.
- 5. the preparation method of malic acid polyalcohol as claimed in claim 1, it is characterised in that:The obtained malic acid is polynary The acid number of alcohol is less than 1mg KOH/g, and hydroxyl value scope is 250~600mg KOH/g.
- A kind of 6. application of malic acid polyalcohol prepared by method as claimed in claim 1, it is characterised in that:The malic acid is more First alcohol is used to prepare rigid polyurethane foam.
- 7. the application of malic acid polyalcohol as claimed in claim 6, it is characterised in that:The rigid polyurethane foam Preparation method is:Sequentially add 100 parts of malic acid polyalcohol in a reservoir, 1 part of catalyst, 2 parts of silicone oil, 1 part of water, 20 parts of foaming agent, 3min is stirred under 1000r/min rotating speeds;Ratio according to hydroxyl in the isocyanates and polyalcohol in polyisocyanates is 1.2:1 adds polyisocyanates, 8s is stirred under 2500r/min rotating speeds, pours into free foaming in mould rapidly, rigid polyurethane foam is made after curing 24h.
- 8. the application of malic acid polyalcohol as claimed in claim 7, it is characterised in that:The foaming agent is the chloroethene of a fluorine two Alkane;Catalyst is N, N- dimethyl cyclohexyl amines;Silicone oil is AK 8805.
- 9. the application of malic acid polyalcohol as claimed in claim 7, it is characterised in that:The water is as CBA;Institute It is polymethylene multi-phenenyl isocyanate to state polyisocyanates.
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CN112225866A (en) * | 2020-10-12 | 2021-01-15 | 江南大学 | Bio-based polyurethane hard foam material and preparation method thereof |
WO2023021973A1 (en) * | 2021-08-17 | 2023-02-23 | 東洋紡株式会社 | Resin composition containing hydroxyl group-containing polyester resin, and coating film |
CN116515379A (en) * | 2023-05-16 | 2023-08-01 | 江苏晨光涂料有限公司 | Bio-based super-hydrophobic conductive anti-corrosion polyurethane coating and preparation method thereof |
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CN106565935A (en) * | 2016-11-07 | 2017-04-19 | 常州大学 | Preparation method of dimer acid polyol and application thereof in polyurethane foam |
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CN116515379A (en) * | 2023-05-16 | 2023-08-01 | 江苏晨光涂料有限公司 | Bio-based super-hydrophobic conductive anti-corrosion polyurethane coating and preparation method thereof |
CN116515379B (en) * | 2023-05-16 | 2024-03-15 | 江苏晨光涂料有限公司 | Bio-based super-hydrophobic conductive anti-corrosion polyurethane coating and preparation method thereof |
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