CN103459462B - The manufacture method of polyester polyol and polyester modification thing, polyester polyol and polyester modification thing - Google Patents
The manufacture method of polyester polyol and polyester modification thing, polyester polyol and polyester modification thing Download PDFInfo
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- CN103459462B CN103459462B CN201280016654.2A CN201280016654A CN103459462B CN 103459462 B CN103459462 B CN 103459462B CN 201280016654 A CN201280016654 A CN 201280016654A CN 103459462 B CN103459462 B CN 103459462B
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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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
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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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a kind of do not use tin metalloid catalyzer and can at short notice depolymerization Starting Material Polyester to manufacture the method for polyester polyol.A manufacture method for polyester polyol, is characterized in that, possesses and heats with the operation of depolymerization Starting Material Polyester containing Starting Material Polyester, polyhydroxy reactant and non-tin metalloid catalyzer or the non-metal kind basic catalyst mixture as neccessary composition.Described non-tin metalloid catalyzer is preferably selected from the compound in the group be made up of zn cpds, manganic compound, lithium compound and calcium cpd.
Description
Technical field
The present invention relates to polyester is the manufacture method of the polyester polyol of raw material and polyester modification thing, polyester polyol and polyester modification thing, is specifically related to the manufacture method of the polyester modification thing not using the manufacture method of the polyester polyol of tin metalloid catalyzer and make the polyester polyol modification obtained by this manufacture method.
Background technology
Be used in the various uses such as products formed, film, fiber with the polyester that polyethylene terephthalate (PET) is representative.Wherein, in recent years, because PET bottle amount is light and transparent, gas barrier property is excellent, intensity is also high, therefore consumption just sharply increases.
On the other hand, following technology has been carried out: utilize polyvalent alcohol depolymerizing polyester to derive various resin to manufacture polyester polyol or make this polyester polyol modification.
Such as, the manufacture utilized based on the coating Synolac of the depolymerization reaction of glycols is disclosed in patent documentation 1, in patent documentation 2 and 3, disclose the manufacture method of the coating vibrin using recycled polyester, in patent documentation 4, disclose the raw material utilizing recycled polyester as light solidified urethane resin.The resin that above-mentioned patent documentation is recorded is all for the purpose of using in the coating composition.
All the time, the depolymerization reaction of polyester is by loading reactor by Starting Material Polyester and polyvalent alcohol, depolymerization catalyst, and heating is carried out.Now, as depolymerization catalyst, use metal catalyst, especially tin class catalyzer.
prior art document
patent documentation
Patent documentation 1: No. 3310661st, Japanese Patent
Patent documentation 2: No. 3443409th, Japanese Patent
Patent documentation 3: No. 3256537th, Japanese Patent
Patent documentation 4: Japanese Unexamined Patent Publication 2004-307779 publication
Summary of the invention
the problem that invention will solve
But, have report point out tin compound particularly organic tin compound to the toxicity of organism, also indicate the impact on environment.Therefore, the exploitation of the catalyzer that can replace tin metalloid catalyzer in the depolymerization reaction of polyester is being sought.
Therefore, the object of the present invention is to provide a kind of do not use tin metalloid catalyzer and can at short notice depolymerization Starting Material Polyester to manufacture the method for polyester polyol.
for the scheme of dealing with problems
For solving the problem, the present inventor etc. conduct in-depth research, and found that, by using non-tin metalloid catalyzer or non-metal kind basic catalyst to solve the problem, so far complete the present invention.
Namely, the manufacture method of polyester polyol of the present invention, it is characterized in that possessing and heat with the operation of depolymerization Starting Material Polyester containing Starting Material Polyester, polyhydroxy reactant and non-tin metalloid catalyzer or the non-metal kind basic catalyst mixture as neccessary composition.
In the manufacture method of polyester polyol of the present invention, preferred above-mentioned non-tin metalloid catalyzer is selected from the compound in the group that is made up of zn cpds, manganic compound, lithium compound and calcium cpd, is more preferably the compound in the group being selected from and being made up of naphthenic acid metal complex, acetylacetone metal complex and sad metallic soap.
And, in the manufacture method of polyester polyol of the present invention, preferred above-mentioned non-tin metalloid catalyzer is selected from the compound in the group that is made up of zinc naphthenate, zinc acetylacetonate, zinc octoate, calcium naphthenate, calcium acetylacetonate, calcium octoate, naphthenic acid lithium, methyl ethyl diketone lithium, sad lithium, Lithium Acetate, manganese naphthenate, manganese acetylacetonate and manganese octoate.
In the manufacture method of polyester polyol of the present invention, preferred above-mentioned non-metal kind basic catalyst is the hetero ring type compound with amidine structure.
In the manufacture method of polyester polyol of the present invention, preferred above-mentioned non-metal kind basic catalyst be selected from the group that is made up of diazabicycloundecene, diazabicyclo-nonene and their derivative more than one.
In addition, in the manufacture method of polyester polyol of the present invention, preferred above-mentioned polyhydroxy reactant comprises the polyvalent alcohol of more than trifunctional.
In addition, in the manufacture method of polyester polyol of the present invention, preferred above-mentioned raw materials polyester is recycled polyester.
In addition, in the manufacture method of polyester polyol of the present invention, preferably add water as in the mixture of neccessary composition, to carry out the depolymerization of Starting Material Polyester to containing Starting Material Polyester, polyhydroxy reactant and non-tin metalloid catalyzer.
In addition, in the manufacture method of polyester polyol of the present invention, preferred above-mentioned depolymerization is carried out at 200 DEG C ~ 300 DEG C.
In addition, in the manufacture method of polyester polyol of the present invention, preferably obtain the mixture of compound shown in following general formula (1).
(in formula, R
1represent the group removing OH base from the polyvalent alcohol of (1+m) valency, R
2represent the alkylidene group of carbonatoms 1 ~ 10 or the arylidene of substituted or unsubstituted carbonatoms 6 ~ 20, R
3represent the arylidene of substituted or unsubstituted carbonatoms 6 ~ 20, the integer that the integer that l is 0 ~ 10, m are 1 ~ 10, n is the integer of 1 ~ 10.）
The feature of polyester polyol of the present invention is, described polyester polyol is obtained by the manufacture method of any one polyester polyol above-mentioned.
The feature of the manufacture method of polyester modification thing of the present invention is, makes to have to react with the polyester polyol obtained by the manufacture method of above-mentioned polyester polyol with the compound of the group of hydroxyl reaction and ethylenically unsaturated group.
The feature of polyester modification thing of the present invention is, described polyester modification thing is obtained by the manufacture method of above-mentioned polyester modification thing.
the effect of invention
According to the manufacture method of polyester polyol of the present invention, do not use tin metalloid catalyzer and Starting Material Polyester can be dissolved easily in organic solvent to convert the polyester polyol that can carry out various chemical modification to.Based on this, compared with the existing polyester polyol utilizing the method for tin class catalyzer obtained of use, the polyester polyol that Theil indices reduces can be obtained.In addition, when employing nonmetal basic catalyst, the deterioration of the electrical insulating property caused because of the impact of kish catalyzer in products obtained therefrom can be avoided.
And, according to the present invention, the manufacture of high efficiency ground photosensitive polyester modification thing can be imparted at lower cost.
Embodiment
The essential characteristic of the manufacture method of polyester polyol of the present invention is, uses non-tin metalloid catalyzer or non-metal kind basic catalyst when utilizing polyhydroxy reactant depolymerization Starting Material Polyester.
［ non-tin metalloid catalyzer ］
As the non-tin metalloid catalyzer used in method of the present invention, preferred zn cpds, manganic compound, lithium compound, calcium cpd, more preferably naphthenic acid metal complex, acetylacetone metal complex, sad metallic soap.Wherein, particularly preferably zinc naphthenate, zinc acetylacetonate, zinc octoate, calcium naphthenate, calcium acetylacetonate, calcium octoate, naphthenic acid lithium, methyl ethyl diketone lithium, sad lithium, Lithium Acetate, manganese naphthenate, manganese acetylacetonate and manganese octoate.
Relative to total amount 100 mass parts of Starting Material Polyester and polyhydroxy reactant, consumption part of above-mentioned non-tin metalloid catalyzer is preferably 0.005 ~ 5 mass parts, is more preferably 0.05 ~ 3 mass parts.
［ non-metal kind basic catalyst ］
As the non-metal kind basic catalyst used in method of the present invention, preferred cyclic nitrogen compound, more preferably has the hetero ring type compound of amidine structure.Wherein, particularly preferably diazabicycloundecene (1,8-diazabicylo [5.4.0] 11 carbon-7-alkene, hereinafter also referred to " DBU "), diazabicyclo-nonene (1,5-diazabicylo [4.3.0] nonene-5, hereinafter also referred to " DBN ") and derivative.DBU and DBN is organic alkali group, structural similitude, is ammonia esterification, the compound that uses of the catalyzer of the identical reaction such as Wittig reaction.
As diazabicycloundecene (DBU), diazabicyclo-nonene (DBN) and their derivative, such as, can list: DBU, DBN, DBU carbonate, DBU carboxylate salt, DBU phenolate, DBU thiolate, DBN carbonate, DBN carboxylate salt, DBN phenolate, DBN thiolate.
As the commercially available product of DBU, DBN and their derivative, such as, can list: U-CATSA1, U-CATSA102, U-CATSA506, U-CATSA603, U-CATSA810, U-CATSA831, U-CATSA841, U-CATSA851, U-CAT881, more than U-CAT5002(trade(brand)name are San-AproLtd. system).
Relative to total amount 100 mass parts of Starting Material Polyester and polyhydroxy reactant, consumption preferably 0.005 ~ 5 mass parts of above-mentioned non-metal kind basic catalyst, more preferably 0.05 ~ 3 mass parts.
［ Starting Material Polyester ］
As long as the known polyester of the Starting Material Polyester used in method of the present invention, be then not particularly limited.As long as can carry out melting by heating, then any polyester is all applicable to method of the present invention.
In addition, as Starting Material Polyester, preferably there is the polyester of repeating unit shown in following general formula (2).
(in formula, R
4represent the alkylidene group of carbonatoms 1 ~ 10 or the arylidene of substituted or unsubstituted carbonatoms 6 ~ 20, R
5represent the arylidene of substituted or unsubstituted carbonatoms 6 ~ 20, O represent more than 1 integer.）
As R in above-mentioned general formula (2)
4the alkylidene group of represented carbon number 1 ~ 10, can list methylene radical, ethylene, trimethylene, tetramethylene, 1,2-butylidene, pentamethylene etc.
As R in above-mentioned general formula (2)
4the arylidene of represented carbon number 6 ~ 20, can list Isosorbide-5-Nitrae-phenylene, 2,6-naphthylidenes etc.These arylidene can by replacements such as alkyl, alkoxyl group, halogen atoms.
As R in above-mentioned general formula (2)
5the arylidene of represented carbon number 6 ~ 20, can list and above-mentioned R
4the group that the group of example is identical.
As the object lesson of preferred Starting Material Polyester, the polycondensate, 4 of polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate), polybutylene terephthalate, PEN, PBN, ethylene glycol terephthalate and P-hydroxybenzoic acid can be listed, the liquid crystalline polymerss etc. such as the polycondensate of the polycondensate of 4-dihydroxybiphenyl phenol and terephthalic acid and P-hydroxybenzoic acid, 2,6-hydroxynaphthoic acids and P-hydroxybenzoic acid.In the middle of above-mentioned, particularly preferably polyethylene terephthalate.
In addition, consider from the angle of environment protection, more preferably using the recirculation PET that reclaimed by Plastic Bottle rejected material the like waste and regenerative PET as Starting Material Polyester.The PET be recovered pulverized and wash, regenerative PET by washed and particle (pellet) change after material can obtain from the market.
［ polyhydroxy reactant ］
As above-mentioned polyhydroxy reactant, be not particularly limited, two sense polyvalent alcohols, the above polyvalent alcohol of trifunctional etc. can be used.Above-mentioned polyhydroxy reactant can be used alone one, also can be used in combination.
As two sense polyvalent alcohols, can list: ethylene glycol, 1,3-PD, 1,2-PD, BDO, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, dipropylene glycol, 1,3 butylene glycol, neopentyl glycol, the spiroglycol, diox glycol, diamantane glycol, 3-methyl isophthalic acid, 5-pentanediol, methyl ethohexadiol, 1,6-hexylene glycol, 1,4 cyclohexane dimethanol, 2-methyl propanediol 1,3, 3-methyl pentanediol 1,5, hexamethylene glycol, ethohexadiol, 9-nonanediol, 2,4-diethyl-1,5-PD, the ethylene-oxide-modified compound of the two sense phenol that dihydroxyphenyl propane is such, the epoxy pronane modification compound of the two sense phenol that dihydroxyphenyl propane is such, the oxyethane of dihydroxyphenyl propane, propylene oxide copolymer modified compound, the Copolymer polyether glycol of oxyethane and propylene oxide, polycarbonate diol, polyether glycol, polyester glycol, polycaprolactone glycol, Isosorbide-5-Nitrae-polyisoprene glycol, 1，4-polybutadiene glycol, 1,2-polybutadiene diol, the C-terminal that the hydrogenation products of Isosorbide-5-Nitrae-or 1,2-polybutadiene diol is such gathers alkane cyclohexadienediol (polyalkanedienediol) class.
As the example of the commercially available product of above-mentioned polycaprolactone glycol, such as, can list: Placcel205, PlaccelL205AL, Placcel205U, Placcel208, PlaccelL208AL, Placcel210, Placcel210N, Placcel212, PlaccelL212AL, Placcel220, Placcel220N, Placcel220NP1, PlaccelL220AL, Placcel230, Placcel240, Placcel220EB, more than Placcel220EC(are Daicel chemical industry (strain) system).
Gather the example of the commercially available product of alkane cyclohexadienediol as above-mentioned C-terminal, such as, エ ポ ー Le (registered trademark can be listed; Hydrogenated polyisoprene glycol, molecular weight 1860, mean polymerisation degree 26, the emerging product of bright dipping (strain) system), PIP(polyisoprene glycol, molecular weight 2200, mean polymerisation degree 34, the emerging product of bright dipping (strain) system), Port リ テ ー Le H(hydrogenated polybutadiene diol, molecular weight 2200, mean polymerisation degree 39, Mitsubishi Chemical's (strain) system), R-45HT(polytetramethylene glycol, molecular weight 2270, mean polymerisation degree 42, the emerging product of bright dipping (strain) system).
As polyvalent alcohol more than trifunctional, can list: glycerine, trimethylolethane, TriMethylolPropane(TMP), Sorbitol Powder, tetramethylolmethane, two TriMethylolPropane(TMP)s, Dipentaerythritol, tripentaerythritol, diamantane triol, polycaprolactonetriol etc.In addition, as the polyvalent alcohol more than trifunctional with aromatic nucleus, the oxyethane of the phenolic compound of more than trifunctional, epoxy pronane modification thing etc. can be listed, as containing the polyvalent alcohol more than trifunctional of heterocycle, four countries can be listed and change into industry (strain) THEIC processed etc.
As the example of the commercially available product of above-mentioned polycaprolactonetriol, such as, can list: Placcel303, Placcel305, Placcel308, Placcel312, PlaccelL312AL, Placcel320ML, PlaccelL320AL (being Daicel chemical industry (strain) system above, trade(brand)name).
As polyhydroxy reactant, the alcohol composition (polyvalent alcohol from plant) from plant can be used.As the alcohol composition from plant, preferred castor seeds oils alcohol composition.As commercially available product, such as, can list: URICH-30, URICH-31, URICH-52, URICH-56, URICH-57, URICH-62, URICH-73X, URICH-92, URICH-420, URICH-854, URICY-202, URICY-403, URICY-406, URICY-563, URICAC-005, URICAC-006, URICPH-5001, URICPH-5002, URICPH-6000, URICF-15, URICF-25, URICF-29, URICF-40, URICSE-2010, URICSE-3510, URICSE-2606, URICSE-3506, URICSE-2003, POLYCASTOR#10, POLYCASTOR#30, URICSE-2003(is her rattan liquefaction Inc.).
The polyhydroxy reactant used in the present invention, preferably containing polyvalent alcohol more than trifunctional, particularly preferably contains TriMethylolPropane(TMP).
The consumption of above-mentioned polyhydroxy reactant is relative to the ester bond 1 mole of Starting Material Polyester, and the hydroxyl of preferred polyol composition is 0.5 mole ~ 7.0 moles, more preferably 1.0 moles ~ 5.0 moles.
［ reaction conditions ］
In the method for the invention, the mixture containing above-mentioned each composition is loaded reactor, and heats, thus carry out the depolymerization of Starting Material Polyester.Heating means can use existing known method.Above-mentioned each composition can be mixed, reheat after being modulated into mixture, also limit heating edge successively each composition can be imported reactor.Heating temperature preferably 150 ~ 350 DEG C, more preferably 200 ~ 300 DEG C.In addition, time with an organic solvent, although existing known solvent can be used, consider from the angle of the impact on environment, preferably when not with an organic solvent react.
In method of the present invention, preferably containing Starting Material Polyester, polyhydroxy reactant and non-tin metalloid catalyzer as the mixture of neccessary composition in add water, to carry out the depolymerization of Starting Material Polyester.By adding water, can make to become pulp-like as the polyester of raw material, polyvalent alcohol, stirring efficiency improves, therefore preferably.
In the manufacture method of polyester polyol of the present invention, preferably obtain the mixture of compound shown in following general formula (1).
(in formula, R
1represent the group removing OH base from the polyvalent alcohol of (1+m) valency, R
2represent the alkylidene group of carbonatoms 1 ~ 10 or the arylidene of substituted or unsubstituted carbonatoms 6 ~ 20, R
3represent the arylidene of substituted or unsubstituted carbonatoms 6 ~ 20, the integer that the integer that l is 0 ~ 10, m are 1 ~ 10, n is the integer of 1 ~ 10.）
Although the R in above-mentioned general formula (1)
1represent the group removing OH base from the polyvalent alcohol of (1+m) valency, but as this polyvalent alcohol, the group illustrated in polyvalent alcohol of more than above-mentioned two sense polyvalent alcohols, trifunctional can be listed.In addition, R
2represented alkylidene group, arylidene, R
3represented arylidene can list the group identical with above-mentioned group.
Compound shown in above-mentioned general formula (1) is the starting material of the manufacture method of applicable polyester modification thing of the present invention.
［ manufacture method of polyester modification thing ］
The feature of the manufacture method of polyester modification thing of the present invention is, makes to have to react with the polyester polyol obtained by the manufacture method of above-mentioned polyester polyol with the compound of the group of hydroxyl reaction and ethylenically unsaturated group.By this modification, polyester photosensitivity can be given.The modified-reaction of polyester polyol is identical with existing known esterification, under the condition of presence or absence organic solvent, usually, adds acid catalyst, stopper, preferably carries out 2 little of 10 hours in the temperature range of 80 DEG C ~ 130 DEG C.Normal pressure or add pressure synthesis can, when pressurize, can temperature of reaction be reduced.And, even if there is the unreacted hydroxyl from depolymerizing substance in the polyester modification thing obtained, characteristically also no problem.
［ have can with the compound of the group of hydroxyl reaction and ethylenically unsaturated group ］
The compound that the modification of the polyester polyol obtained in above-mentioned manufacture method uses be have in a part can with the compound of the group of hydroxyl reaction and ethylenically unsaturated group.Preferred can have 1 in the molecule with the group of hydroxyl reaction, and ethylenically unsaturated group has more than 1 in the molecule.As above-mentioned can with the group of hydroxyl reaction, cyclic ether group, the hydroxyls etc. such as carboxyl, isocyanate group, epoxy group(ing) can be listed.
As long as have in a part can with the compound of the group of hydroxyl reaction and ethylenically unsaturated group; just can be used in the modification of the polyester polyol that above-mentioned manufacture method obtains; therefore; be not particularly limited; but consider that particularly preferably there is the compound of acryl or methacryloyl from viewpoints such as the reactivities with above-mentioned polyester polyol.
As the compound with 1 carboxyl and more than 1 ethylenically unsaturated group, can list: half ester (halfester) compound etc. in vinylformic acid, acrylic acid dimer, methacrylic acid, β-styrene acrylic, β-furfuryl acrylic acid, β-crotonic acid, alpha-cyano styracin, styracin, (methyl) caprolactone affixture and saturated or unsaturated dicarboxylic acid anhydride and a part with (methyl) esters of acrylic acid of 1 hydroxyl.As (methyl) esters of acrylic acid with hydroxyl for the manufacture of half ester compound, such as, can list: (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) hy-droxybutyl, TriMethylolPropane(TMP) two (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, (methyl) phenylethyl glycidyl ester etc.As the dibasic acid anhydride for the manufacture of half ester compound, such as, can list: succinyl oxide, maleic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride (methylendomethylenetetrahydrophthalicanhydride) etc.These compounds can be used alone one, also can be used in combination.
In addition, in this manual, (methyl) acrylate refers to the term summarizing acrylate, methacrylic ester and their mixture, and other similar statements too.
As the compound with 1 isocyanate group and more than 1 ethylenically unsaturated group in a part; such as, can list: (methyl) acryl oxygen base ethyl isocyanate, (methyl) acryl oxygen base oxethyl ethyl isocyanate, two (acryloyloxymethyl) ethyl isocyanate or their modifier etc.In addition, half urethane compound of the vulcabond such as the compound with 1 hydroxyl and more than 1 ethylenically unsaturated group and isophorone diisocyanate, tolylene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate can be also used in a part.These compounds can be used alone one, also can be used in combination.
As the above-mentioned commercially available product having the compound of 1 isocyanate group and more than 1 ethylenically unsaturated group in a part concurrently, commercially available " KarenzMOI " (methacryloyl oxygen base ethyl isocyanate) having Showa electrician (strain) to provide, " KarenzAOI " (acryl oxygen base oxethyl ethyl isocyanate), " KarenzMOI-EG " (methacryloyl oxygen base oxethyl ethyl isocyanate), " KarenzMOI-BM " (isocyanate-terminated body of KarenzMOI), " KarenzMOI-BP " (isocyanate-terminated body of KarenzMOI), " KarenzBEI " (1, two (acryloyloxymethyl) ethyl isocyanate of 1-).In addition, these trade(brand)names are registered trademark.
As the compound having 1 cyclic ether group and more than 1 ethylenically unsaturated group in a part concurrently, can list: (methyl) vinylformic acid 2-hydroxyl ethyl ester glycidyl ether, (methyl) vinylformic acid 2-hydroxypropyl acrylate glycidyl ether, (methyl) vinylformic acid 3-hydroxypropyl acrylate glycidyl ether, (methyl) vinylformic acid 2-hydroxy butyl ester glycidyl ether, (methyl) vinylformic acid 4-hydroxy butyl ester glycidyl ether, (methyl) vinylformic acid 2-hydroxyl peopentyl ester glycidyl ether, the own ester glycidyl ether of (methyl) vinylformic acid 6-hydroxyl or (methyl) glycidyl acrylate, 3, 4-epoxycyclohexyl-methyl acrylate etc.These compounds can be used alone one, also can be used in combination.
As the above-mentioned compound with hydroxyl and ethylenically unsaturated group, as long as have the compound of 1 hydroxyl and more than 1 ethylenically unsaturated group in a part, be not particularly limited.As object lesson, hydroxyalkyl (methyl) acrylate such as (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) hy-droxybutyl, TriMethylolPropane(TMP) two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate can be listed.These compounds can be used alone one, also can be used in combination.
The polyester modification thing of manufacture method manufacture of the present invention can react to carry out chemical modification with the compound of the group of hydroxyl reaction and more than 1 ethylenically unsaturated group and above-mentioned polyester polyol by making to have, thus impart photosensitive photosensitive compounds, therefore, the photosensitivity composition as Photocurable resin composition or light solidifying/heat solidifying resin composition is useful.Such as; by existing known conventional Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizing agents such as oxime ester class Photoepolymerizationinitiater initiater compounding in above-mentioned polyester modification thing, alpha-aminoacetophenone class Photoepolymerizationinitiater initiater, acylphosphine oxide class Photoepolymerizationinitiater initiater, bitter almond oil camphor compound, acetophenone compound, anthraquinone compounds, thioxanthone compounds, ketal compound, benzophenone cpd, xanthone compound, tertiary amine compounds, thus Photocurable resin composition can be obtained.
Embodiment
Below illustrate that embodiment and comparative example are to be specifically described the present invention, but the invention is not restricted to following embodiment.In addition, described below " part " and " % " is quality criteria unless otherwise noted.
［ embodiment 1 ］
To be provided with agitator, nitrogen ingress pipe, prolong 500ml four mouthfuls of removable flasks of round bottom in load PET sheet 192 parts (Mitsubishi Chemical Ind's system: Novapex(trade(brand)name)), TriMethylolPropane(TMP) 67 parts, zinc octoate 0.52 part, be after nitrogen atmosphere in flask, immerse the oil bath being warming up to 220 DEG C, sustained reaction, until transparent in flask, obtains polyester oligomer.
［ embodiment 2 ］
Use the zinc acetylacetonate of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
［ embodiment 3 ］
Use the calcium acetylacetonate of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
［ embodiment 4 ］
Use the methyl ethyl diketone lithium of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
［ embodiment 5 ］
Use the zinc naphthenate of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
［ embodiment 6 ］
Use the calcium naphthenate of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
［ embodiment 7 ］
Use the calcium octoate of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
［ embodiment 8 ］
Use the naphthenic acid lithium of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
［ embodiment 9 ］
Use the sad lithium of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
［ embodiment 10 ］
Use the manganese naphthenate of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
［ embodiment 11 ］
Use the manganese acetylacetonate of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
［ embodiment 12 ］
Use the manganese octoate of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
［ embodiment 13 ］
Use the Lithium Acetate of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
［ embodiment 14 ］
Be provided with agitator, nitrogen ingress pipe, prolong 500ml four mouthfuls of removable flasks of round bottom in load polyester oligomer 225 parts, 187 parts, vinylformic acid, tosic acid 1.87 parts, the p methoxy phenol 1.50 parts that embodiment 2 obtains, and stir, after making it dissolve equably, immerse and be warming up to the oil bath of 118 DEG C, and sustained reaction 16.5 hours.After reaction terminates, the acid number of assaying reaction liquid, to add the alkaline aqueous solution of acid equivalent in flask, neutralizes.Then, add salt solution (20wt%), stir.Then, solution is moved to separating funnel, and add the methyl iso-butyl ketone (MIBK) of reaction solution 1.4 times, give up aqueous phase.Again clean oil phase with salt solution (5wt%), give up aqueous phase.Then, in hexane after redeposition oil phase, make it be dissolved in methyl ethyl ketone, remove impurity by suction filtration.After tap water again precipitation filtrates, give up supernatant liquor, stir further with tap water, wash redeposition thing, be finally diluted to solids component 70% with carbitol acetate, obtain acrylate resin varnish.
［ comparative example 1 ］
Use the Dibutyltin oxide of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
［ comparative example 2 ］
Use the dibutyl tin laurate of identical amount to replace the zinc octoate of embodiment 1, obtain polyester oligomer.
< depolymerization time >
The time required for depolymerization of embodiment 1 ~ 13 and comparative example 1,2 as described in Table 1.Even if carry out reaction in more than 10 hours, the situation that raw material also remains is designated as "×".
< Wuxi (tinfree) >
The concentration (ppm) of the tin that the depolymerizing substance determining embodiment 1 ~ 13 and comparative example 1,2 comprises.The record method evaluated is as follows.
Zero: the concentration of tin is less than 10ppm
△: the concentration of tin is 10ppm ~ 500ppm
×: the concentration of tin is more than 500ppm
< molecular weight >
Use GPC(gel permeation chromatography) measure the molecular weight of the depolymerizing substance of embodiment 1 ~ 13 and comparative example 1.Condition determination is: ShodexGPCKF-806L × 3 that use Showa electrician (strain) is made as post, and use at column temperature 40 DEG C.Use polystyrene standard as primary standard, elutriant is that the flow velocity divided with 1ml/ uses tetrahydrofuran (THF).Measurement result is shown in following table 1.
< solvent solubility test >
Confirm the solvent solubility of the depolymerizing substance of embodiment 1 ~ 13 and comparative example 1,2.
Confirmation method is, relative to depolymerizing substance 50 parts, adds all kinds of SOLVENTS 50 parts, stirs, makes the 50wt% solution of depolymerizing substance, evaluate the transparency of its solution.The record method evaluated is as follows.
Completely transparent: zero
Slightly muddy: △
Muddy: ×
[table 1]
By confirming above, for solvent solubility, have compared with muddiness with comparative example 2 to each solvent, the comparative example 1 of embodiment all with stanniferous is identical, completely transparent to each solvent.
［ reference example 1 ］
Make 100 parts, acrylate resin varnish obtaining in above-described embodiment 14 and 5 parts of Photoepolymerizationinitiater initiater (Irgacure184; BASF Japanese firm system) mixing after, use applicator be coated with in the mode of thickness 20 μm on a glass.After coating, in the hot-blast circulation dry furnace of 80 DEG C, drying 20 minutes, uses the exposure apparatus being equipped with high voltage mercury lamp, with 1J/cm
2exposure expose, obtain evaluate film.
< rub(bing)test >
Use containing acetone rag to above-mentioned evaluation film rub 50 times time, surface without dissolve, can confirm fully to solidify.
< pencil hardness test >
With the front end of pencil-lead by the pencil from B to 9H polished, being that the angle of 45 degree applies 1kg load to film and presses relative to above-mentioned evaluation film.Under the state being applied with this load, delineate about about 1cm to film, measure the tack-free pencil hardness of film, result is 6H.
< thermal test >
Above-mentioned evaluation film is dropped in the hot-blast circulation dry furnace of 200 DEG C, heats 3 minutes.Take out after heating, by the sign of visual observation melting, to carry out thermal test, now confirm the thermotolerance at 200 DEG C with 3 minutes.
As mentioned above, according to method of the present invention, by using non-tin metalloid catalyzer, polyester can be dissolved in easily organic solvent, convert the polyester polyol of the various chemical modification of energy to.
［ embodiment 15 ］
Be provided with agitator, nitrogen ingress pipe, prolong 500ml four mouthfuls of removable flasks of round bottom in load recirculation PET sheet 192 parts that IV value is (inherent viscosity) 0.6 ~ 0.7, TriMethylolPropane(TMP) 67 parts, DBU0.52 part, be after nitrogen atmosphere in flask, immersing has been warming up in the oil bath of 220 DEG C, sustained reaction, until transparent in flask, obtain polyester oligomer.
［ embodiment 16 ］
Be provided with agitator, nitrogen ingress pipe, prolong 500ml four mouthfuls of removable flasks of round bottom in load PET sheet (Inc. of Mitsubishi: Novapex(trade(brand)name)) 192 parts, TriMethylolPropane(TMP) 67 parts, DBU0.52 part, be after nitrogen atmosphere in flask, immersing has been warming up in the oil bath of 220 DEG C, sustained reaction, until transparent in flask, obtain polyester oligomer.
［ embodiment 17 ］
Load in the four mouthfuls of removable flasks of round bottom being provided with agitator, nitrogen ingress pipe, prolong 500ml IV value be 0.6 ~ 0.7 recirculation PET sheet 192 parts, TriMethylolPropane(TMP) 67 parts, DBU0.52 part, 30 parts, water, be after nitrogen atmosphere in flask, immersing has been warming up in the oil bath of 180 DEG C, slow in anhydrating on one side, while oil bath is warming up to 220 DEG C, sustained reaction, until transparent in flask, obtains polyester oligomer.
［ embodiment 18 ］
Be provided with agitator, nitrogen ingress pipe, prolong 500ml four mouthfuls of removable flasks of round bottom in load IV value be 0.6 ~ 0.7 recirculation PET sheet 192 parts, TriMethylolPropane(TMP) 67 parts, tetramethylolmethane 68 parts, DBU0.52 part, 30 parts, water, be after nitrogen atmosphere in flask, immersing has been warming up in the oil bath of 180 DEG C, slow in anhydrating on one side, while oil bath is warming up to 220 DEG C, sustained reaction, until transparent in flask, obtains polyester oligomer.
［ embodiment 19 ］
Use the DBN of identical amount to replace the DBU of embodiment 17, obtain polyester oligomer.
［ embodiment 20 ］
Be equipped with agitator, nitrogen ingress pipe, prolong 500ml four mouthfuls of removable flasks of round bottom in load the polyester oligomer 225 parts, 187 parts, vinylformic acid, tosic acid 1.87 parts, the p methoxy phenol 1.50 parts that obtain in embodiment 15, stir, after making its uniform dissolution, immersing has been warming up in the oil bath of 118 DEG C, sustained reaction 16.5 hours.After reaction terminates, the acid number of assaying reaction liquid, to add the alkaline aqueous solution of acid equivalent in flask, neutralizes.Then, add salt solution (20wt%), stir.Then, solution is moved to separating funnel, add the methyl iso-butyl ketone (MIBK) of 1.4 times of reaction solution, give up aqueous phase.Again wash oil phase with salt solution (5wt%), give up aqueous phase.Then, after oil phase in hexane redeposition, make it be dissolved in methyl ethyl ketone, remove impurity by suction filtration.After making filtrate redeposition with tap water, give up supernatant liquor, again stir with tap water, wash redeposition thing, being finally diluted to solids component with carbitol acetate is 70%, obtains acrylate resin varnish.
［ comparative example 3 ］
Use the Dibutyltin oxide of identical amount to replace the DBU of embodiment 17, obtain polyester oligomer.
［ comparative example 4 ］
Use the dibutyl tin laurate of identical amount to replace the DBU of embodiment 17, obtain polyester oligomer.
［ comparative example 5 ］
Be provided with agitator, nitrogen ingress pipe, prolong 500ml four mouthfuls of removable flasks of round bottom in load recirculation PET sheet 192 parts, TriMethylolPropane(TMP) 67 parts, 30 parts, the water of IV value 0.6 ~ 0.7, be after nitrogen atmosphere in flask, immersing has been warming up in the oil bath of 180 DEG C, slow in anhydrating on one side, while oil bath is warming up to 220 DEG C, react.
< depolymerization time >
Time required for the depolymerization of embodiment 15 ~ 19 and comparative example 3 ~ 5 is shown in following table 2.Even if carry out reaction in more than 10 hours, the situation that raw material also remains is designated as "×".
< is without metal >
Determine the concentration (ppm) of the metal contained by depolymerizing substance of embodiment 15 ~ 19 and comparative example 3 ~ 5.The record method evaluated is as follows.
Zero: the concentration of metal is less than 10ppm
△: the concentration of metal is 10ppm ~ 500ppm
×: the concentration of metal is more than 500ppm
< molecular weight >
Use GPC(gel permeation chromatography) measure the molecular weight of the depolymerizing substance of embodiment 15 ~ 19 and comparative example 3 ~ 5.Condition determination is: ShodexGPCKF-806L × 3 that use Showa electrician (strain) is made as post, and use at column temperature 40 DEG C.Use polystyrene standard as primary standard, elutriant is that the flow velocity divided with 1ml/ uses tetrahydrofuran (THF).Measurement result is shown in following table 2.
< solvent solubility test >
Confirm the solvent solubility of the depolymerizing substance of embodiment 15 ~ 19 and comparative example 3 ~ 5.Confirmation method is, relative to depolymerizing substance 50 parts, adds all kinds of SOLVENTS 50 parts, stirs, makes the 50wt% solution of depolymerizing substance, evaluate the transparency of its solution.The record method evaluated is as follows.
Completely transparent: zero
Slightly muddy: △
Muddy: ×
[table 2]
By confirming above, for solvent solubility, have compared with muddiness with comparative example 4,5 to each solvent, embodiment is all identical with metallic comparative example 3, completely transparent to each solvent.
［ reference example 2 ］
Make 100 parts, acrylate resin varnish obtaining in above-described embodiment 20 and 5 parts of Photoepolymerizationinitiater initiater (Irgacure184; BASF Japanese firm system) mixing after, use applicator be coated with in the mode of thickness 20 μm on a glass.After coating, in the hot-blast circulation dry furnace of 80 DEG C, drying 20 minutes, uses the exposure apparatus being equipped with high voltage mercury lamp, with 1J/cm
2exposure expose, obtain evaluate film.
< rub(bing)test >
Use containing acetone rag to above-mentioned evaluation film rub 50 times time, surface without dissolve, can confirm fully to solidify.
< pencil hardness test >
With the front end of pencil-lead by the pencil from B to 9H polished, being that the angle of 45 degree applies 1kg load to film and presses relative to above-mentioned evaluation film.Under the state being applied with this load, delineate about about 1cm to film, measure the tack-free pencil hardness of film, result is 6H.
< thermal test >
Above-mentioned evaluation film is dropped in the hot-blast circulation dry furnace of 200 DEG C, heats 3 minutes.Take out after heating, by the sign of visual observation melting, to carry out thermal test, now confirm the thermotolerance at 200 DEG C with 3 minutes.
As mentioned above, according to method of the present invention, by using nonmetal basic catalyst, polyester can be dissolved in easily organic solvent, convert the polyester polyol of the various chemical modification of energy to.
Claims (11)
1. a manufacture method for polyester polyol, is characterized in that, possesses heating with the operation of depolymerization Starting Material Polyester containing Starting Material Polyester, polyhydroxy reactant and non-tin metalloid catalyzer or non-metal kind basic catalyst as the mixture of neccessary composition,
Described non-tin metalloid catalyzer is selected from the compound in the group that is made up of naphthenic acid metal complex, acetylacetone metal complex.
2. the manufacture method of polyester polyol according to claim 1, wherein, described naphthenic acid metal complex is selected from the compound in the group that is made up of zn cpds, manganic compound, lithium compound and calcium cpd.
3. the manufacture method of polyester polyol according to claim 1, wherein, described acetylacetone metal complex is selected from the compound in the group that is made up of zn cpds, manganic compound, lithium compound and calcium cpd.
4. the manufacture method of polyester polyol according to claim 1, wherein, described non-tin metalloid catalyzer is selected from the compound in the group that is made up of zinc naphthenate, zinc acetylacetonate, calcium naphthenate, calcium acetylacetonate, naphthenic acid lithium, methyl ethyl diketone lithium, manganese naphthenate, manganese acetylacetonate.
5. the manufacture method of polyester polyol according to claim 1, wherein, described non-metal kind basic catalyst is the hetero ring type compound with amidine structure.
6. the manufacture method of polyester polyol according to claim 5, wherein, described non-metal kind basic catalyst be selected from the group that is made up of diazabicycloundecene, diazabicyclo-nonene and their derivative more than one.
7. the manufacture method of polyester polyol according to claim 1, wherein, described polyhydroxy reactant comprises the polyvalent alcohol of more than trifunctional.
8. the manufacture method of polyester polyol according to claim 1, wherein, described Starting Material Polyester is recycled polyester.
9. the manufacture method of polyester polyol according to claim 1, wherein, adds water as in the mixture of neccessary composition, to carry out the depolymerization of Starting Material Polyester to containing Starting Material Polyester, polyhydroxy reactant and non-tin metalloid catalyzer.
10. the manufacture method of polyester polyol according to claim 1, wherein, described depolymerization is carried out at 150 ~ 350 DEG C.
The manufacture method of 11. polyester polyols according to claim 1, wherein, obtains the mixture of compound shown in following general formula (1),
In formula (1), R
1represent the group removing OH base from the polyvalent alcohol of (1+m) valency, R
2represent the alkylidene group of carbonatoms 1 ~ 10 or the arylidene of substituted or unsubstituted carbonatoms 6 ~ 20, R
3represent the arylidene of substituted or unsubstituted carbonatoms 6 ~ 20, the integer that the integer that l is 0 ~ 10, m are 1 ~ 10, n is the integer of 1 ~ 10.
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| JP2011081292 | 2011-03-31 | ||
| PCT/JP2012/056019 WO2012132824A1 (en) | 2011-03-31 | 2012-03-08 | Method for producing polyester polyol, method for producing modified polyester, polyester polyol and modified polyester |
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| CN103265708B (en) * | 2013-04-24 | 2015-07-29 | 高松文 | A kind of modified poly ester polyvalent alcohol and its preparation method and application |
| CN115594811A (en) * | 2022-09-07 | 2023-01-13 | 广东大盈新材料科技有限公司（Cn） | Polyurethane fabric resin for weather-resistant synthetic leather and preparation method thereof |
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| US4539341A (en) * | 1984-02-22 | 1985-09-03 | Jim Walter Resources, Inc. | Digestion products of polyalkylene terephthalate polymers and polycarboxylic acid-containing polyols and polymeric foams obtained therefrom |
| CN87101849A (en) * | 1987-03-10 | 1988-09-21 | 陕西省化学研究所 | The method and the catalyzer that are used for depolymerizing waste and old polyester plastics |
| JP2919539B2 (en) * | 1990-03-16 | 1999-07-12 | ユニチカ株式会社 | Polyester production method |
| JPH10251491A (en) * | 1997-03-12 | 1998-09-22 | Daiabondo Kogyo Kk | Thermosetting polyester resin composition |
| JP2000191766A (en) * | 1998-12-25 | 2000-07-11 | Nippon Polyurethane Ind Co Ltd | Production of terephthalic acid-based polyester polyol |
| JP2000229916A (en) * | 1999-02-05 | 2000-08-22 | Mitsui Chemicals Inc | Ester group-containing dicarboxylic acid compound and its production |
| JP2002128880A (en) * | 2000-10-30 | 2002-05-09 | Kansai Paint Co Ltd | Method for producing alkyd resin |
| KR100765744B1 (en) * | 2001-12-15 | 2007-10-15 | 김도균 | Method for producing polymer for toner, ink and coating agent by recycling waste polyester |
| TW200906873A (en) * | 2007-05-30 | 2009-02-16 | Toagosei Co Ltd | Active energy ray curable composition, coating composition, coating member, and optical material |
| JP5748941B2 (en) * | 2009-04-14 | 2015-07-15 | 太陽ホールディングス株式会社 | Photosensitive compound and photocurable resin composition containing the same |
| JP5620656B2 (en) * | 2009-08-19 | 2014-11-05 | 太陽ホールディングス株式会社 | Photocurable resin composition |
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| TW201422668A (en) | 2014-06-16 |
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