CN1708529A - Polyester polyol, polyurethane obtained therefrom, and rigid polyurethane foam - Google Patents
Polyester polyol, polyurethane obtained therefrom, and rigid polyurethane foam Download PDFInfo
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- CN1708529A CN1708529A CNA2003801021626A CN200380102162A CN1708529A CN 1708529 A CN1708529 A CN 1708529A CN A2003801021626 A CNA2003801021626 A CN A2003801021626A CN 200380102162 A CN200380102162 A CN 200380102162A CN 1708529 A CN1708529 A CN 1708529A
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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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—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
- C08G18/4283—Hydroxycarboxylic acid or ester
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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
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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
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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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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- 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)
- Polyesters Or Polycarbonates (AREA)
Abstract
A polyester polyol which, when used as a starting-material polyol for polyurethanes, especially rigid polyurethane foams, not only has a low viscosity and satisfactory handleability but has high compatibility with blowing agents, especially an HFC blowing agent such as HFC-245fa and/or HFC-365mfc. The polyester polyol is one obtained by esterifying a polycarboxylic acid with alcohols, the alcohols containing 2 to 40% by weight at least one member selected from the group consisting of 1-hydroxy-2-acetoxybutane, 1-acetoxy-2-hydroxybutane, and 1,2-diacetoxybutane.
Description
Technical field
The present invention relates to polyester polyol.Specifically, the present invention relates to following polyester polyol, it shows the intermiscibility with the excellence of whipping agent when urethane especially uses in hard polyurethane foams, and low, the easy processing of viscosity.
Background technology
Because hard polyurethane foams has excellent insulative properties, so be widely used in the lagging material etc. of buildings in general.Hard polyurethane foams utilizes following method manufacturing: normally prepare polyisocyanates earlier and become separatory (being designated hereinafter simply as A liquid) and mixed solution (being designated hereinafter simply as B liquid), this mixed solution is mixed with polyether polyol and/or polyester polyol, whipping agent, also be mixed with catalyzer and surfactant etc. as required, mix A liquid and B liquid then, make its curing after the short period of time foaming.For this reason, can seek polyester polyol in that to have on the basis of excellent intermiscibility its viscosity low, easy to operate with whipping agent.
As whipping agent, use the nonpolar organic solvent of lower boiling usually, specifically, except that HCFC series whipping agent, can also use stable hydrocarbon series solvents such as pentane, pentamethylene.But according to creating conditions of purposes and hard polyurethane foams, burning-point is low and have volatile stable hydrocarbon series solvent to have problems when reality is used, so in most cases use HCFC series whipping agent.
Since the problem that depletion of the ozone layer occurs, the CFC that once was widely used series whipping agent particularly CFC-11E etc. now by the little HCFC series whipping agent of ozone layer destroying coefficient particularly HCFC-141b replace.But the ozone layer destroying coefficient of HCFC-141b is not zero, so its use can be restricted after estimating for the year ends 2003.Particularly HFC-245fa, HFC-365mfc will be as the substitutes of HCFC-141b to estimate HFC series whipping agent now.
That use now and estimate that in the future all there is the common problem in use in the whipping agent that uses, that is, polyhydroxy reactant comprises polyether polyol and/or polyester polyol as B liquid main component, and the intermiscibility of itself and these whipping agent is poor.Especially poor with the intermiscibility of HFC such as HFC-245fa, the HFC-365mfc series whipping agent of the substitute of estimating to become HCFC series whipping agent, this becomes big problem from now on.
For making B liquid uniform and stable, particularly nonionic surface active agent is as surfactant to add tensio-active agent usually, though this method is widely used, its effect is also insufficient.In addition, begin to propose to improve certain phase solvation of intermiscibility in recent years, it has the surfactivity effect.But these phase solvation major parts are compounds of hydroxyl not.So, even its ancillary component as B liquid helps to improve the intermiscibility with above-mentioned whipping agent, but because it does not participate in urethane esterification reaction, so it still is present in the hard polyurethane foams, the especially situation of intensity and thermotolerance etc. of its physical properties appears sometimes significantly reducing.
Therefore, on the low problem of the intermiscibility that solves whipping agent and B liquid, also can be used as the compound that intramolecularly has the polyvalent alcohol performance function of hydroxyl when improving intermiscibility, is extremely important in actual applications.
With the thermotolerance of the hard polyurethane foams that improves gained etc. is purpose, use polyester polyol especially during aromatic polyester type polyvalent alcohol often with polyether polyol and usefulness.But, because the common viscosity height of aromatic polyester type polyvalent alcohol uses difficulty, and low with the intermiscibility of whipping agent, so it is difficult being equipped with the polyester polyol of necessary amount in the scope of the intermiscibility that satisfies whipping agent and B liquid in B liquid, and various problems are arranged in practical application.
On the other hand, for raising comprises the physical properties of the polyester polyol of intermiscibility, it also is effective that raw alcohol is selected glycol, triol etc., especially in order to improve intermiscibility, all or part of alcohol uses 1, and (be designated hereinafter simply as 1,2-BG) be effective to the 2-butyleneglycol.But, use 1, under the situation of 2-BG, the reduction of the viscosity of the polyester polyol of gained is limited, usually near the polyester polyol of widely used hydroxyl value 250 (mgKOH/g), be difficult to the polyester polyol of synthetic viscosity smaller or equal to 20,000 mPa s (25 ℃).This can not satisfy the needs when modulation B liquid.
So, if the new polyester polyol that intermiscibility is good and viscosity is low with whipping agent is arranged, its part as polyhydroxy reactant is suitably used, just can obtain the good B liquid of uniform and stable property, and then can improve the proportioning degree of freedom of each composition in the B liquid, finally obtain having the hard polyurethane foams of excellent physical properties.
Summary of the invention
In order to solve these problems, found that of researchs such as the inventor, the alcohol that uses a kind of mixture to make raw material as polyester polyol can obtain intermiscibility height and the low polyester polyol of viscosity with whipping agent, thereby realizes the present invention.Described mixture contains being selected from by 1-hydroxyl-2-acetoxyl butane of specified quantitative and (is designated hereinafter simply as 1,2-HAB), 1-acetoxyl-2-hydroxyl butane (is designated hereinafter simply as 1,2-AHB) with 1,2-diacetoxyl butane (is designated hereinafter simply as 1,2-DAB) at least a compound in the group of Zu Chenging.The polyester polyol of gained is the same with former widely used polyester polyol, and its constituent as urethane is attached to the intramolecularly of urethane, so do not damage the physical properties of urethane, can bring into play described characteristic again.
That is, the present invention relates to the material that is characterized as main idea with following.
(1) a kind of polyester polyol, it is characterized in that, make polycarboxylic acid and alcohol that esterification take place and make, as alcohol, contain being selected from of 2 weight %～40 weight %, at least a material in the group that 2-diacetoxyl butane is formed by 1-hydroxyl-2-acetoxyl butane, 1-acetoxyl-2-hydroxyl butane and 1.
(2) a kind of polyester polyol, wherein, described alcohol is mixture and contains 1,2-butyleneglycol and being selected from by 1-hydroxyl-2-acetoxyl butane, 1-acetoxyl-2-hydroxyl butane and 1, at least a material in the group that 2-diacetoxyl butane is formed, in this mixture 1, the content of 2-butyleneglycol is 60 weight %～98 weight %.
(3) as above-mentioned (2) described polyester polyol, wherein, mixture makes by the following method: in the presence of molecular oxygen and palladium class catalyzer, make 1,3-divinyl and the reaction of acetic acid generation acetoxylation, with reaction product hydrogenation additions in the presence of noble metal catalyst such as the diacetoxyl butylene class reaction product that obtains and single acetoxyl butylene classes, then with reaction product hydrolysis in the presence of solid acid catalyst such as the diacetoxyl butanes reaction product of gained and single acetoxyl butanes, after heating up in a steamer acetic acid and water, fractionation by distillation.
(4) a kind of urethane is characterized in that, the polyvalent alcohol and the isocyanate compound reaction that contain as each described polyester polyol of above-mentioned (1)～(3) are made.
(5) a kind of hard polyurethane foams is to use as above-mentioned (4) described urethane to obtain.
(6) as above-mentioned (5) described hard polyurethane foams, it also contains the ozone layer destroying coefficient and is less than or equal to 0.8 whipping agent.
(7) as above-mentioned (6) described hard polyurethane foams, wherein whipping agent is HFC-245fa and/or HFC-365mfc.
Utilize the present invention, a kind of polyester polyol can be provided, it is as the raw polyol of urethane especially hard polyurethane foams, low, the easy use of viscosity, and with the whipping agent intermiscibility height of HFC such as HFC-245fa and/or HFC-365mfc series whipping agent particularly.
Embodiment
Describe the present invention below in detail.
Polyester polyol among the present invention is to be adapted at the polyester polyol that urethane especially uses in the hard polyurethane foams, and it is made by polycarboxylic acid and alcohol.
＜polycarboxylic acid 〉
As polycarboxylic acid of the present invention, can exemplify di-carboxylic acid or tribasic carboxylic acid.The acid anhydrides of aromatic binary carboxylic acid such as preferred phthalic acid, m-phthalic acid, terephthalic acid, trimellitic acid or tribasic carboxylic acid and these compounds.Wherein more preferably phthalic acid, phthalic acid acid anhydrides or terephthalic acid.
In addition, these aromatic carboxylic acid classes can be material after 1～8 the monohydroxy-alcohol esterification by carbonatomss such as methyl alcohol, ethanol, 2-Ethylhexyl Alcohols also, for example dimethyl terephthalate (DMT) etc.
And, aliphatic dicarboxylic acids such as succsinic acid, toxilic acid, hexanodioic acid can be mixed use with above-mentioned aromatic carboxylic acid class, according to circumstances also can use separately.
＜alcohol 〉
Contain and be selected from by 1 2-HAB, 1,2-AHB and 1, at least a material in the group that 2-DAB forms
The alcohol that is used as starting raw material among the present invention contains being selected from by 1 of 2 weight %～40 weight %, 2-HAB, 1,2-AHB and 1, at least a material in the group that 2-DAB forms.
Be selected from by 1,2-HAB, 1, the content of at least a compound in the group that 2-AHB and 1,2-DAB form is preferably greater than and equals 5 weight %, more preferably greater than equaling 10 weight %, and preferably smaller or equal to 35 weight %, is more preferably less than and equals 30 weight %.If its content is very few, almost can't see the effect that reduces polyester polyol viscosity.If its content is too much, during synthesizing polyester type polyvalent alcohol, the hydroxyl in the polyester polyol of gained significantly reduces, and then based on the usage rate with respect to used polycarboxylic acid, the compound that does not just have hydroxyl fully that obtains sometimes, promptly non-polyvalent alcohol.If use the polyester polyol that in the scope that shows this tendency, obtains, when it is further reacted with the esterification of polyisocyanates generation urethane, bring tangible detrimentally affect might for performances such as the intensity of hard polyurethane foams of gained and thermotolerance.
1,2-HAB, 1,2-AHB and 1 is among the 2-DAB, the total amount of relative these three kinds of materials, 1, the amount of 2-DAB is usually more than or equal to 1 weight %, is preferably greater than to equal 5 weight %, more preferably greater than equaling 10 weight %, usually smaller or equal to 50 weight %,, be more preferably less than and equal 25 weight % preferably smaller or equal to 33 weight %.
More particularly, such alcohol is a kind of mixture, contains 1,2-BG and being selected from by 1, and 2-HAB, 1,2-AHB and 1, at least a material in the group that 2-DAB forms, and in this mixture 1, the content of 2-BG is preferred 60 weight %～98 weight % usually.This mixture mainly makes by the following method: in the presence of molecular oxygen and palladium class catalyzer, make the reaction of 1,3-butadiene and acetic acid generation acetoxylation; With reaction product hydrogenation additions in the presence of precious metal catalyst such as the diacetoxyl butylene class reaction product that obtains and single acetoxyl butylene classes; Then reaction product such as the diacetoxyl butanes reaction product of gained and single acetoxyl butanes are added water decomposition in the presence of solid acid catalyst, heat up in a steamer acetic acid and water after, fractionation by distillation.That is to say, can be to make 1,3-butadiene and acetic acid reaction make 1, the form of the by product that generates in the time of the 4-butyleneglycol obtains.
Palladium class catalyzer as using among the present invention can use metallic palladium or its salt separately, or be used in combination as metals such as the bismuth of catalyst aid, selenium, antimony, tellurium, copper or its salt.Catalyzer is loaded with on carriers such as tripoli, aluminum oxide, gac to be used.
Containing 1,2-BG and being selected from by 1,2-HAB, 1,2-AHB and 1, common 1 in the mixture of at least a material in the group that 2-DAB forms, the content of 2-BG is preferably 60 weight %～98 weight %.1, if the content of 2-BG is very few, during synthesizing polyester type polyvalent alcohol, the hydroxyl in the polyester polyol of gained significantly reduces, and then based on the usage rate with respect to used polycarboxylic acid, has to not exist fully the compound of hydroxyl sometimes, promptly non-polyvalent alcohol.If use the polyester polyol that in the scope that shows this tendency, obtains, when it is further reacted with the esterification of polyisocyanates generation urethane, bring tangible detrimentally affect might for performances such as the intensity of hard polyurethane foams of gained and thermotolerance.If its content is too much, almost can't see the effect that reduces polyester polyol viscosity.
Therefore, the relative gross weight of mixture, 1, the content of 2-BG is preferably greater than and equals 65 weight %, more preferably greater than equaling 70 weight %, and preferably smaller or equal to 95 weight %, is more preferably less than the scope that equals 90 weight %.
In the mixture, except containing 1,2-BG and being selected from by 1,2-HAB, 1,2-AHB and 1 beyond at least a material in the group that 2-DAB forms, can also contain acetic acid, the water, 1 of trace, 4-butyleneglycol, 1, the acetic ester of 4-butyleneglycol etc.
Usually in mixture, preferably contain being selected from of 2 weight %～40 weight %, 2-HAB, 1,2-AHB and 1, at least a material in the group that 2-DAB forms by 1.If be selected from by 1,2-HAB, 1,2-AHB and 1, the content of at least a material in the group that 2-DAB forms is too much, during synthesizing polyester type polyvalent alcohol, the hydroxyl in the polyester polyol of gained obviously reduces, so based on the usage rate of used polycarboxylic acid, sometimes have to not exist fully the compound of hydroxyl, promptly non-polyvalent alcohol.If use the polyester polyol that in the scope that shows this tendency, obtains, when it is further reacted with the esterification of polyisocyanates generation urethane, bring significant detrimentally affect might for performances such as the intensity of hard polyurethane foams of gained and thermotolerance.If its content is very few, almost can't see the effect that reduces polyester polyol viscosity.
Therefore, the gross weight of relative mixture, be selected from by 1,2-HAB, 1,2-AHB and 1, the content of at least a material in the group that 2-DAB forms is preferably greater than and equals 5 weight %, more preferably greater than equaling 10 weight %, and preferably, be more preferably less than the scope that equals 30 weight % smaller or equal to 35 weight %.
＜other alcohol 〉
As the alcohol among the present invention, except that above-mentioned mixture, can also and use other alcohol.The alcohol of other of common conduct and usefulness, can exemplify ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1, trivalent alcohol such as dibasic alcohol such as 6-hexylene glycol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol and glycerol, TriMethylolPropane(TMP) etc.
Also can use long-chain polyether polyols such as polyoxyethylene glycol, polypropylene glycol, polyoxyethylene/oxypropylene copolymerization ethylene glycol and polytetramethylene ether glycol.
And with these under the pure situation, the total amount of raw alcohol if the content of described mixture is very few, is then almost can't see and is improved and the intermiscibility of whipping agent and the unusual effect of reduction viscosity relatively.That is, the relative total amount of raw alcohol, the usage quantity of said mixture be usually more than or equal to 40 weight %, is preferably greater than to equal 50 weight %.But according to the balance of properties degree of desired lowering viscousity of polyester polyol and/or intermiscibility, the usage quantity of described mixture also can be lower than above-mentioned scope.
As the method for viscosity that reduces polyester polyol, also can use monohydroxy-alcohols such as methyl alcohol, ethanol, Virahol, 2-Ethylhexyl Alcohol, reduce yield beyond the reaction system but when synthesizing polyester type polyvalent alcohol, can distillate, thereby bring detrimentally affect for the intensity and the thermotolerance of urethane.
＜esterifying catalyst 〉
In esterification of the present invention, use esterifying catalyst usually.
As catalyzer, use acid catalyst usually.As Lewis acid, can exemplify metallic compounds such as tin based compounds such as orthotitanates such as titanium isopropylate, tetra-n-butyl titanate and diethyl stannic oxide, Dibutyltin oxide and zinc oxide.
Except that Lewis acid, can also use Brnsted acids such as tosic acid.
The polyester polyol of gained and polyisocyanates generation urethane esterification reaction generate urethane, but wish that the used catalyzer of synthesizing polyester type polyvalent alcohol can not influence the reaction process of urethane esterification reaction this moment.In above-mentioned esterifying catalyst, preferred orthotitanate, the total amount of polycarboxylic acid that uses in the raw material and alcohol relatively, its usage quantity is usually smaller or equal to 1.0 weight %, preferably smaller or equal to 0.2 weight %, and usually more than or equal to 0.01 weight %, be preferably greater than and equal 0.03 weight %.
According to the purposes of urethane, also can not use these esterifying catalysts to react.
＜reaction conditions 〉
Polyester polyol of the present invention is by adding above-mentioned esterifying catalyst usually in polycarboxylic acid and alcohol, esterification taking place obtain.
Usage ratio for polycarboxylic acid and alcohol, according to the hydroxyl value of target product polyester polyol and viscosity etc. and different, but the carboxyl of relative 1 equivalent polycarboxylic acid, the hydroxyl equivalent number of alcohol is usually more than or equal to 1.1 equivalents, be preferably greater than and equal 1.3 equivalents, more preferably greater than equaling 1.5 equivalents, and usually smaller or equal to 4.0 equivalents, preferably smaller or equal to 3.0 equivalents, be more preferably less than and equal 2.7 equivalents.Especially at mixture of the present invention relatively under the alcohol situation of its usage quantity more than or equal to 40 weight %, if this value is too small, hydroxyl in the polyester polyol of gained obviously reduces, based in the mixture 1,2-HAB, 1,2-AHB and 1, the content of 2-DAB, might have to not exist fully the compound of hydroxyl, promptly non-polyvalent alcohol.If use the polyester polyol that in the scope that shows this tendency, obtains, when it is further reacted with the esterification of polyisocyanates generation urethane, bring tangible detrimentally affect might for performances such as the intensity of hard polyurethane foams of gained and thermotolerance.On the other hand, if this value is excessive, will the residual free alcohol that does not participate in esterification in a large number in the polyester polyol.If use the polyester polyol obtain like this, when it further react with the esterification of polyisocyanates generation urethane, still might bring tangible detrimentally affect to performances such as the intensity of the hard polyurethane foams of gained and thermotolerances.In addition, under the situation of mixture of the present invention as alcohol of using, according to 1, monoesters classes such as 2-HAB are as 1 equivalent hydroxyl, 1, and 2-DAB calculates the hydroxyl equivalent number of mixture as the conversion of 0 equivalent hydroxyl.
Temperature of reaction is usually more than or equal to 150 ℃, is preferably greater than to equal 180 ℃, and usually smaller or equal to 250 ℃, preferably smaller or equal to 230 ℃.For example, 180 ℃ of initiation reactions, follow the carrying out of reaction, temperature slowly rises to 200 ℃, just control reaction easily under this condition.
Reaction pressure can be a normal pressure, for the acetic acid with water byproduct and trace distillates outside the system, and simultaneously for reaction is finished fast, also can be along with the carrying out of reaction slowly reduced pressure.But, if the decompression deficiency in when reaction then can reduce the reactivity of esterification, and cause generating the high polyester polyol of acid number.On the other hand, if the excessive decompression in when reaction, then 1,2-BG, 1,2-HAB, 1, pure composition such as 2-AHB is distillated outside the reaction system, not only reduces yield, and under extreme case, participate in 1 of esterification, 2-HAB and 1, the acetoxyl of 2-AHB etc. takes off acetic acid owing to further transesterification reaction causes, generates the high-molecular weight polyester polyol.The polyester polyol that obtains so not only viscosity obviously raises, and might show the tendency of the intermiscibility of reduction and whipping agent.Suitable realization response pressure is different because of temperature of reaction, and for example, when temperature of reaction was 200 ℃, pressure was usually more than or equal to 20kPa, be preferably greater than to equal 30kPa, and usually smaller or equal to 60kPa, preferably smaller or equal to 50kPa.But, according to being selected from by 1 2-HAB, 1,2-AHB and 1 in the usage quantity of the viscosity of target product polyester polyol and hydroxyl value, used mixture, the mixture, the content of at least a compound in the group that 2-DAB forms also can react under the condition beyond the above-mentioned pressure range.
In addition, replace decompression, also can by and with organic solvents such as small amount of toluene, dimethylbenzene, make water byproduct and acetate in minute azeotropic and from system, be removed.
Under the situation of polyester polyol, usually by the amount decision reaction end of the unreacted carboxyl groups of used polycarboxylic acid.On the other hand, in the purposes of urethane, for reacting with the urethane esterification of polyisocyanates, the existence of acid reduces reactivity etc., is not preferred under the situation mostly.Therefore, for polyester polyol, the amount of unreacted carboxylic acid is that acid number is preferably low as far as possible.In the purposes of hard polyurethane foams, acid number is usually smaller or equal to 10mgKOH/g, preferably smaller or equal to 5mgKOH/g, is more preferably less than and equals 3mgKOH/g.In the reaction conditions of stricter urethane esterification reaction, wish smaller or equal to 1mgKOH/g sometimes.
The polyester polyol that above-mentioned condition obtains normally makes by ester cpds and the unreacted alcohol with the structure that is made of used polycarboxylic acid and alcohol.The polyester polyol of gained of the present invention, only by containing 1,2-BG and being selected from by 1,2-HAB, 1,2-AHB and 1, under the mixture and divalent polycarboxylic acid synthetic situation of at least a compound in the group that 2-DAB forms, the average functional group number of described ester cpds is usually more than or equal to 0.8, be preferably greater than and equal 1.1, more preferably greater than equaling 1.5.If the average functional group number of ester cpds is too small, the polymerization degree of its urethane that further obtains with polyisocyanates generation urethane esterification reaction is reduced, for example, under the situation of hard polyurethane foams, might make obviously variation such as intensity and thermotolerance.
For the average functional group number of keeping ester cpds in certain target value and/or keep molecular-weight average smaller or equal to certain value, importantly not making as far as possible follows transesterification reaction to be in 1 of equilibrium state in the esterification, 2-HAB, 1,2-AHB and 1, the acetic acid of the acetic ester of 2-DAB heats up in a steamer outside the reaction system.If distilled acetic acid is too much, the average functional group number of ester cpds will be different with initial goods design, and the mean molecule quantitative change is big, the viscosity of gained polyester polyol also obviously becomes big, so be not preferred.Therefore, with respect to being combined in 1,2-HAB, 1,2-AHB and 1, the acetic acid total amount on the 2-DAB, the amount that distillates the outer acetic acid of reaction system in the esterification be usually smaller or equal to 30%, preferably smaller or equal to 20%, is more preferably less than and equals 10%.But, according to being selected from by 1 2-HAB, 1,2-AHB and 1 in the usage quantity of the viscosity of target product polyester polyol and hydroxyl value, used mixture, the mixture, the content of at least a compound in the group that 2-DAB forms, distilled acetic acid amount also can exceed above-mentioned scope.
In addition, painted for the polyester polyol that prevents to generate when the reaction beginning, preferably the nitrogen exchange is carried out in the space of reaction vessel, and removed the oxygen that is dissolved in the reaction solution.
In addition, after reaction finishes, can also under suitable reduced pressure, unreacted free alcohol be distillated outside the reaction system, thus the physical properties and the performance of regulating polyester polyol.
＜reaction formation 〉
The reaction formation of polyester polyol can be used equipment or continuous device at common intermittence among the present invention, but because long reaction time, and the alcohol that uses in the viscosity ratio raw material of gained polyester polyol is high a lot of etc., so the form of preferred rhythmic reaction.
＜purposes 〉
The polyester polyol of gained of the present invention suits to use when polyvalent alcohol and isocyanate compound prepared in reaction urethane especially hard polyurethane foams, not only viscosity is low easily uses, and is useful as the high polyester polyol of the intermiscibility of whipping agents such as HFC-245fa that will be used especially from now on smaller or equal to 0.8 whipping agent with the ozone layer destroying coefficient and/or HFC-365mfc.
Hard polyurethane foams utilizes following method manufacturing: will contain the A liquid of polyisocyanates composition and be mixed with polyhydroxy reactant, whipping agent, catalyzer and surfactants such as polyether polyol and/or polyester polyol, also be mixed with the B liquid of other additives, auxiliary agent as required, with the short period of time mixing, and make its foaming, curing.
As the polyisocyanates composition, so long as contain in 1 molecule more than the organic compound that equals 2 isocyanate group, just there is no particular limitation.For example, can exemplify the modifier of aliphatics series, alicyclic series and aromatic series series polyisocyanates or these compounds.Specifically, as aliphatics series and alicyclic serial polyisocyanates, can exemplify hexamethylene diisocyanate, isophorone diisocyanate etc.As aromatic series series polyisocyanates, can exemplify tolylene diisocyanate, diphenylmethanediisocyanate and polyphenylene polymethylene polyisocyanates etc., also comprise modifiers such as the carbodiimide modified thing of these compounds and prepolymer.
Preferred polyisocyanates is aromatic polyisocyanate or its modifier among the present invention, the modifier of preferred especially diphenylmethanediisocyanate, polyphenylene polymethylene polyisocyanates, tolylene diisocyanate and these compounds, these materials can use separately also can mix use.
As polyphenylene polymethylene polyisocyanates, use NCO group containing ratio to be generally 29 weight %～32 weight % and viscosity usually smaller or equal to this material of 250mPa s (25 ℃).
In these modifiers, the carbodiimide modified thing is with the material behind the introducing carbodiimide keys such as well-known phosphorus catalyst series.Prepolymer is to make above-mentioned polyisocyanates and polyol reaction, endways the material of residual isocyanate base.The polyvalent alcohol that use when used polyvalent alcohol can use preparation urethane usually this moment.
Except these polyisocyanates, according to purposes mixed additive, auxiliary agent in the polyisocyanates composition sometimes.
For example, in order to improve the Combination with B liquid, sometimes and with the surfactant that uses in the B liquid as the phase solvation.In such cases, usually preferred nonionic surface active agent, particularly siloxane-based surfactant often is used.
In order to improve flame retardant resistance and to adjust viscosity, sometimes and use fire retardant.In the purposes of hard polyurethane foams, use chlorine alkyl phosphate class usually, for example, tricresyl phosphate (β-chloroethyl) ester, tricresyl phosphate (β-chloropropyl) ester etc.
For additive, auxiliary agent beyond above-mentioned, there is no particular limitation, is to be used in order to improve physical properties and operability etc. in common resin, so as long as urethane esterification reaction is not had significant detrimentally affect, can use any material.
As polyhydroxy reactant, can use that hydroxyl value is generally 200～800, functional group's number is generally 2～8 polyether polyol and polyester polyol etc., also can mix use more than 2 kinds or 2 kinds.As polyether polyol, can exemplify oxyethane, propylene oxide, 1, the alkylene oxide polymer that 2-butylene oxide ring and tetrahydrofuran (THF) etc. are used alone or in combination; Sucrose and sorbyl alcohol and glycerol etc. have 3 or more than the polyvalent alcohol of 3 functional group and the affixture of above-mentioned oxirane; The affixture of fatty amine and aromatic amine and above-mentioned oxirane etc.
As polyester polyol, can use the material of polycarboxylic acid and polyvalent alcohol generation esterification gained in the invention described above, in whole polyhydroxy reactants, usually its content is more than or equal to 2 weight %, be preferably greater than and equal 5 weight %, more preferably greater than equaling 10 weight %, and usually smaller or equal to 50 weight %, preferred 30 smaller or equal to weight %, is more preferably less than to equal 20 weight %.
Except that polyester polyol of the present invention, polyester polyol as frequent use, can enumerate by generation esterifications such as the polycarboxylic acid of aromatic binary carboxylic acids such as Tetra hydro Phthalic anhydride, terephthalic acid and trimellitic acid or tribasic carboxylic acid and independent or blended ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol etc. and glycerol, TriMethylolPropane(TMP)s and make, its hydroxyl value is generally 200～400, and average functional group number is generally 2～3.
In addition, can also with 1 molecule in have more than or equal the compound and the usefulness of 2 reactive hydrogen, as alkanolamines such as pure and mild diethanolamine such as ethylene glycol, Diethylene Glycol, propylene glycol, glycerol, trolamine etc.
For whipping agent, be improved with the consistency of ozone layer destroying coefficient smaller or equal to 0.8 whipping agent, for example, and except that HCFC-141b, pentamethylene and Skellysolve A etc., whipping agents such as HFC-245fa, HFC-365mfc that use from now on particularly.In addition, these whipping agents can be used alone, but also also mix together.
As catalyzer, can use any used, well-known catalyzer in the manufacturing of common urethane foam.For example, remove triethylamine, N, beyond the amine catalyst series such as N-dimethylhexylamine, can also exemplify metal catalyst series such as plumbous series such as tin series such as dibutyl tin laurate, stannous octoate and lead octoate 36 etc.
As surfactant, can use non-ionic type, anionic, cationic surfactant, preferred nonionic surface active agent, especially the silicone-type tensio-active agent often is used.
In addition, according to purposes, also use all cpds sometimes as additive, auxiliary agent.
For example, as representational additive, can exemplify fire retardant.In the purposes of hard polyurethane foams, use chlorine alkyl phosphate class usually, for example, tricresyl phosphate (β-chloroethyl) ester, tricresyl phosphate (β-chloropropyl) ester etc.
For additive, auxiliary agent beyond above-mentioned, there is no particular limitation, is to be used in order to improve physical properties and operability etc. in common resin, as long as urethane esterification reaction is not had significant detrimentally affect, can use any material.
Embodiment
Below, utilize embodiment to illustrate in greater detail the specific embodiment of the present invention, only otherwise exceed above main idea, the present invention is not limited to these embodiment.
＜contain and be selected from by 1,2-HAB, 1,2-AHB and 1, the mixture of at least a compound in the group that 2-DAB forms
Be selected from by 1 as containing, 2-HAB, 1,2-AHB and 1, the mixture of at least a compound in the group that 2-DAB forms use has 3 kinds of crude products 1 forming below, and (Mitsubishi chemical Co., Ltd's system is hereinafter to be referred as crude product 1,2-BG) for the 2-butyleneglycol
3 kinds of crude products 1, the composition that 2-BG contained is as follows.
Crude product 1,2-BG are 1.
1,2-BG 91.0 weight %
1,2-HAB and 1,2-AHB 2.4 weight %
1,2-DAB 0.3 weight %
Other 6.3 weight %
Crude product 1,2-BG are 2.
1,2-BG 75.0 weight %
1,2-HAB and 1,2-AHB 19.8 weight %
1,2-DAB 4.5 weight %
Other 0.7 weight %
Crude product 1,2-BG are 3.
1,2-BG 76.0 weight %
1,2-HAB and 1,2-AHB 18.7 weight %
1,2-DAB 3.9 weight %
Other 1.4 weight %
<1，2-BG>
Use the special grade chemical 1 of Wako Pure Chemical Industries, Ltd.'s system, 2-BG.The purity of mark is more than or equal to 98% on the reagent label, but uses the purity of gc analysis more than or equal to 99.5% in this society.
＜evaluation method 〉
(1) acid number
According to JIS K1557
1970Measure.
(2) hydroxyl value
According to JIS K1557
1970Measure.
(3) viscosity
According to JIS K1557
1970Use rotational viscosimeter (Brookfield viscometer) to measure down at 25 ℃.
(4) solubleness of whipping agent in polyester polyol
The 100g polyester polyol is added in the beaker of 300ml, open system under room temperature, normal atmosphere stirs with 400rpm with the triangle swept-back wing (being the flat slurries of 30 φ in embodiment 1～4 and the comparative example 1～3) of 30 φ, slowly add simultaneously whipping agent, with visual inspection and measure and to form transparent homogeneous maximum addition in 30 seconds, with the index of measured solubleness as the intermiscibility of polyester polyol and whipping agent.
In embodiment 1～4 and comparative example 1～3, owing to use the flat slurry of diameter as 30mm, stirring efficiency is low, so bubble and white casse are difficult to distinguish, is difficult to judge the HFC-365mfc intermiscibility.Therefore, in embodiment 5～14 and comparative example 4 and 5, use the triangle swept-back wing of the good diameter of stirring efficiency, can obtain correct evaluation as 30mm.
Embodiment 1
To having whipping appts, reflux cooler, thermometer, pressure warning unit, heating unit etc. and volume is in 1 liter the glass reaction vessel, add 222g Tetra hydro Phthalic anhydride, 299g crude product 1,2-BG is the (equivalence ratio of adding: hydroxyl/carboxyl=1.81) 2., the nitrogen exchange is carried out in the space of reactor, begun the content in the reactor heating then.When the inside reactor temperature reaches 180 ℃, in reactor, add the 0.3g titanium isopropylate as catalyzer, initiation reaction.With 3 hours internal temperature is raised to 200 ℃, keeps this temperature to reaction to finish.Internal temperature from 180 ℃ to 200 ℃ during, the pressure of inside reactor remains on 97.3kPa.After this, slowly be decompressed to 37.3kPa with 2 hours, and keep this pressure to reaction to finish.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, measures the acid number of extracting test portion out, carries out the index of situation as definite reaction with this.Finish when acid number is considered as reaction smaller or equal to 3 the time, will in reactor, add catalyzer to reaction and finish the used time as reaction times (the following examples are identical with this point in the comparative example).The reaction times of this moment is 7.5 hours.After reaction finishes, stop heating, be cooled to about 100 ℃, extract reaction product out, measure viscosity, acid number and the hydroxyl value of extracting test portion out.Measure the solubleness of whipping agent (HFC-245fa, HFC-365mfc) in the polyester polyol of gained then.
Embodiment 2
With 275g crude product 1,1. 2-BG replaces the composition 299g crude product 1 of adding among the embodiment 1, and 2. 2-BG reacts the (equivalence ratio of adding: hydroxyl/carboxyl=1.87) with order similarly to Example 1 in addition.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, determines reaction end by measuring the acid number of extracting test portion out, finishes reaction.Reaction times is 7.5 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc) solubleness is shown in table-1.
Comparative example 1
With 1 of 270g, 2-BG reagent replaces the composition 299g crude product 1 of adding among the embodiment 1, and 2. 2-BG reacts the (equivalence ratio of adding: hydroxyl/carboxyl=2.00) with order similarly to Example 1 in addition.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, determines reaction end by measuring the acid number of extracting test portion out, finishes reaction.Reaction times is 7.5 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc) solubleness is shown in table-1.
Embodiment 3
To having whipping appts, reflux cooler, thermometer, pressure warning unit, heating unit etc. and volume is in 1 liter the glass reaction vessel, add 222g Tetra hydro Phthalic anhydride, 150g crude product 1,2-BG 2. with the 159g Diethylene Glycol (equivalence ratio of adding: hydroxyl/carboxyl=1.91), the nitrogen exchange is carried out in the space of reactor, begun the content in the reactor heating then.When the inside reactor temperature reaches 180 ℃, in reactor, add the 0.3g titanium isopropylate as catalyzer, initiation reaction.With 3 hours internal temperature is raised to 200 ℃, keeps this temperature to reaction to finish.On the other hand, internal temperature from 180 ℃ to 200 ℃ during, the pressure of inside reactor remains on 97.3kPa.After this, slowly be decompressed to 25.3kPa with 3 hours, and keep this pressure to reaction to finish.The reaction times of this moment is 7.5 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc) solubleness is shown in table-1.
Comparative example 2
With 1 of 135g, 2-BG reagent replaces the composition 150g crude product 1 that adds among the embodiment 3,2-BG 2., in addition to react (the equivalence ratio of adding: hydroxyl/carboxyl=2.00) with the order identical with embodiment 3.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, measures the acid number of extracting test portion out and determines reaction end, finishes reaction.Reaction times is 7.5 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc) solubleness is shown in table-1.
Embodiment 4
To having whipping appts, reflux cooler, thermometer, pressure warning unit, heating unit etc. and volume is to add 249g terephthalic acid, 299g crude product 1 in 1 liter the glass reaction vessel, 2-BG is the (equivalence ratio of adding: hydroxyl/carboxyl=1.81) 2., the nitrogen exchange is carried out in the space of reactor, begun the content in the reactor heating then.When the inside reactor temperature reaches 180 ℃, in reactor, add the 0.3g titanium isopropylate as catalyzer, initiation reaction.With 8 hours internal temperature is raised to 200 ℃, keeps this temperature to reaction to finish.Internal temperature from 180 ℃ to 200 ℃ during, the pressure of inside reactor remains on 97.3kPa.After this, slowly be decompressed to 37.3kPa, keep this pressure to reaction to finish through 2 hours.Reaction times is 17.5 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc) solubleness is shown in table-1.
Comparative example 3
With 1 of 270g, 2-BG reagent replaces the composition 299g crude product 1 that adds among the embodiment 4, and 2. 2-BG reacts the (equivalence ratio of adding: hydroxyl/carboxyl=2.00) with the order identical with embodiment 4 in addition.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, measures the acid number of extracting test portion out and determines reaction end, finishes reaction.Reaction times is 7.5 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc) solubleness is shown in table-1.
Table-1
| Equivalence ratio | 1,2-BG purity | The content of acetoxyl material | Viscosity (25 ℃) | Acid number | Hydroxyl value | Whipping agent solubleness | ||
| ???HFC-245fa | ??HFC-365mfc | |||||||
| (weight %) | (weight %) | ??(mPa?s) | ????(mgKOH/g) | ????(mgKOH/g) | (g/100g polyester polyol) | |||
| Embodiment 1 | ????1.82 | ????75 | ????24 | ??7,500 | ????0.84 | ????203 | ????≥100 | ????30 |
| Embodiment 2 | ????1.87 | ????91 | ????3 | ??16,500 | ????0.70 | ????250 | ????70 | ????13 |
| Comparative example 1 | ????2.00 | ????99.5 | ????＜0.5 | ??20,000 | ????0.65 | ????341 | ????50 | ????8 |
| Embodiment 3 | ????1.91 | ????75 | ????15 | ??4,200 | ????0.48 | ????279 | ????80 | ????14 |
| Comparative example 2 | ????2.00 | ????75 | ????＜0.5 | ??7,500 | ????0.65 | ????332 | ????30 | ????5 |
| Embodiment 4 | ????1.82 | ????75 | ????24 | ??7,500 | ????0.89 | ????209 | ????≥100 | ????45 |
| Comparative example 3 | ????2.00 | ????99.5 | ????＜0.5 | ??22,000 | ????1.14 | ????342 | ????65 | ????9 |
In the table-1, " equivalence ratio " is that expression adds the hydroxyl and the equivalence ratio (hydroxyl/carboxyl) of carboxyl in the composition, " content of acetoxyl material " be represent to contain in the alcohol 1,2-HAB, 1,2-AHB and 1, the total amount of 2-DAB.
Embodiment 5
To having whipping appts, reflux cooler, thermometer, pressure warning unit, heating unit etc. and volume is to add 458g Tetra hydro Phthalic anhydride, 598g crude product 1 in 2 liters the glass reaction vessel, 2-BG is the (equivalence ratio of adding: hydroxyl/carboxyl=1.77) 3., the nitrogen exchange is carried out in the space of reactor, begun the content in the reactor heating then.When the inside reactor temperature reaches 180 ℃, in reactor, add the 0.5g titanium isopropylate as catalyzer, initiation reaction.With 3 hours internal temperature is raised to 200 ℃, keeps this temperature to reaction to finish.Internal temperature from 180 ℃ to 200 ℃ during, the pressure of inside reactor remains on 93.3kPa.After this, slowly be decompressed to 33.3kPa with 2.5 hours, keep this pressure to reaction to finish.The judgement that reaction finishes is identical with embodiment 1 with the operation of reacting after finishing, and the reaction times of this reaction is 8 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc, HCFC141b and pentamethylene) solubleness is shown in table-2.
When reaction finishes, add up to 0.54g acetic acid to distillate outside the system, and be present in the distillate.This amount is for crude product 1, among the 2-BG about 0.8% of the amount of the pairing acetic acid of acetoxyl of contained monoesters material and dibasic acid esters material.In order to measure more accurately, between reliever and reactor, to have designed with dry ice and acetone refrigerative vacuum trap, but wherein do not had acetic acid.
Embodiment 6
Except the added ingredients among the embodiment 5 being become 429g Tetra hydro Phthalic anhydride, 623g crude product 1,2-BG 3. and resulting pressure become beyond the 44.0kPa, react (the equivalence ratio of adding: hydroxyl/carboxyl=1.97) with the order identical with embodiment 5.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, measures the acid number of extracting test portion out and determines reaction end, finishes reaction.Reaction times is 8 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc, HCFC141b and pentamethylene) solubleness is shown in table-2.
Embodiment 7
Except the added ingredients among the embodiment 5 being become 439g Tetra hydro Phthalic anhydride, 164g crude product 1,2-BG 1., 450g crude product 1,2-BG 3. and resulting pressure become beyond the 38.7kPa, react (the equivalence ratio of adding: hydroxyl/carboxyl=1.95) with the order identical with embodiment 5.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, measures the acid number of extracting test portion out and determines reaction end, finishes reaction.Reaction times is 8 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc, HCFC141b and pentamethylene) solubleness is shown in table-2.
Embodiment 8
Except the added ingredients among the embodiment 5 being become 459g Tetra hydro Phthalic anhydride, 358g crude product 1,2-BG 1., 239g crude product 1,2-BG 3. and resulting pressure become beyond the 42.7kPa, react (the equivalence ratio of adding: hydroxyl/carboxyl=1.88) with the order identical with embodiment 5.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, measures the acid number of extracting test portion out and determines reaction end, finishes reaction.Reaction times is 8 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc, HCFC141b) solubleness is shown in table-2.
Embodiment 9
Except the added ingredients among the embodiment 5 being become 428g Tetra hydro Phthalic anhydride, 375g crude product 1,2-BG 1., 250g crude product 1,2-BG 3. and resulting pressure become beyond the 44.0kPa, react (the equivalence ratio of adding: hydroxyl/carboxyl=2.11) with the order identical with embodiment 5.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, measures the acid number of extracting test portion out and determines reaction end, finishes reaction.Reaction times is 8 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc, HCFC141b and pentamethylene) solubleness is shown in table-2.
Embodiment 10
Except the added ingredients among the embodiment 5 being become 397g Tetra hydro Phthalic anhydride, 391g crude product 1,2-BG 1., 261g crude product 1,2-BG 3. and resulting pressure become beyond the 48.0kPa, react (the equivalence ratio of adding: hydroxyl/carboxyl=2.38) with the order identical with embodiment 5.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, measures the acid number of extracting test portion out and determines reaction end, finishes reaction.Reaction times is 8 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc, HCFC141b and pentamethylene) solubleness is shown in table-2.
Embodiment 11
Except the added ingredients among the embodiment 5 being become 482g Tetra hydro Phthalic anhydride, 577g crude product 1,2-BG 1. and resulting pressure become beyond the 34.7kPa, react (the equivalence ratio of adding: hydroxyl/carboxyl=1.81) with the order identical with embodiment 5.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, measures the acid number of extracting test portion out and determines reaction end, finishes reaction.Reaction times is 8 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc, HCFC141b) solubleness is shown in table-2.
Embodiment 12
Except the added ingredients among the embodiment 5 being become 423g Tetra hydro Phthalic anhydride, 628g crude product 1,2-BG 1. and resulting pressure become beyond the 44.9kPa, react (the equivalence ratio of adding: hydroxyl/carboxyl=2.24) with the order identical with embodiment 5.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, measures the acid number of extracting test portion out and determines reaction end, finishes reaction.Reaction times is 8 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc, HCFC141b and pentamethylene) solubleness is shown in table-2.
Embodiment 13
Except the added ingredients among the embodiment 5 being become 489g Tetra hydro Phthalic anhydride, 342g crude product 1,2-BG 1., 228g crude product 1,2-BG 3. and resulting pressure become beyond the 33.3kPa, react (the equivalence ratio of adding: hydroxyl/carboxyl=1.69) with the order identical with embodiment 5.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, measures the acid number of extracting test portion out and determines reaction end, finishes reaction.Reaction times is 8 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc, HCFC141b and pentamethylene) solubleness is shown in table-2.
Comparative example 4
Except the added ingredients among the embodiment 5 is become 1 of 559g Tetra hydro Phthalic anhydride, 509g, beyond the 2-BG reagent, react (the equivalence ratio of adding: hydroxyl/carboxyl=1.50) with the order identical with embodiment 5.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, measures the acid number of extracting test portion out and determines reaction end, finishes reaction.Reaction times is 8 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc, HCFC141b and pentamethylene) solubleness is shown in table-2.
Comparative example 5
Except the added ingredients among the embodiment 5 is become 1 of 528g Tetra hydro Phthalic anhydride, 523g, 2-BG reagent and resulting pressure become beyond the 37.3kPa, react (the equivalence ratio of adding: hydroxyl/carboxyl=1.63) with the order identical with embodiment 5.Reaction is carried out in the process, extracts a part of reaction mixture from reactor out, measures the acid number of extracting test portion out and determines reaction end, finishes reaction.Reaction times is 8 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc, HCFC141b and pentamethylene) solubleness is shown in table-2.
Embodiment 14
To having whipping appts, reflux cooler, thermometer, pressure warning unit, heating unit etc. and volume is in 2 liters the glass reaction vessel, add 201g succsinic acid, 281g terephthalic acid, 641g crude product 1,2-BG is the (equivalence ratio of adding: hydroxyl/carboxyl=1.73) 3., the nitrogen exchange is carried out in the space of reactor, begun the content in the reactor heating then.When the inside reactor temperature reaches 150 ℃, in reactor, add the 0.5g titanium isopropylate as catalyzer, initiation reaction.With 8 hours internal temperature is raised to 210 ℃, keeps this temperature to reaction to finish.Internal temperature from 180 ℃ to 210 ℃ during, the pressure of inside reactor remains on 80.0kPa.After this, slowly be decompressed to 40.0kPa with 4 hours, and keep this pressure to reaction to finish.The judgement that reaction finishes is identical with embodiment 1 with the operation of reacting after finishing, and the reaction times of this reaction is 14 hours.The measurement result of the viscosity of reaction product, acid number, hydroxyl value and whipping agent (HFC-245fa, HFC-365mfc, HCFC141b) solubleness is shown in table-2.
Table-2
| Equivalence ratio | 1,2-BG purity | The content of acetoxyl material | Viscosity (25 ℃) | Acid number | Hydroxyl value | Whipping agent solubleness | ||||
| ????HFC-245fa | ????HFC-365mfc | ????HCFC-141b | The c-pentane | |||||||
| (weight %) | (weight %) | ????(mPa?s) | ????(mgKOH/g) | ????(mgKOH/g) | (g/100g polyester polyol) | |||||
| Embodiment 5 | ??1.77 | ????76 | ????23 | ????9,200 | ????0.45 | ????197 | ????≥100 | ????≥100 | ????≥100 | ????16 |
| Embodiment 6 | ??1.97 | ????76 | ????23 | ????3,300 | ????0.59 | ????246 | ????≥100 | ????≥100 | ????≥100 | ????17 |
| Embodiment 7 | ??1.95 | ????80 | ????17 | ????4,900 | ????0.56 | ????254 | ????≥100 | ????≥100 | ????≥100 | ????16 |
| Embodiment 8 | ??1.88 | ????85 | ????11 | ????8,610 | ????0.57 | ????250 | ????≥100 | ????75 | ????≥100 | ????- |
| Embodiment 9 | ??2.11 | ????85 | ????11 | ????3,200 | ????0.36 | ????302 | ????≥100 | ????80 | ????≥100 | ????19 |
| Embodiment 10 | ??2.38 | ????85 | ????11 | ????1,600 | ????0.48 | ????348 | ????≥100 | ????85 | ????≥100 | ????19 |
| Embodiment 11 | ??1.81 | ????91 | ????3 | ????20,000 | ????0.75 | ????239 | ????65 | ????55 | ????≥100 | ????- |
| Embodiment 12 | ??2.24 | ????91 | ????3 | ????3,100 | ????0.37 | ????347 | ????75 | ????55 | ????≥100 | ????17 |
| Embodiment 13 | ??1.69 | ????85 | ????11 | ????27,300 | ????1.24 | ????206 | ????90 | ????65 | ????≥100 | ????14 |
| Comparative example 4 | ??1.50 | ????99.5 | ????＜0.5 | 〉=20 ten thousand | ????0.50 | ????200 | The viscosity height can't be measured | |||
| Comparative example 5 | ??1.63 | ????99.5 | ????＜0.5 | ????160,000 | ????2.60 | ????239 | ????35 | ????25 | ????50 | ????5 |
| Embodiment 14 | ??1.73 | ????76 | ????23 | ????2.430 | ????1.74 | ????209 | ????≥100 | ????≥100 | ????≥100 | ????- |
In the table-2, " equivalence ratio " is that expression adds the hydroxyl and the equivalence ratio (hydroxyl/carboxyl) of carboxyl in the composition, " content of acetoxyl material " be represent to contain in the alcohol 1,2-HAB, 1,2-AHB and 1, the total amount of 2-DAB, " c-pentane " is the representative ring pentane.
Table-1 and table-2 show following result.
(1) comparative result of embodiment and comparative example
In the alcohol 1,2-HAB, 1,2-AHB and 1, the total content of 2-DAB are the embodiment of 3 weight %～24 weight %, compare with its comparative example that contains quantity not sufficient 0.5 weight %, can obtain the low and high polyester polyol of solubleness whipping agent of viscosity.
(2) embodiment 1,2 and 5～13 with comparative example 1,4 and 5 comparative result
With the equivalence ratio (hydroxyl/carboxyl) or the hydroxyl value that add is comparing of par, crude product 1, among the 2-BG contained 1, the content of 2-BG (purity) be the situation of 70 weight %～95 weight % with the special grade chemical 1 of purity more than or equal to 99.5 weight %, 2-BG is that the situation of raw material is compared, and the former can obtain the low and high polyester polyol of solubleness whipping agent of viscosity.
(3) comparative result of embodiment 3 and comparative example 2
Remove crude product 1 even the part of raw alcohol is used, the alcohol (Diethylene Glycol) beyond the 2-BG also can obtain the low and high polyester polyol of solubleness whipping agent of viscosity.
(4) comparative result and the embodiment 14 of embodiment 4 and comparative example 3
As aromatic carboxylic acid in the raw material,, obtain the low and high polyester polyol of solubleness whipping agent of viscosity equally even use terephthalic acid rather than use phthalic acid or Tetra hydro Phthalic anhydride.
Part with aromatic carboxylic acid in aliphatic carboxylic acid (succsinic acid) the replacement raw material also can obtain the lower and high polyester polyol of solubleness whipping agent of viscosity.
Utilizability on the industry
Low, the easy use of polyester polyol viscosity of the present invention, and with blowing agent particularly the intermiscibility of the HFC such as HFC-245fa and/or HFC-365mfc series blowing agent is high, be useful as the raw polyol of polyurethane especially hard polyurethane foams.
In addition, as disclosing of specification sheets of the present invention, quote become the Japanese Patent of the application's basis for priority 2002-313420 number content of specification sheets of (application on October 28th, 2002) here.
Claims (7)
1, a kind of polyester polyol, it is characterized in that, make polycarboxylic acid and alcohol that esterification take place and make, described alcohol contains being selected from by 1-hydroxyl-2-acetoxyl butane, 1-acetoxyl-2-hydroxyl butane and 1 of 2 weight %～40 weight %, at least a material in the group that 2-diacetoxyl butane is formed.
2, a kind of polyester polyol, wherein, alcohol is mixture and contains 1,2-butyleneglycol and being selected from by 1-hydroxyl-2-acetoxyl butane, 1-acetoxyl-2-hydroxyl butane and 1, at least a material in the group that 2-diacetoxyl butane is formed, in this mixture 1, the content of 2-butyleneglycol is 60 weight %～98 weight %.
3, polyester polyol as claimed in claim 2, wherein, mixture makes by the following method: in the presence of molecular oxygen and palladium class catalyzer, make the reaction of 1,3-butadiene and acetic acid generation acetoxylation; With diacetoxyl butylene class reaction product and the hydrogenation addition in the presence of noble metal catalyst of single acetoxyl butylene class reaction product that obtains; Then with the diacetoxyl butanes reaction product and the hydrolysis in the presence of solid acid catalyst of single acetoxyl butanes reaction product of gained, heat up in a steamer acetic acid and water after, fractionation by distillation.
4, a kind of urethane is characterized in that, the polyvalent alcohol and the isocyanate compound reaction that contain just like each described polyester polyol of claim 1～3 are made.
5, a kind of hard polyurethane foams is to use urethane as claimed in claim 4 to obtain.
6, hard polyurethane foams as claimed in claim 5, it also contains the ozone layer destroying coefficient smaller or equal to 0.8 whipping agent.
7, hard polyurethane foams as claimed in claim 6, wherein whipping agent is HFC-245fa and/or HFC-365mfc.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002313420 | 2002-10-28 | ||
| JP313420/2002 | 2002-10-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1708529A true CN1708529A (en) | 2005-12-14 |
| CN1322020C CN1322020C (en) | 2007-06-20 |
Family
ID=32171163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801021626A Expired - Fee Related CN1322020C (en) | 2002-10-28 | 2003-10-28 | Polyester polyol, polyurethane obtained therefrom, and rigid polyurethane foam |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP4512491B2 (en) |
| KR (1) | KR100997066B1 (en) |
| CN (1) | CN1322020C (en) |
| AU (1) | AU2003275714A1 (en) |
| TW (1) | TW200415170A (en) |
| WO (1) | WO2004037890A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172816A (en) * | 2008-12-01 | 2013-06-26 | 三菱化学株式会社 | Process for production of polyurethane and uses of polyurethane produced thereby |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008133372A (en) * | 2006-11-28 | 2008-06-12 | Mitsubishi Chemicals Corp | Polyester-based plasticizer, and vinyl chloride-based resin composition containing the same |
| KR101190850B1 (en) * | 2010-10-11 | 2012-10-15 | 오씨아이 주식회사 | Manufacturing method of aromatic ester type polyol and foams using the same for water-blown polyurethane |
| JP5709045B2 (en) * | 2011-04-20 | 2015-04-30 | 川崎化成工業株式会社 | Method for producing polyurethane foam |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08311183A (en) * | 1995-05-17 | 1996-11-26 | Mitsui Toatsu Chem Inc | Ester polyol and its production |
| CN1113073C (en) * | 1997-03-27 | 2003-07-02 | 协和油化株式会社 | Polyurethanes and polyester polyols |
| CN1322022C (en) * | 1999-05-20 | 2007-06-20 | 大赛璐化学工业株式会社 | Polyester diol,acrylic-based copolymer, polyurethane composition and spandex composition |
| JP4746787B2 (en) * | 2000-07-31 | 2011-08-10 | 三井化学株式会社 | Polyester polyol production method and polyester polyol production apparatus |
| JP2002220430A (en) * | 2001-01-26 | 2002-08-09 | Asahi Glass Co Ltd | Method for producing rigid synthetic resin foam and polyol composition |
-
2003
- 2003-10-28 CN CNB2003801021626A patent/CN1322020C/en not_active Expired - Fee Related
- 2003-10-28 AU AU2003275714A patent/AU2003275714A1/en not_active Abandoned
- 2003-10-28 WO PCT/JP2003/013783 patent/WO2004037890A1/en active Application Filing
- 2003-10-28 KR KR1020057007359A patent/KR100997066B1/en not_active IP Right Cessation
- 2003-10-28 JP JP2004546492A patent/JP4512491B2/en not_active Expired - Fee Related
- 2003-10-28 TW TW092129926A patent/TW200415170A/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172816A (en) * | 2008-12-01 | 2013-06-26 | 三菱化学株式会社 | Process for production of polyurethane and uses of polyurethane produced thereby |
| CN103172816B (en) * | 2008-12-01 | 2015-05-27 | 三菱化学株式会社 | Process for production of polyurethane and uses of polyurethane produced thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20050071634A (en) | 2005-07-07 |
| CN1322020C (en) | 2007-06-20 |
| AU2003275714A8 (en) | 2004-05-13 |
| WO2004037890A1 (en) | 2004-05-06 |
| TW200415170A (en) | 2004-08-16 |
| TWI316066B (en) | 2009-10-21 |
| KR100997066B1 (en) | 2010-11-29 |
| AU2003275714A1 (en) | 2004-05-13 |
| JPWO2004037890A1 (en) | 2006-02-23 |
| JP4512491B2 (en) | 2010-07-28 |
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