JP2010533760A - Pvc用共安定化剤としてのカルボキシ変性ポリビニルアルコール - Google Patents
Pvc用共安定化剤としてのカルボキシ変性ポリビニルアルコール Download PDFInfo
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- JP2010533760A JP2010533760A JP2010516516A JP2010516516A JP2010533760A JP 2010533760 A JP2010533760 A JP 2010533760A JP 2010516516 A JP2010516516 A JP 2010516516A JP 2010516516 A JP2010516516 A JP 2010516516A JP 2010533760 A JP2010533760 A JP 2010533760A
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- Prior art keywords
- polyvinyl alcohol
- modified polyvinyl
- thermoplastically processable
- acid
- mixture according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 48
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 48
- 239000003381 stabilizer Substances 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 36
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 35
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 238000007127 saponification reaction Methods 0.000 claims abstract description 7
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- -1 alkaline earth metal salt Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000009757 thermoplastic moulding Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- 229940018557 citraconic acid Drugs 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 239000010433 feldspar Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims 1
- 150000003751 zinc Chemical class 0.000 claims 1
- 229920001169 thermoplastic Polymers 0.000 abstract description 4
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 0 **CCC(N)O Chemical compound **CCC(N)O 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241001562081 Ikeda Species 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- DLAHAXOYRFRPFQ-UHFFFAOYSA-N dodecyl benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1 DLAHAXOYRFRPFQ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000006077 pvc stabilizer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
Landscapes
- 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)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
−アルカリ又はアルカリ土類金属塩
−分子内又は分子間無水物
−炭素数1−20のアルコールとのモノ又はジエステル
R2、R3、R4、R5=独立して、H、−CH3、−C2H5、−CO2R6、−CH2CO2R6、
R6=H、−CH3、−C2H5、アルカリ金属又はアルカリ土類金属
但し、少なくとも一つの残基R2、R3、R4、R5はカルボキシル基を含む。
−1%のPVAを水に溶解させた。
−PVCを上記溶液に添加した後、8時間50℃で乾燥させた。
−上記PVC/PVA混合物へ、DOP(フタル酸ジオクチル)、ステアリン酸亜鉛及びステアリン酸カルシウムを添加し、ドライブレンドした。
−得られた混合物60gを、5分間160℃でオープンロールを用いて粉砕した。
酢酸ビニル(1200部)、メタノール(1800部)、イタコン酸(IA)の20重量%メタノール溶液(3部)及びアゾビスイソブチロニトリル(1.5部)を、還流冷却器及び撹拌機を備えた重合容器に供給した。IAの20重量%メタノール溶液を15mL/hrの速度で連続的に添加した。窒素気流下、60℃で撹拌を行いながら4.5時間(重合率65%)重合を行った。未反応の酢酸ビニルを取り除き、ポリマーのメタノール溶液(樹脂量40%)を得た。この溶液を反応器に供給した。水酸化ナトリウム(ポリマー中の酢酸ビニル単位あたり5mmol)をそれに添加し、40℃で加水分解を行った。生成したポリビニルアルコールゲルを粉砕し、メタノールで十分に洗浄して熱風乾燥機で乾燥させ、IA変性ポリビニルアルコール樹脂を得た。
酢酸ビニル(1200部)、メタノール(1800部)及びアゾビスイソブチロニトリル(1.5部)を、還流冷却器及び撹拌機を備えた重合容器に供給した。窒素気流下、60℃で撹拌を行いながら4.5時間(重合率65%)重合を行った。未反応の酢酸ビニルを取り除き、ポリマーのメタノール溶液(樹脂量40%)を得た。この溶液を反応器に供給した。水酸化ナトリウム(ポリマー中の酢酸ビニル単位あたり5mmol)をそれに添加し、40℃で加水分解を行った。生成したポリビニルアルコールゲルを粉砕し、メタノールで十分に洗浄して熱風乾燥機で乾燥させ、ポリビニルアルコール樹脂を得た。
Claims (11)
- 少なくとも一種のビニルエステル及び少なくとも一種のオレフィン性不飽和カルボン酸又はその金属塩、無水物又はエステルを共重合させ、次いでその共重合体を部分的にケン化して得られる少なくとも一種の変性ポリビニルアルコールをポリ塩化ビニル100部に対して0.1−15部添加することを特徴とする、安定化剤として少なくとも一種の金属イオンを含有するポリ塩化ビニルベースの熱可塑的に加工可能な混合物。
- 前記変性ポリビニルアルコールが、少なくとも一種のオレフィン性不飽和カルボン酸又はその金属塩、無水物又はエステルを0.01−5モル%含有することを特徴とする、請求項1記載の熱可塑的に加工可能な混合物。
- 前記変性ポリビニルアルコールが、少なくとも一種の炭素数3−20のオレフィン性不飽和カルボン酸、そのアルカリ又はアルカリ土類金属塩、その無水物又はそれと炭素数1−20のアルコールとのエステルを0.01−5モル%含有することを特徴とする、請求項1又は2記載の熱可塑的に加工可能な混合物。
- 前記変性ポリビニルアルコールが、イタコン酸、フマル酸、マレイン酸、クロトン酸、シトラコン酸、アクリル酸、メタクリル酸、及びそれらのエステル及び金属塩から選択される少なくとも一種のモノマーと酢酸ビニルとを共重合させ、次いでケン化することによって得られたものであることを特徴とする、請求項1又は3記載の熱可塑的に加工可能な混合物。
- 前記変性ポリビニルアルコールのケン化度が少なくとも60モル%であることを特徴とする、請求項1から4のいずれかに記載の熱可塑的に加工可能な混合物。
- 前記変性ポリビニルアルコールの重合度が200−1500であることを特徴とする、請求項1から5のいずれかに記載の熱可塑的に加工可能な混合物。
- バリウム、亜鉛、カルシウム又は錫から選択される少なくとも一種の金属イオンを安定化剤として使用することを特徴とする、請求項1から6のいずれかに記載の熱可塑的に加工可能な混合物。
- 炭素数1−25のカルボン酸、アセチルアセトン又はβ―ジケトンの亜鉛塩、及び炭素数1−25のカルボン酸、アセチルアセトン又はβ―ジケトンのカルシウム塩の混合物を安定化剤として使用することを特徴とする、請求項1から7のいずれかに記載の熱可塑的に加工可能な混合物。
- TiO2、CaCO3、ZrO2,カオリン、タルク、K/Alケイ酸塩、長石、ケイ酸塩、硫酸バリウム、金属粉、黒鉛、硫酸カルシウム、セラミック及びガラス粒子、又は木材から選択される充填材をポリ塩化ビニル100部に対して5−20部含有することを特徴とする、請求項1から8のいずれかに記載の熱可塑的に加工可能な混合物。
- 少なくとも120℃で前記成分を混合する請求項1から9のいずれかに記載の熱可塑的に加工可能な混合物の製造方法。
- 180−240℃での熱可塑性的な成形加工中に混合することを特徴とする請求項10記載の方法。
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DE102007033971A DE102007033971A1 (de) | 2007-07-19 | 2007-07-19 | Verwendung von Carboxylgruppen-haltigen Polyvinylalkoholen als Stabilisatorzusatz von PVC |
DE102007033971.4 | 2007-07-19 | ||
PCT/EP2008/059432 WO2009010578A1 (en) | 2007-07-19 | 2008-07-18 | Carboxy-modified polyvinyl alcohol as co-stabilizer for pvc |
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US (1) | US20100234508A1 (ja) |
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JP5755152B2 (ja) * | 2010-02-01 | 2015-07-29 | 株式会社クラレ | ポリ塩化ビニル用熱安定剤およびその製造方法 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2135896A1 (en) * | 2008-06-16 | 2009-12-23 | Kuraray Europe GmbH | Polyvinyl alcohol as co-stabilizer for PVC |
ES2401246T3 (es) * | 2008-06-23 | 2013-04-18 | Kuraray Co., Ltd. | Composición de resina de policloruro de vinilo y método para su producción |
US8288465B2 (en) | 2008-10-08 | 2012-10-16 | Kuraray Co., Ltd. | Polyvinyl chloride resin compositions and manufacturing method therefor |
US8273175B2 (en) | 2011-01-26 | 2012-09-25 | Empire Technology Development, Llc | Compositions and methods for protection of reinforced concrete |
CN102731710B (zh) * | 2011-04-07 | 2015-03-04 | 中国石油化工集团公司 | 一种羧基改性聚乙烯醇及其制备方法 |
FR2974101B1 (fr) | 2011-04-18 | 2015-01-16 | Arkema France | Composition de polymere contenant un halogene avec stabilisant a base d'etain et co-stabilisant |
KR101676087B1 (ko) * | 2013-09-30 | 2016-11-14 | 주식회사 엘지화학 | 환류 냉각기 제열 보조제를 포함하는 염화비닐 수지의 제조방법 |
US10487157B2 (en) | 2016-03-08 | 2019-11-26 | Oxy Vinyls, Lp | Methods for chlorinating polyvinyl chloride |
WO2017155989A1 (en) | 2016-03-08 | 2017-09-14 | Oxy Vinyls, Lp | Methods for providing polyvinyl chloride particles for preparing chlorinated polyvinyl chloride |
CN105936679B (zh) * | 2016-06-16 | 2019-03-01 | 浙江海普顿新材料股份有限公司 | 一种马来酸单聚乙烯醇酯钡盐及其在pvc热稳定剂中的应用 |
WO2018124241A1 (ja) * | 2016-12-28 | 2018-07-05 | 株式会社クラレ | ポリビニルアルコール組成物及びその用途 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS533442A (en) * | 1976-06-28 | 1978-01-13 | Rhone Poulenc Ind | Composition based on thermally stabilized polyvinyl chloride polymer |
JPS5433580A (en) * | 1977-08-19 | 1979-03-12 | Denki Kagaku Kogyo Kk | Polymerization of vynyl chloride |
JPS57119902A (en) * | 1981-01-16 | 1982-07-26 | Kuraray Co Ltd | Dispersion stabilizer for suspension polymerization of vinyl compound |
JPS60238345A (ja) * | 1984-05-10 | 1985-11-27 | Kuraray Co Ltd | 樹脂組成物 |
JPH01178543A (ja) * | 1987-12-29 | 1989-07-14 | Nippon Synthetic Chem Ind Co Ltd:The | 含ハロゲン熱可塑性樹脂組成物 |
JPH0229448A (ja) * | 1988-07-19 | 1990-01-31 | Nippon Synthetic Chem Ind Co Ltd:The | 含ハロゲン熱可塑性樹脂組成物 |
JPH0229447A (ja) * | 1988-07-19 | 1990-01-31 | Nippon Synthetic Chem Ind Co Ltd:The | 含ハロゲン熱可塑性樹脂組成物 |
JPH02167315A (ja) * | 1988-09-08 | 1990-06-27 | Shin Etsu Chem Co Ltd | 白化の少ない塩化ビニル系樹脂成形品 |
US5143959A (en) * | 1990-04-20 | 1992-09-01 | Rhone-Poulenc Chimie | Compositions for use with chlorinated polymers |
JP2002097210A (ja) * | 2000-07-19 | 2002-04-02 | Kuraray Co Ltd | ビニル系化合物の懸濁重合用分散安定剤 |
JP2002097208A (ja) * | 2000-07-19 | 2002-04-02 | Kuraray Co Ltd | ビニル系化合物の懸濁重合用分散安定剤 |
JP2002097209A (ja) * | 2000-07-19 | 2002-04-02 | Kuraray Co Ltd | ビニル系化合物の懸濁重合用分散安定剤 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PT91654B (pt) | 1988-09-08 | 1995-05-31 | Shinetsu Chemical Co | Processo de preparacao de resina a base de cloreto de vinilo |
US5478900A (en) * | 1993-05-07 | 1995-12-26 | Shin-Etsu Chemical Co., Ltd. | Process for preparing vinyl chloride polymer of quality |
DE60134089D1 (de) * | 2000-07-19 | 2008-07-03 | Kuraray Co | Dispersionsstabilisator für die Suspensionspolymerisation von Vinyl-Verbindungen |
DE10050023A1 (de) * | 2000-10-06 | 2002-04-11 | Basf Ag | Mischvorrichtung und Verfahren zur Herstellung von thermoplastisch verarbeitbaren Formmassen, insbesondere Additivbatches |
CA2452218C (en) * | 2002-12-12 | 2011-08-30 | Kuraray Co., Ltd. | Thermoplastic polymer composition, molded product, and multilayer structure |
-
2007
- 2007-07-19 DE DE102007033971A patent/DE102007033971A1/de not_active Withdrawn
-
2008
- 2008-07-18 CN CN2008800243400A patent/CN101743279B/zh not_active Expired - Fee Related
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- 2008-07-18 WO PCT/EP2008/059432 patent/WO2009010578A1/en active Application Filing
- 2008-07-18 PL PL08786232T patent/PL2176343T3/pl unknown
- 2008-07-18 JP JP2010516516A patent/JP5512518B2/ja not_active Expired - Fee Related
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Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS533442A (en) * | 1976-06-28 | 1978-01-13 | Rhone Poulenc Ind | Composition based on thermally stabilized polyvinyl chloride polymer |
JPS5433580A (en) * | 1977-08-19 | 1979-03-12 | Denki Kagaku Kogyo Kk | Polymerization of vynyl chloride |
JPS57119902A (en) * | 1981-01-16 | 1982-07-26 | Kuraray Co Ltd | Dispersion stabilizer for suspension polymerization of vinyl compound |
JPS60238345A (ja) * | 1984-05-10 | 1985-11-27 | Kuraray Co Ltd | 樹脂組成物 |
JPH01178543A (ja) * | 1987-12-29 | 1989-07-14 | Nippon Synthetic Chem Ind Co Ltd:The | 含ハロゲン熱可塑性樹脂組成物 |
JPH0229448A (ja) * | 1988-07-19 | 1990-01-31 | Nippon Synthetic Chem Ind Co Ltd:The | 含ハロゲン熱可塑性樹脂組成物 |
JPH0229447A (ja) * | 1988-07-19 | 1990-01-31 | Nippon Synthetic Chem Ind Co Ltd:The | 含ハロゲン熱可塑性樹脂組成物 |
JPH02167315A (ja) * | 1988-09-08 | 1990-06-27 | Shin Etsu Chem Co Ltd | 白化の少ない塩化ビニル系樹脂成形品 |
US5143959A (en) * | 1990-04-20 | 1992-09-01 | Rhone-Poulenc Chimie | Compositions for use with chlorinated polymers |
JP2002097210A (ja) * | 2000-07-19 | 2002-04-02 | Kuraray Co Ltd | ビニル系化合物の懸濁重合用分散安定剤 |
JP2002097208A (ja) * | 2000-07-19 | 2002-04-02 | Kuraray Co Ltd | ビニル系化合物の懸濁重合用分散安定剤 |
JP2002097209A (ja) * | 2000-07-19 | 2002-04-02 | Kuraray Co Ltd | ビニル系化合物の懸濁重合用分散安定剤 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5755152B2 (ja) * | 2010-02-01 | 2015-07-29 | 株式会社クラレ | ポリ塩化ビニル用熱安定剤およびその製造方法 |
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PT2176343E (pt) | 2011-05-24 |
EP2176343A1 (en) | 2010-04-21 |
DK2176343T3 (da) | 2011-08-01 |
DE602008005030D1 (de) | 2011-03-31 |
JP5512518B2 (ja) | 2014-06-04 |
CN101743279B (zh) | 2012-07-11 |
WO2009010578A1 (en) | 2009-01-22 |
PL2176343T3 (pl) | 2011-07-29 |
CN101743279A (zh) | 2010-06-16 |
ATE498653T1 (de) | 2011-03-15 |
KR101194614B1 (ko) | 2012-10-29 |
KR20100045998A (ko) | 2010-05-04 |
EP2176343B1 (en) | 2011-02-16 |
US20100234508A1 (en) | 2010-09-16 |
ES2361462T3 (es) | 2011-06-17 |
DE102007033971A1 (de) | 2009-01-22 |
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