JP5940858B2 - Polyvinyl alcohol polymer, dispersant for suspension polymerization, vinyl chloride resin and method for producing the same - Google Patents
Polyvinyl alcohol polymer, dispersant for suspension polymerization, vinyl chloride resin and method for producing the same Download PDFInfo
- Publication number
- JP5940858B2 JP5940858B2 JP2012077179A JP2012077179A JP5940858B2 JP 5940858 B2 JP5940858 B2 JP 5940858B2 JP 2012077179 A JP2012077179 A JP 2012077179A JP 2012077179 A JP2012077179 A JP 2012077179A JP 5940858 B2 JP5940858 B2 JP 5940858B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- polymerization
- dispersant
- polyvinyl alcohol
- alcohol polymer
- 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.)
- Expired - Fee Related
Links
- 239000002270 dispersing agent Substances 0.000 title claims description 56
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 54
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims description 53
- 229920005989 resin Polymers 0.000 title claims description 37
- 239000011347 resin Substances 0.000 title claims description 37
- 238000010557 suspension polymerization reaction Methods 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 43
- 239000000178 monomer Substances 0.000 claims description 30
- 238000007127 saponification reaction Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 11
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 11
- 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 10
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- -1 alkyl vinyl ethers Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 238000011156 evaluation 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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 125000003010 ionic group Chemical group 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- DBUPOCYLUHVFHU-UHFFFAOYSA-N carboxyoxy 2,2-diethoxyethyl carbonate Chemical compound CCOC(OCC)COC(=O)OOC(O)=O DBUPOCYLUHVFHU-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- YSRHGDWWCIXLEA-UHFFFAOYSA-N 2-methylpentan-2-yl 3,3-dimethylbutanoate Chemical compound CCCC(C)(C)OC(=O)CC(C)(C)C YSRHGDWWCIXLEA-UHFFFAOYSA-N 0.000 description 1
- YMMLZUQDXYPNOG-UHFFFAOYSA-N 2-methylpentan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)CCCCCC(C)(C)C YMMLZUQDXYPNOG-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- MAQJIKPZBNFNKZ-UHFFFAOYSA-N C(C)(C)(C1=CC=CC=C1)OOCCCCCCC(C)(C)C Chemical compound C(C)(C)(C1=CC=CC=C1)OOCCCCCCC(C)(C)C MAQJIKPZBNFNKZ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明は、懸濁重合用分散剤として好適に使用出来るポリビニルアルコール系重合体、このポリビニルアルコール系重合体からなる分散剤、この分散剤を使用して製造された塩化ビニル系樹脂及びその製造方法に関する。 The present invention relates to a polyvinyl alcohol polymer that can be suitably used as a dispersant for suspension polymerization, a dispersant comprising the polyvinyl alcohol polymer, a vinyl chloride resin produced using the dispersant, and a method for producing the same. About.
塩化ビニル系樹脂は、一般に、塩化ビニルモノマーを、重合開始剤及び分散剤などと共に水性媒体中に分散させて、重合を行う懸濁重合法により製造されている。その際使用される分散剤としては、塩化ビニルモノマーの分散性を安定化して、製造される塩化ビニル系樹脂の粒径を調節するために添加されるいわゆる「一次分散剤」と、製造される塩化ビニル系樹脂粒子中の空孔率（ポロシティ）を上げるために添加されるいわゆる「二次分散剤」とがある。 The vinyl chloride resin is generally produced by a suspension polymerization method in which a vinyl chloride monomer is dispersed in an aqueous medium together with a polymerization initiator and a dispersant, and polymerization is performed. The dispersant used at that time is a so-called “primary dispersant” which is added to stabilize the dispersibility of the vinyl chloride monomer and adjust the particle size of the vinyl chloride resin produced. There is a so-called “secondary dispersant” added to increase the porosity in the vinyl chloride resin particles.
従来、「一次分散剤」としては、ポリビニルアルコール（ＰＶＡ）やヒドロキシプロピルメチルセルロースなどが使用されており（特許文献１〜３参照）、「二次分散剤」としては、前述した一次分散剤よりも鹸化度が低いＰＶＡが使用されている（特許文献４参照）。例えば、特許文献４に記載の塩化ビニル系重合体の製造方法では、一次分散剤には、鹸化度が７５〜８５ｍｏｌ％のＰＶＡを使用し、二次分散剤には鹸化度が２０〜５７ｍｏｌ％のＰＶＡを使用している。 Conventionally, as the “primary dispersant”, polyvinyl alcohol (PVA), hydroxypropylmethylcellulose and the like have been used (see Patent Documents 1 to 3), and as the “secondary dispersant”, more than the primary dispersant described above. PVA having a low saponification degree is used (see Patent Document 4). For example, in the method for producing a vinyl chloride polymer described in Patent Document 4, PVA having a saponification degree of 75 to 85 mol% is used as the primary dispersant, and the saponification degree is 20 to 57 mol% as the secondary dispersant. The PVA is used.
更に、特許文献５〜７には、分子内にカルボン酸基、スルホン酸基、アミノ基などのイオン性基を導入したケン化度の低いＰＶＡを二次分散剤として使用して、塩化ビニル樹脂を製造する方法が提案されている。 Further, in Patent Documents 5 to 7, PVA having a low saponification degree in which an ionic group such as a carboxylic acid group, a sulfonic acid group, or an amino group is introduced into the molecule is used as a secondary dispersant, There has been proposed a method of manufacturing.
これらの技術には、以下に示す問題点が残されている。即ち特許文献４に記載された様なイオン性基を導入していない二次分散剤を使用した場合には、二次分散剤を用いる本来の目的である空孔率は充分に改善されるが、二次分散剤そのものの水溶性／水分散性が不足しているために、溶液／分散液として使用するためにはアルコール等の有機溶剤を併用しなければならない欠点があった。 The following problems remain in these technologies. That is, when a secondary dispersant that does not introduce an ionic group as described in Patent Document 4 is used, the original porosity that uses the secondary dispersant is sufficiently improved. Further, since the water-dispersibility / water-dispersibility of the secondary dispersant itself is insufficient, there is a disadvantage that an organic solvent such as alcohol must be used in combination for use as a solution / dispersion.
特許文献５〜７に記載された様なイオン性基を導入した二次分散剤では、水溶性／水分散性は改善されているものの、二次分散剤としての本来の働きである空孔率の改善が不十分であったり、一次分散剤の効果に対し悪影響を与え、塩化ビニル系樹脂の粒径を粗くしたりする問題点があった。 In the secondary dispersant introduced with ionic groups as described in Patent Documents 5 to 7, the water solubility / water dispersibility is improved, but the porosity which is the original function as the secondary dispersant is There is a problem that the improvement of the above is insufficient, the effect of the primary dispersant is adversely affected, and the particle size of the vinyl chloride resin is increased.
近年、環境に対する配慮や作業性の向上の観点から、アルコール類などの有機溶剤を使用しなくとも、水単独で溶解／分散が可能であり、かつ「二次分散剤」の本来の使用目的である塩化ビニル系樹脂の空孔率を高める効果に優れた二次分散剤の開発が望まれていた。 In recent years, from the viewpoint of environmental considerations and workability improvement, it is possible to dissolve / disperse with water alone without using organic solvents such as alcohols, and for the intended use of the “secondary dispersant”. Development of a secondary dispersant excellent in the effect of increasing the porosity of a certain vinyl chloride resin has been desired.
本発明は、水に対する溶解性／分散性が良好でありながら、塩化ビニル系樹脂の空孔率を向上させることが可能なポリビニルアルコール系重合体、それを主成分とする懸濁重合用分散剤、塩化ビニル系樹脂及びその製造方法を提供することを主目的とする。 The present invention relates to a polyvinyl alcohol polymer capable of improving the porosity of a vinyl chloride resin while having good solubility / dispersibility in water, and a dispersant for suspension polymerization comprising the same as a main component The main object is to provide a vinyl chloride resin and a method for producing the same.
本発明に係る懸濁重合用分散剤として好適に使用し得るポリビニルアルコール系重合体は、酢酸ビニルと不飽和カルボン酸とからなる重合体をケン化してなるポリビニルアルコール系重合体であって、不飽和カルボン酸の共重合量が０．１５ｍｏｌ％以上０．４ｍｏｌ％以下であり、重合度が２００から３５０の範囲であり、かつケン化度が３０ｍｏｌ％以上５０ｍｏｌ％以下であることを特徴とするものである。ポリビニルアルコール系重合体における不飽和カルボン酸は、イタコン酸を用いることが好ましい。 The polyvinyl alcohol polymer that can be suitably used as the dispersant for suspension polymerization according to the present invention is a polyvinyl alcohol polymer obtained by saponifying a polymer comprising vinyl acetate and an unsaturated carboxylic acid, The copolymerization amount of the saturated carboxylic acid is 0.15 mol% or more and 0.4 mol% or less, the polymerization degree is in the range of 200 to 350, and the saponification degree is 30 mol% or more and 50 mol% or less. Is. It is preferable to use itaconic acid as the unsaturated carboxylic acid in the polyvinyl alcohol polymer.
本発明によるポリビニルアルコール系重合体は、不飽和カルボン酸を０．１５ｍｏｌ％以上０．４ｍｏｌ％以下共重合することによって水に対する十分な溶解性／分散性を有しており、懸濁重合用分散剤として使用する際に水溶液／水分散液として使用することが可能である。水溶液／水分散液での使用が可能となることから、取り扱いが容易であるのみならず、環境にも優しく安全上も好ましいものである。 The polyvinyl alcohol polymer according to the present invention has sufficient solubility / dispersibility in water by copolymerizing an unsaturated carboxylic acid in an amount of 0.15 mol% or more and 0.4 mol% or less. When used as an agent, it can be used as an aqueous solution / aqueous dispersion. Since it can be used in an aqueous solution / aqueous dispersion, it is not only easy to handle but also environmentally friendly and preferable in terms of safety.
本発明のポリビニルアルコール系重合体は、更に重合度が２００から３５０の範囲であり、かつケン化度が３０ｍｏｌ％以上５０ｍｏｌ％以下に制御することにより、懸濁重合により塩化ビニル系樹脂を製造した際に、一次分散剤の効果を損ねることなく十分な空孔率を与えることが可能となる。 The polyvinyl alcohol polymer of the present invention further produced a vinyl chloride resin by suspension polymerization by controlling the polymerization degree to be in the range of 200 to 350 and controlling the saponification degree to 30 mol% or more and 50 mol% or less. In this case, sufficient porosity can be provided without impairing the effect of the primary dispersant.
本発明によれば、十分な水溶性／水分散性を有することから水溶液／水分散液としての使用が可能であり、一次分散剤の性能を損ねることなしに懸濁重合を行うことが可能であり、かつ十分な空孔率を塩化ビニル系樹脂に与え得る懸濁重合用分散剤を実現することができる。 According to the present invention, since it has sufficient water solubility / water dispersibility, it can be used as an aqueous solution / water dispersion, and suspension polymerization can be performed without impairing the performance of the primary dispersant. There can be realized a dispersant for suspension polymerization that can provide a sufficient porosity to the vinyl chloride resin.
以下、本発明を実施するための形態について、詳細に説明する。なお、本発明は、以下に説明する実施形態に限定されるものではない。 Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that the present invention is not limited to the embodiments described below.
（第１の実施形態）
本発明の第１の実施形態に係るポリビニルアルコール系重合体、及び懸濁重合用分散剤について説明する。本実施形態は、ポリビニルアルコール系重合体であり、懸濁重合により塩化ビニル系樹脂を製造する際に、分散剤として使用されるものである。該重合体は、重合液中において、塩化ビニル系樹脂の空孔率を向上させる「二次分散剤」として作用する。
(First embodiment)
The polyvinyl alcohol polymer and the dispersant for suspension polymerization according to the first embodiment of the present invention will be described. The present embodiment is a polyvinyl alcohol polymer, and is used as a dispersant when producing a vinyl chloride resin by suspension polymerization. The polymer acts as a “secondary dispersant” for improving the porosity of the vinyl chloride resin in the polymerization solution.
［構成単位］
本実施形態のポリビニルアルコール系重合体は、具体的には、酢酸ビニルと不飽和カルボン酸とからなる重合体をケン化してなるポリビニルアルコール系重合体であって、不飽和カルボン酸の共重合量が０．１５ｍｏｌ％以上０．４ｍｏｌ％以下であり、重合度が２００から３５０の範囲であり、かつケン化度が３０ｍｏｌ％以上５０ｍｏｌ％以下である。懸濁重合用分散剤は、上記ポリビニルアルコール系重合体を懸濁重合用分散剤として使用するものである。
[Unit]
The polyvinyl alcohol polymer of the present embodiment is specifically a polyvinyl alcohol polymer formed by saponifying a polymer composed of vinyl acetate and an unsaturated carboxylic acid, and the copolymerization amount of the unsaturated carboxylic acid. Is 0.15 mol% or more and 0.4 mol% or less, the polymerization degree is in the range of 200 to 350, and the saponification degree is 30 mol% or more and 50 mol% or less. The dispersant for suspension polymerization uses the polyvinyl alcohol polymer as a dispersant for suspension polymerization.
本発明に用いる不飽和カルボン酸としては、例えばイタコン酸、マレイン酸、フマル酸、（メタ）アクリル酸、クロトン酸、イソクロトン酸等が挙げられるが、これらに限定されるものではない。酢酸ビニルとの共重合性比やハンドリングの容易さから、イタコン酸の使用が最も好ましい。 Examples of the unsaturated carboxylic acid used in the present invention include, but are not limited to, itaconic acid, maleic acid, fumaric acid, (meth) acrylic acid, crotonic acid, and isocrotonic acid. Itaconic acid is most preferred because of its copolymerizability ratio with vinyl acetate and ease of handling.
不飽和カルボン酸の共重合量は、０．１５ｍｏｌ％以上０．４ｍｏｌ％以下の範囲であり、この範囲を外れると本発明の効果は得られない。不飽和カルボン酸の共重合量が０．１５ｍｏｌ％未満の場合、得られるポリビニルアルコール系重合体の水溶性／水分散性が不十分であり、水溶液／水分散液としての取り扱いが出来ないか、水溶液／水分散液の安定性が悪く、実用上問題となる。 The copolymerization amount of the unsaturated carboxylic acid is in the range of 0.15 mol% or more and 0.4 mol% or less, and if it is out of this range, the effect of the present invention cannot be obtained. When the copolymerization amount of the unsaturated carboxylic acid is less than 0.15 mol%, the water-soluble / water-dispersibility of the resulting polyvinyl alcohol polymer is insufficient, and can be handled as an aqueous solution / water dispersion, The stability of the aqueous solution / aqueous dispersion is poor, which causes a practical problem.
不飽和カルボン酸の共重合量が０．４ｍｏｌ％を超えると、一次分散剤に対する悪影響が生じ始める。具体的には、塩化ビニル系樹脂の粒径が肥大化し始める。 When the copolymerization amount of the unsaturated carboxylic acid exceeds 0.4 mol%, an adverse effect on the primary dispersant begins to occur. Specifically, the particle size of the vinyl chloride resin begins to enlarge.
本実施形態のポリビニルアルコール系重合体の重合度は、２００以上３５０以下である。重合度が２００未満の場合には、得られるポリビニルアルコール系重合体の軟化温度が低くなり過ぎて固形状態で得られなり、製品のハンドリングが著しく悪化する。重合度が３５０を超えた場合は、一次分散剤の効果を阻害し始め、塩化ビニル系樹脂の粒径が粗くなってしまう。 The degree of polymerization of the polyvinyl alcohol polymer of this embodiment is 200 or more and 350 or less. When the degree of polymerization is less than 200, the softening temperature of the obtained polyvinyl alcohol polymer becomes too low to be obtained in a solid state, and the handling of the product is significantly deteriorated. When the degree of polymerization exceeds 350, the effect of the primary dispersant begins to be impaired, and the particle size of the vinyl chloride resin becomes coarse.
本実施形態のポリビニルアルコール系重合体のケン化度は、３０ｍｏｌ％以上５０ｍｏｌ％以下である。ケン化度が３０ｍｏｌ％未満の場合、水溶性／水分散性が不十分であり、水溶液／水分散液としての取り扱いが困難となる。ケン化度が５０ｍｏｌ％を超えると、一次分散剤の働きを阻害する効果を示し始め、塩化ビニル系樹脂の粒径が肥大化する結果を生じる。 The saponification degree of the polyvinyl alcohol polymer of the present embodiment is 30 mol% or more and 50 mol% or less. When the saponification degree is less than 30 mol%, the water solubility / water dispersibility is insufficient, and handling as an aqueous solution / water dispersion becomes difficult. When the degree of saponification exceeds 50 mol%, the effect of inhibiting the function of the primary dispersant begins to be exhibited, resulting in an increase in the particle size of the vinyl chloride resin.
前述の如く、本実施形態のポリビニルアルコール系重合体の懸濁重合用分散剤としての優れた効果を発現せしめるには、不飽和カルボン酸の共重合量、重合度、ケン化度を狭い範囲の中で制御することが必須である。特に不飽和カルボン酸の共重合量を増加させたり、ケン化度を高めることは、水溶性／水分散性を向上させるには良い方向であるが、一次分散剤の主要な働きである塩化ビニル系樹脂の粒径を安定化させる効果を阻害してしまうため、避けなければならない。 As described above, in order to exhibit the excellent effect as the dispersant for suspension polymerization of the polyvinyl alcohol polymer of the present embodiment, the copolymerization amount, polymerization degree, and saponification degree of unsaturated carboxylic acid are set within a narrow range. It is essential to control inside. In particular, increasing the copolymerization amount of unsaturated carboxylic acid or increasing the saponification degree is a good direction for improving water solubility / water dispersibility, but vinyl chloride is the main function of the primary dispersant. Since the effect which stabilizes the particle size of a resin is inhibited, it must be avoided.
本実施形態のポリビニルアルコール系重合体は、酢酸ビニル単量体と不飽和カルボン酸とを共重合させた後、その共重合体をケン化することにより得られる。 The polyvinyl alcohol polymer of this embodiment is obtained by copolymerizing a vinyl acetate monomer and an unsaturated carboxylic acid and then saponifying the copolymer.
この際、本発明の効果を損なわない範囲でなら、他の単量体をさらに共重合させても良い。他の単量体としては、具体的には、蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、ピバリン酸ビニル及びバーサティック酸ビニル等のビニルエステル系単量体や、エチレン、プロピレン等のオレフィン類、マレイン酸ジアルキルエステル類、フマル酸ジアルキルエステル類、アルキルビニルエーテル類などが挙げられる。 At this time, other monomers may be further copolymerized as long as the effects of the present invention are not impaired. Specific examples of other monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, and versatic acid. Examples thereof include vinyl ester monomers such as vinyl, olefins such as ethylene and propylene, maleic acid dialkyl esters, fumaric acid dialkyl esters, and alkyl vinyl ethers.
また、これらの単量体の重合方法は、特に限定するものではなく、公知の重合方法を採用することができる。一般には、メタノール、エタノール及びイソプロピルアルコールなどのアルコールを溶媒とする溶液重合により製造されるが、バルク重合や乳化重合や懸濁重合などで製造してもよい。また、溶液重合を行う場合には、連続重合でもよいし、バッチ重合でもよい。更に、単量体は一括して仕込んでもよいし、分割して仕込んでもよく、あるいは連続的又は断続的に添加してもよい。 Moreover, the polymerization method of these monomers is not specifically limited, A well-known polymerization method is employable. Generally, it is produced by solution polymerization using alcohol such as methanol, ethanol and isopropyl alcohol as a solvent, but may be produced by bulk polymerization, emulsion polymerization, suspension polymerization or the like. Moreover, when performing solution polymerization, continuous polymerization may be sufficient and batch polymerization may be sufficient. Furthermore, the monomers may be charged all at once, may be charged separately, or may be added continuously or intermittently.
不飽和カルボン酸としてイタコン酸を用いる場合には、イタコン酸単位を重合体中に出来るだけ均一に分散させるために、酢酸ビニル単独で重合を開始し、重合が始まった時点から重合終了の直前に掛けてイタコン酸の重合系内への供給を連続的または断続的に行うことが好ましい。 When itaconic acid is used as the unsaturated carboxylic acid, in order to disperse the itaconic acid unit as uniformly as possible in the polymer, polymerization is started with vinyl acetate alone, and from the time when the polymerization starts to immediately before the end of the polymerization. It is preferable to feed itaconic acid into the polymerization system continuously or intermittently.
溶液重合において使用する重合開始剤は、特に限定するものではないが、アゾビスイソブチロニトリル、アゾビス−２，４−ジメチルパレロニトリル、アゾビス（４−メトキシ−２，４−ジメチルパレロニトリル）などのアゾ化合物、アセチルパーオキサイド、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、アセチルシクロヘキシルスルホニルパーオキシド、２，４，４−トリメチルペンチル−２−パーオキシフェノキシアセテートなどの過酸化物、ジイソプピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジエトキシエチルパーオキシジカーボネートなどのパーカーボネート化合物、ｔ−ブチルパーオキシネオデカネート、α−クミルパーオキシネオデカネート、ｔ−ブチルパーオキシネオデカネートなどのパーエステル化合物、アゾビスジメチルバレロニトリル、アゾビスメトキシバレロニトリルなどの公知のラジカル重合開始剤を使用することができる。また、重合反応温度は、特に限定するものではないが、通常３０〜９０℃程度の範囲で設定することができる。操作の容易さ、及び重合の制御の点からは使用溶剤の沸点で重合を行うことが推奨される。 The polymerization initiator used in the solution polymerization is not particularly limited, but azobisisobutyronitrile, azobis-2,4-dimethylpareronitrile, azobis (4-methoxy-2,4-dimethylpareronitrile). ), Etc., peroxides such as acetyl peroxide, benzoyl peroxide, lauroyl peroxide, acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, diisopropylpropyloxy Percarbonate compounds such as dicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate, t-butylperoxyneodecanate, α-cumylperoxyneodecane, t-butylperoxyneo Perester compounds such as Kaneto, azobisdimethylvaleronitrile can be used a known radical polymerization initiator such as azo-bis-methoxy valeronitrile. In addition, the polymerization reaction temperature is not particularly limited, but can usually be set in a range of about 30 to 90 ° C. From the viewpoint of ease of operation and control of polymerization, it is recommended to perform polymerization at the boiling point of the solvent used.
一方、変性ＰＶＡを製造する際の鹸化条件も特に限定されるものではなく、前述した方法で得られた重合体を、公知の方法で鹸化すればよい。一般的には、アルカリ触媒又は酸触媒の存在下で、分子中のエステル部を加水分解及び／または加アルコール分解することで行うことができる。このとき、重合溶媒であるアルコール中の共重合体の濃度は、特に限定されないが、１０〜８０質量％であることが望ましい。 On the other hand, the saponification conditions for producing the modified PVA are not particularly limited, and the polymer obtained by the above-described method may be saponified by a known method. In general, it can be carried out by hydrolysis and / or alcoholysis of the ester moiety in the molecule in the presence of an alkali catalyst or an acid catalyst. At this time, although the density | concentration of the copolymer in alcohol which is a polymerization solvent is not specifically limited, It is desirable that it is 10-80 mass%.
その際使用されるアルカリ触媒としては、例えば、水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、ナトリウムエチラート及びカリウムメチラートなどのアルカリ金属の水酸化物や、アルコラートなどを用いることができる。また、酸触媒としては、例えば、塩酸及び硫酸などの無機酸水溶液、ｐ−トルエンスルホン酸などの有機酸を用いることができるが、特に水酸化ナトリウムを用いることが望ましい。 Examples of the alkali catalyst used in this case include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate and potassium methylate, alcoholates, and the like. As the acid catalyst, for example, an inorganic acid aqueous solution such as hydrochloric acid and sulfuric acid, or an organic acid such as p-toluenesulfonic acid can be used, and sodium hydroxide is particularly preferable.
更に、鹸化反応の温度も、特に限定されないが、好ましくは１０〜７０℃、より好ましくは３０〜４０℃の範囲であることが望ましい。反応時間は、特に限定されないが、３０分〜３時間の範囲で行なうことが望ましい。 Further, the temperature of the saponification reaction is not particularly limited, but is preferably in the range of 10 to 70 ° C, more preferably 30 to 40 ° C. Although reaction time is not specifically limited, It is desirable to carry out in 30 minutes-3 hours.
（第２の実施形態）
本発明の第２の実施形態に係る塩化ビニル系樹脂について説明する。本実施形態の塩化ビニル系樹脂は、前述した第１の実施形態のポリビニルアルコール系重合体を二次分散剤として使用し、塩化ビニル単量体又は塩化ビニル単量体を含む単量体混合物を水中に分散させて懸濁重合することにより得られたものであり、可塑剤吸収量が１８質量部以上のものである。
(Second Embodiment)
A vinyl chloride resin according to the second embodiment of the present invention will be described. The vinyl chloride resin of the present embodiment uses the polyvinyl alcohol polymer of the first embodiment described above as a secondary dispersant, and a vinyl chloride monomer or a monomer mixture containing a vinyl chloride monomer is used. It is obtained by dispersing in water and performing suspension polymerization, and has a plasticizer absorption of 18 parts by mass or more.
この塩化ビニル系樹脂は、以下に示す方法で製造される。先ず、本実施形態の塩化ビニル系樹脂の原料となる単量体は、塩化ビニル単量体単独、又は塩化ビニル単量体とこれと共重合可能な他の単量体との混合物である。混合物の場合は、塩化ビニル単量体を５０質量％以上含むことが望ましい。塩化ビニル単量体と共重合可能な他の単量体の種類は限定されず、例えば、酢酸ビニル、プロピオン酸メチル、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸、エチレン、プロピレン、無水マレイン酸、アクリロニトリル、スチレン、塩化ビニリデンなどを用いることができる。 This vinyl chloride resin is produced by the following method. First, the monomer used as the raw material of the vinyl chloride resin of this embodiment is a vinyl chloride monomer alone or a mixture of a vinyl chloride monomer and another monomer copolymerizable therewith. In the case of a mixture, it is desirable to contain 50% by mass or more of vinyl chloride monomer. There are no limitations on the types of other monomers copolymerizable with the vinyl chloride monomer, such as vinyl acetate, methyl propionate, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid. , Ethylene, propylene, maleic anhydride, acrylonitrile, styrene, vinylidene chloride, and the like can be used.
また、本実施形態の塩化ビニル系樹脂は懸濁重合によって得ることができるが、懸濁重合において用いられる重合開始剤は限定されず、例えば、ジイソプロピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジエトキシエチルパーオキシジカーボネートなどのパーカーボネート化合物、ｔ−ブチルパーオキシネオデカノエート、ｔ−ヘキシルパーオキシネオデカノエート、ｔ−ヘキシルパーオキシピバレート、α−クミルパーオキシネオデカノエート、ｔ−ヘキシルネオヘキサノエート、２，４，４−トリメチルペンチル−２−パーオキシ−２−ネオデカノエートなどのパーオキシエステル化合物、アゾビス（２，４−ジメチルバレロニトリル）、アゾビスイソブチロニトリルなどのアゾ化合物など、ラウリルパーオキシド、ベンゾイルパーオキシド、クメンハイドロパーオキシド、２，４，４−トリメチルペンチル−２−パーオキシフェノキシアセテートなどのパーオキシド化合物が挙げられる。 The vinyl chloride resin of this embodiment can be obtained by suspension polymerization, but the polymerization initiator used in the suspension polymerization is not limited. For example, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxy Percarbonate compounds such as dicarbonate and diethoxyethyl peroxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-hexylperoxypivalate, α-cumylperoxyneo Peroxyester compounds such as decanoate, t-hexyl neohexanoate, 2,4,4-trimethylpentyl-2-peroxy-2-neodecanoate, azobis (2,4-dimethylvaleronitrile), azobisisobuty Azo compounds such as ronitrile, Peroxide, benzoyl peroxide, cumene hydroperoxide, peroxide compounds such as 2,4,4-trimethylpentyl-2-peroxy phenoxy acetate.
更に、重合開始剤は、水又は単量体を仕込む前と仕込む後のどちらに添加してもよい。又は、予め水性エマルジョンとしてから重合槽に添加してもよい。重合開始剤の添加量は、塩化ビニル単量体又はそれを含む単量体混合物１００質量部に対して、０．０２〜０．２質量部であることが好ましい。 Further, the polymerization initiator may be added either before or after the water or monomer is charged. Alternatively, an aqueous emulsion may be added in advance to the polymerization tank. It is preferable that the addition amount of a polymerization initiator is 0.02-0.2 mass part with respect to 100 mass parts of vinyl chloride monomers or a monomer mixture containing the same.
懸濁重合用の分散剤としては、本発明のポリビニルアルコール系重合体を二次分散剤として使用する以外に、一次分散剤も併用される。一次分散剤としては、ケン化度７０〜９０ｍｏｌ％であるポリビニルアルコール系重合体、メチルセルロース類、カルボキシルメチルセルロース類等が単独、あるいはこれらを組合せて用いられる。これら一次分散剤の使用量は、塩化ビニル単量体に対して０．０３〜０．１５質量％の範囲で用いることが望ましい。一次分散剤の使用量が０．０３質量％未満の場合、塩化ビニル単量体の水への分散性が低下することがある。また、一次分散剤の量が０．１５質量％を超えると、得られる塩化ビニル系樹脂の粒子径が小さくなりすぎて、排水に塩化ビニル系樹脂が混入し、排水処理が困難になる恐れがある。 As a dispersant for suspension polymerization, besides using the polyvinyl alcohol polymer of the present invention as a secondary dispersant, a primary dispersant is also used in combination. As the primary dispersant, polyvinyl alcohol polymers having a saponification degree of 70 to 90 mol%, methyl celluloses, carboxymethyl celluloses and the like are used alone or in combination. The amount of these primary dispersants used is desirably in the range of 0.03 to 0.15% by mass relative to the vinyl chloride monomer. When the amount of the primary dispersant used is less than 0.03% by mass, the dispersibility of the vinyl chloride monomer in water may be lowered. In addition, if the amount of the primary dispersant exceeds 0.15% by mass, the particle size of the obtained vinyl chloride resin may be too small, and the vinyl chloride resin may be mixed into the waste water, making it difficult to treat the waste water. is there.
本発明のポリビニルアルコール系重合体（懸濁重合用分散剤）は、二次分散剤として使用され、塩化ビニル単量体に対して、０．００１〜０．０６質量％の範囲で用いることが好ましい。添加量が０．００１質量％未満の場合、得られる塩化ビニル系樹脂の空孔率が十分ではなく、０．０６質量％を超えて加えた場合には得られた塩化ビニル系樹脂の加工性が悪化する恐れがある。 The polyvinyl alcohol polymer (dispersant for suspension polymerization) of the present invention is used as a secondary dispersant, and is used in the range of 0.001 to 0.06% by mass with respect to the vinyl chloride monomer. preferable. When the addition amount is less than 0.001% by mass, the porosity of the resulting vinyl chloride resin is not sufficient, and when added over 0.06% by mass, the processability of the obtained vinyl chloride resin is obtained. May get worse.
なお、本実施形態の塩化ビニル系樹脂の製造方法における種々の条件は、公知の技術を用いることができる。例えば、各原料化合物の仕込み方法や、単量体と水との仕込み比率や、重合温度や、重合転化率や、攪拌回転数等の重合条件は、特に限定されない。また、必要に応じて、消泡剤、重合度調節剤、連鎖移動剤、酸化防止剤、耐電防止剤等を用いてもよい。 In addition, a well-known technique can be used for the various conditions in the manufacturing method of the vinyl chloride resin of this embodiment. For example, the charging method of each raw material compound, the charging ratio of the monomer and water, the polymerization temperature, the polymerization conversion rate, the polymerization conditions such as the stirring rotation speed are not particularly limited. Moreover, you may use an antifoamer, a polymerization degree regulator, a chain transfer agent, antioxidant, an antistatic agent etc. as needed.
本実施形態の塩化ビニル系樹脂は、懸濁重合の際に、前述した第１の実施形態の分散剤を使用したことに伴い、高い空孔率を持ち、脱モノマー性に優れ、フィッシュアイが発生しにくい等の優れた特性を持っている。 The vinyl chloride resin of this embodiment has a high porosity, excellent demonomerization, and fish eyes due to the use of the dispersant of the first embodiment described above during suspension polymerization. It has excellent characteristics such as being difficult to occur.
以下、本発明の実施例及び比較例を挙げて、本発明の効果について具体的に説明する。本実施例においては、本発明の範囲内のポリビニルアルコール系重合体Ａ〜Ｇ及び本発明の範囲から外れるポリビニルアルコール系重合体Ｈ〜Ｌを製造した。続いて、これら実施例及び比較例のポリビニルアルコール系重合体を分散剤として使用し、塩化ビニル系樹脂の懸濁重合を行い、得られた塩化ビニル樹脂の物性などを評価した。なお、特に断りがない限り、「部」及び「％」は質量基準である。 Hereinafter, the effects of the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention. In this example, polyvinyl alcohol polymers A to G within the scope of the present invention and polyvinyl alcohol polymers H to L outside the scope of the present invention were produced. Subsequently, the polyvinyl alcohol polymers of these Examples and Comparative Examples were used as dispersants, suspension polymerization of vinyl chloride resins was performed, and the physical properties of the obtained vinyl chloride resins were evaluated. Unless otherwise specified, “part” and “%” are based on mass.
［実施例１〜７］
＜ポリビニルアルコール系重合体Ａの製造＞
酢酸ビニル１０部、メタノール４５部及びアゾビスイソブチロニトリル０．０１２部を重合缶に仕込み、窒素置換後加熱して沸点まで昇温した。そして、反応液温度が６０℃以上になったら、重合缶上部より、酢酸ビニル１４０部、メタノール４９部及びイタコン酸０．６８部の混合物を、１３時間かけて少しずつ連続的に滴下した。滴下が終了してから１時間後、重合率９５％に達した時点で重合を停止した。
[Examples 1-7]
<Production of polyvinyl alcohol polymer A>
10 parts of vinyl acetate, 45 parts of methanol, and 0.012 part of azobisisobutyronitrile were charged into a polymerization vessel, and after heating with nitrogen, the mixture was heated to the boiling point. And when the reaction liquid temperature became 60 degreeC or more, the mixture of 140 parts of vinyl acetate, 49 parts of methanol, and 0.68 part of itaconic acid was dripped little by little over 13 hours from the superposition | polymerization can top. One hour after the completion of the dropping, the polymerization was stopped when the polymerization rate reached 95%.
次に、常法により未反応の酢酸ビニルを除去し、得られた重合体を、水酸化ナトリウムを使用し、反応温度、反応時間及び水酸化ナトリウム量を調節して、常法により鹸化した。ケン化反応終了後、９０℃で９０分熱風乾燥して、ポリビニルアルコール系重合体Ａを得た。 Next, unreacted vinyl acetate was removed by a conventional method, and the resulting polymer was saponified by a conventional method using sodium hydroxide, adjusting the reaction temperature, reaction time, and amount of sodium hydroxide. After completion of the saponification reaction, it was dried with hot air at 90 ° C. for 90 minutes to obtain a polyvinyl alcohol polymer A.
＜ポリビニルアルコール系重合体Ｂ〜Ｇの製造＞
表１に記載したイタコン酸変性量、重合度、ケン化度となるように重合およびケン化条件を調整して、ポリビニルアルコール系重合体Ａと同様に重合、ケン化を行い、ポリビニルアルコール系重合体Ｂ〜Ｇを得た。
<Production of polyvinyl alcohol polymers B to G>
Polymerization and saponification conditions were adjusted so that the itaconic acid modification amount, polymerization degree, and saponification degree shown in Table 1 were obtained, and polymerization and saponification were performed in the same manner as the polyvinyl alcohol polymer A. Combined B to G were obtained.
＜ＰＶＡの特性評価＞
得られた変性ポリビニルアルコールＡ〜Ｇについて、重合度、ケン化度、４％水溶液／水分散液の安定性を、それぞれ下記の方法によって確認、測定した。
<Characteristic evaluation of PVA>
For the obtained modified polyvinyl alcohols A to G, the degree of polymerization, the degree of saponification, and the stability of a 4% aqueous solution / water dispersion were confirmed and measured by the following methods, respectively.
ａ）重合度：ＪＩＳ Ｋ６７２６に準拠して測定した。
ｂ）鹸化化度：ＪＩＳ Ｋ６７２６に準拠して測定した。
ｃ）４％水溶液／水分散液の安定性：濃度４質量％のポリビニルアルコール系重合体水溶液／水分散液を調製した。該水溶液／水分散液を試験管に１００ｍＬ取り分けた後に密栓し、２３℃の暗所に保管し、沈殿が発生するまでの日数を調べた。
a) Degree of polymerization: measured in accordance with JIS K6726.
b) Degree of saponification: Measured according to JIS K6726.
c) Stability of 4% aqueous solution / water dispersion: A polyvinyl alcohol polymer aqueous solution / water dispersion having a concentration of 4% by mass was prepared. 100 mL of the aqueous solution / aqueous dispersion was placed in a test tube, sealed, and stored in a dark place at 23 ° C., and the number of days until precipitation occurred was examined.
＜塩化ビニル単量体の懸濁重合＞
翼幅３７．５ｍｍのパドル撹拌翼を備えた内容量３０リットルの反応器に、水１２０００ｇと、一次分散剤としてケン化度８０％のポリビニルアルコール（電気化学社製Ｗ−２４Ｎ）６．０ｇ，二次分散剤としてポリビニルアルコール系重合体Ａ２．０ｇを入れて溶解した。次に、重合開始剤としてクミルパーオキシネオデカノエート０．５ｇとｔ−ブチルパーオキシネオデカノエート２．３ｇを仕込み、系内の窒素置換を行った後、塩化ビニル単量体５０００ｇを仕込み、回転数６５０ｒｐｍで撹拌しながら、温度５７．５℃で４時間反応させた。そして、内圧が０．７８ＭＰａ以下になった時点で重合反応を終了させ、反応器から樹脂スラリーを取り出し、脱水乾燥して塩化ビニル樹脂の粉末を得た。
<Suspension polymerization of vinyl chloride monomer>
In a reactor having an internal volume of 30 liters equipped with a paddle stirring blade having a blade width of 37.5 mm, 12,000 g of water and 6.0 g of polyvinyl alcohol having a saponification degree of 80% as a primary dispersant (W-24N manufactured by Electrochemical Co., Ltd.) As a secondary dispersant, 2.0 g of polyvinyl alcohol polymer A was added and dissolved. Next, 0.5 g of cumylperoxyneodecanoate and 2.3 g of t-butylperoxyneodecanoate were charged as polymerization initiators, and after nitrogen substitution in the system, 5000 g of vinyl chloride monomer was added. The mixture was stirred and reacted at a temperature of 57.5 ° C. for 4 hours while stirring at a rotation speed of 650 rpm. Then, when the internal pressure became 0.78 MPa or less, the polymerization reaction was terminated, the resin slurry was taken out from the reactor, dehydrated and dried to obtain a vinyl chloride resin powder.
＜塩化ビニル樹脂の特性評価＞
得られた塩化ビニル系樹脂の平均粒子径、嵩比重及び可塑剤吸収量について評価した。平均粒径の測定はＪＩＳ Ｋ６７２１に準拠して、６０メッシュ（目開き２５０μｍ）、８０メッシュ（目開き１８０μｍ）、１００メッシュ（目開き１５０μｍ）、１５０メッシュ（目開き１０６μｍ）、２００メッシュ（目開き７５μｍ）の篩を用いて、累積頻度５０％の粒子径を平均粒子径とした。また、嵩比重は、ＪＩＳ Ｋ６７２０−２に準拠して測定した。なお、平均粒子径が２００μｍ以上は粗粒とした。
<Characteristic evaluation of vinyl chloride resin>
The average particle diameter, bulk specific gravity, and plasticizer absorption of the obtained vinyl chloride resin were evaluated. The average particle size is measured according to JIS K6721, 60 mesh (aperture 250 μm), 80 mesh (aperture 180 μm), 100 mesh (aperture 150 μm), 150 mesh (aperture 106 μm), 200 mesh (aperture) 75 μm) was used, and the particle size with a cumulative frequency of 50% was defined as the average particle size. The bulk specific gravity was measured according to JIS K6720-2. The average particle size of 200 μm or more was coarse.
ポリビニルアルコール系重合体Ｂ〜Ｇについても、ポリビニルアルコール系重合体Ａと同様に評価を行った。評価の結果は表１にまとめて示した。 The polyvinyl alcohol polymers B to G were also evaluated in the same manner as the polyvinyl alcohol polymer A. The evaluation results are summarized in Table 1.
［比較例１］
本発明のポリビニルアルコール系重合体を使用せずに、一次分散剤のみを用いて実施例１と同様に塩化ビニル単量体の重合試験を実施した。結果は、表２にまとめて示した。
[Comparative Example 1]
A vinyl chloride monomer polymerization test was conducted in the same manner as in Example 1 using only the primary dispersant without using the polyvinyl alcohol polymer of the present invention. The results are summarized in Table 2.
［比較例２〜６］
＜ポリビニルアルコール系重合体Ｈ〜Ｌの製造＞
表２に記載したイタコン酸変性量、重合度、ケン化度となるように重合およびケン化条件を調整して、実施例１と同様に重合、ケン化を行い、ポリビニルアルコール系重合体Ｈ〜Ｌを得た。
[Comparative Examples 2 to 6]
<Production of polyvinyl alcohol polymers H to L>
Polymerization and saponification conditions were adjusted so that the itaconic acid modification amount, polymerization degree, and saponification degree described in Table 2 were obtained, and polymerization and saponification were performed in the same manner as in Example 1. L was obtained.
ポリビニルアルコール系重合体Ｈ〜Ｌについても、ポリビニルアルコール系重合体Ａと同様に評価を行った。評価の結果は表２にまとめて示した。 The polyvinyl alcohol polymers H to L were also evaluated in the same manner as the polyvinyl alcohol polymer A. The evaluation results are summarized in Table 2.
表１および表２から、実施例は比較例に対して優れていることが判る。結果の概要について下記の通り記す。
比較例１： 本発明の分散剤を使用しておらず、可塑剤吸収性が劣る。
比較例２： カルボン酸を共重合していないことから、水溶性／水分散性が不足。
比較例３： カルボン酸共重合量が多過ぎるため、粒子径が粗大化している。
比較例４： 重合度が高過ぎるため、粒子径が粗大化している。
比較例５： ケン化度が低過ぎるため、水溶液／水分散液の安定性が悪い。
比較例６： ケン化度が高過ぎるため、粒子径が粗大化している。
From Table 1 and Table 2, it can be seen that the example is superior to the comparative example. The summary of the results is as follows.
Comparative Example 1: The dispersant of the present invention is not used, and the plasticizer absorbability is inferior.
Comparative Example 2: Since water is not copolymerized with carboxylic acid, water solubility / water dispersibility is insufficient.
Comparative Example 3: Since the amount of carboxylic acid copolymerization is too large, the particle diameter is coarsened.
Comparative Example 4: Since the degree of polymerization is too high, the particle size is coarsened.
Comparative Example 5: Since the degree of saponification is too low, the stability of the aqueous solution / aqueous dispersion is poor.
Comparative Example 6: Since the degree of saponification is too high, the particle size is coarsened.
これらの結果の様に、実施例１〜７のポリビニルアルコール系重合体は、比較例１〜６に比べて、水溶性／水分散性、塩化ビニル系樹脂の空孔率が高く、結果として可塑剤吸収量が多い、一次分散剤への悪影響が少ないことから、塩化ビニル系樹脂の平均粒径が肥大化しない等の優れた特性を示すことが判る。なお、これらの表には示さなかったが、ポリビニルアルコール系重合体の重合度を１９０に調整した場合は、重合体を固形状態で得られなかったためその後の評価を中止した。 Like these results, the polyvinyl alcohol polymers of Examples 1 to 7 have higher water solubility / water dispersibility and higher porosity of vinyl chloride resins than Comparative Examples 1 to 6, resulting in plasticity. From the fact that the agent absorption is large and the adverse effect on the primary dispersant is small, it can be seen that the vinyl chloride resin exhibits excellent properties such as the average particle size does not enlarge. Although not shown in these tables, when the polymerization degree of the polyvinyl alcohol polymer was adjusted to 190, the subsequent evaluation was stopped because the polymer was not obtained in a solid state.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012077179A JP5940858B2 (en) | 2012-03-29 | 2012-03-29 | Polyvinyl alcohol polymer, dispersant for suspension polymerization, vinyl chloride resin and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012077179A JP5940858B2 (en) | 2012-03-29 | 2012-03-29 | Polyvinyl alcohol polymer, dispersant for suspension polymerization, vinyl chloride resin and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013203994A JP2013203994A (en) | 2013-10-07 |
| JP5940858B2 true JP5940858B2 (en) | 2016-06-29 |
Family
ID=49523438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012077179A Expired - Fee Related JP5940858B2 (en) | 2012-03-29 | 2012-03-29 | Polyvinyl alcohol polymer, dispersant for suspension polymerization, vinyl chloride resin and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5940858B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6543004B2 (en) | 2016-11-02 | 2019-07-10 | 日本酢ビ・ポバール株式会社 | Dispersion aid for suspension polymerization and method for producing vinyl polymer using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53136089A (en) * | 1977-05-02 | 1978-11-28 | Nippon Synthetic Chem Ind Co Ltd:The | Suspension polymerization of vinyl chloride |
| JP3558440B2 (en) * | 1995-12-28 | 2004-08-25 | 日本合成化学工業株式会社 | Dispersion aid for suspension polymerization of vinyl compounds |
| JP3753272B2 (en) * | 1996-11-18 | 2006-03-08 | 日本合成化学工業株式会社 | Dispersing aid for suspension polymerization of vinyl compounds |
| EP1300421B1 (en) * | 2001-10-05 | 2005-08-31 | Kuraray Co., Ltd. | Dispersion stabilizer for suspension polymerization of vinyl compound |
-
2012
- 2012-03-29 JP JP2012077179A patent/JP5940858B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013203994A (en) | 2013-10-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI513503B (en) | Dispersing agent for suspension polymerization, vinyl chloride resin and method for producing the same | |
| US9834629B1 (en) | Dispersion stabilizer for suspension polymerization and method for producing vinyl resin | |
| JP5548677B2 (en) | Dispersion stabilizer for suspension polymerization | |
| WO2015019613A1 (en) | Dispersion stabilizer for suspension polymerization, and manufacturing method for vinyl resin | |
| JP5288683B2 (en) | Dispersion stabilizer for suspension polymerization of vinyl compounds | |
| WO2019156006A1 (en) | Modified vinyl alcohol polymer and dispersion stabilizer for suspension polymerization | |
| JP6906528B2 (en) | Modified vinyl alcohol polymer and dispersion stabilizer for suspension polymerization | |
| JP5236250B2 (en) | Dispersant for polymerization, method for producing vinyl chloride resin using the same, vinyl chloride resin and molded product | |
| JP5940858B2 (en) | Polyvinyl alcohol polymer, dispersant for suspension polymerization, vinyl chloride resin and method for producing the same | |
| JP5632830B2 (en) | Dispersion stabilizer for suspension polymerization | |
| KR0146676B1 (en) | Stirrer for suspension polymerization of vinyl chloride resins | |
| CN111868103B (en) | Dispersion stabilizer for suspension polymerization | |
| JP2017061656A (en) | Dispersion auxiliary agent for suspension polymerization and its aqueous liquid, and method for producing vinyl resin using them | |
| JP7337075B2 (en) | Dispersing aid for suspension polymerization and method for producing vinyl resin | |
| JP3629065B2 (en) | Dispersion stabilizer for suspension polymerization of vinyl compounds | |
| JP5363244B2 (en) | Dispersion stabilizer for suspension polymerization of styrenic polymer and method for producing styrenic polymer using the same | |
| JP7488183B2 (en) | Polyvinyl alcohol polymer and molded body using same | |
| JP5465615B2 (en) | Dispersion stabilizer for suspension polymerization | |
| WO2018225796A1 (en) | Method of producing modified vinyl alcohol polymer | |
| JPS62235303A (en) | Method for feeding suspension stabilizer in vinyl chloride suspension polymerization method | |
| JP2022003139A (en) | Dispersion auxiliary agent for suspension polymerization and its aqueous liquid, and method for producing vinyl resin using them | |
| KR20090033468A (en) | Dispersion stabilizer for vinyl compound suspension polymerization | |
| JP2004196892A (en) | Dispersion stabilizer for suspension polymerization of vinyl compound | |
| WO2010113570A1 (en) | Method for producing vinyl-based resin | |
| JPS60240702A (en) | Dispersion stabilizer for suspension polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20141218 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20151208 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20151215 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160215 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20160215 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160302 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160510 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160519 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5940858 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |