JP2007197495A - Emulsifier for emulsion polymerization, manufacturing method of polymer emulsion and polymer emulsion - Google Patents
Emulsifier for emulsion polymerization, manufacturing method of polymer emulsion and polymer emulsion Download PDFInfo
- Publication number
- JP2007197495A JP2007197495A JP2006014477A JP2006014477A JP2007197495A JP 2007197495 A JP2007197495 A JP 2007197495A JP 2006014477 A JP2006014477 A JP 2006014477A JP 2006014477 A JP2006014477 A JP 2006014477A JP 2007197495 A JP2007197495 A JP 2007197495A
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- JP
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- Prior art keywords
- emulsion
- emulsifier
- polymerization
- emulsion polymerization
- 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.)
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- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 78
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims abstract description 72
- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- 239000000839 emulsion Substances 0.000 title claims description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 238000006116 polymerization reaction Methods 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 31
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 125000001483 monosaccharide substituent group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 229920006254 polymer film Polymers 0.000 abstract description 13
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 150000002772 monosaccharides Chemical class 0.000 abstract description 5
- -1 2-ethylhexyl Chemical group 0.000 description 46
- 150000002118 epoxides Chemical group 0.000 description 23
- 239000004711 α-olefin Substances 0.000 description 22
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- BZANQLIRVMZFOS-ZKZCYXTQSA-N (3r,4s,5s,6r)-2-butoxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound CCCCOC1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O BZANQLIRVMZFOS-ZKZCYXTQSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 125000002947 alkylene group Chemical group 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229920001542 oligosaccharide Polymers 0.000 description 5
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- OPLYWMWNKOERMH-UHFFFAOYSA-N 1-prop-1-enylcyclohexa-2,4-dien-1-ol Chemical compound CC=CC1(O)CC=CC=C1 OPLYWMWNKOERMH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000012874 anionic emulsifier Substances 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002771 monosaccharide derivatives Chemical class 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 150000002482 oligosaccharides Chemical class 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- WHGXZPQWZJUGEP-UHFFFAOYSA-N 2-prop-1-enylphenol Chemical compound CC=CC1=CC=CC=C1O WHGXZPQWZJUGEP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- CTYRPMDGLDAWRQ-UHFFFAOYSA-N phenyl hydrogen sulfate Chemical compound OS(=O)(=O)OC1=CC=CC=C1 CTYRPMDGLDAWRQ-UHFFFAOYSA-N 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 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
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 0 *C(COc1ccccc1)O* Chemical compound *C(COc1ccccc1)O* 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- 125000006019 1-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-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
- MSWZFWKMSRAUBD-GASJEMHNSA-N 2-amino-2-deoxy-D-galactopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@H](O)[C@@H]1O MSWZFWKMSRAUBD-GASJEMHNSA-N 0.000 description 1
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- DBTMGCOVALSLOR-UHFFFAOYSA-N 32-alpha-galactosyl-3-alpha-galactosyl-galactose Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(OC2C(C(CO)OC(O)C2O)O)OC(CO)C1O DBTMGCOVALSLOR-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- JEORMZJMVZUJLA-UHFFFAOYSA-N 6-methyl-6-prop-1-enylcyclohexa-2,4-dien-1-ol Chemical compound CC=CC1(C)C=CC=CC1O JEORMZJMVZUJLA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- WQZGKKKJIJFFOK-WHZQZERISA-N D-aldose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-WHZQZERISA-N 0.000 description 1
- WQZGKKKJIJFFOK-IVMDWMLBSA-N D-allopyranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-IVMDWMLBSA-N 0.000 description 1
- LKDRXBCSQODPBY-JDJSBBGDSA-N D-allulose Chemical compound OCC1(O)OC[C@@H](O)[C@@H](O)[C@H]1O LKDRXBCSQODPBY-JDJSBBGDSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-YMDCURPLSA-N D-galactopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-YMDCURPLSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-AQKNRBDQSA-N D-glucopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-AQKNRBDQSA-N 0.000 description 1
- RXVWSYJTUUKTEA-UHFFFAOYSA-N D-maltotriose Natural products OC1C(O)C(OC(C(O)CO)C(O)C(O)C=O)OC(CO)C1OC1C(O)C(O)C(O)C(CO)O1 RXVWSYJTUUKTEA-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-VANFPWTGSA-N D-mannopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-VANFPWTGSA-N 0.000 description 1
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Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
本発明は、乳化重合する際に用いられる乳化重合用乳化剤、その乳化重合用乳化剤を使用したポリマーエマルションの製造方法、及びその製造方法により得られるポリマーエマルションに関する。 The present invention relates to an emulsifier for emulsion polymerization used in emulsion polymerization, a method for producing a polymer emulsion using the emulsifier for emulsion polymerization, and a polymer emulsion obtained by the method.
従来、ノニオン性の乳化重合用乳化剤としては、ノニルフェノールやオクチルフェノールにアルキレンオキサイドを付加したポリオキシアルキレンアルキルフェニルエーテルや高級アルコールにアルキレンオキサイドを付加したポリオキシアルキレンアルキルエーテルが単独あるいは併用で使用されているが、ポリマーエマルションの安定性、また該エマルションから得られたポリマーフィルムの性質等は、必ずしも充分に満足し得るものではなく、多くの解決すべき問題点が残されている。 Conventionally, as nonionic emulsifiers for emulsion polymerization, polyoxyalkylene alkyl phenyl ethers obtained by adding alkylene oxide to nonylphenol or octylphenol and polyoxyalkylene alkyl ethers obtained by adding alkylene oxide to higher alcohols are used alone or in combination. However, the stability of the polymer emulsion and the properties of the polymer film obtained from the emulsion are not always satisfactory, and many problems to be solved remain.
例えば、エマルションの重合安定性、得られたエマルションの機械安定性、化学安定性、凍結融解安定性、顔料混和性、貯蔵安定性等の問題が挙げられる。特に、機械的安定性については、改善すべき問題点が残されている。さらに、エマルションからポリマーフィルムを作成した際、使用した乳化剤が遊離の状態でポリマーフィルム中に残留するため、フィルムの耐水性、接着性が劣る等の問題を生じている。また、エマルションを塩析または酸析等の手段によって破壊し、ポリマーを取り出す際、排水中に多くの乳化剤が含有され、河川汚濁の原因となるため、乳化剤の除去処理に多大の労力が必要となる。 Examples thereof include problems such as polymerization stability of the emulsion, mechanical stability of the obtained emulsion, chemical stability, freeze-thaw stability, pigment miscibility, and storage stability. In particular, the mechanical stability remains a problem to be improved. Furthermore, when a polymer film is prepared from the emulsion, the used emulsifier remains in the polymer film in a free state, causing problems such as poor water resistance and adhesion of the film. In addition, when the emulsion is destroyed by means such as salting out or aciding out and the polymer is taken out, a large amount of emulsifier is contained in the waste water, which causes river pollution. Become.
このような観点から従来の乳化剤の問題点を改善するため、反応基として共重合性の不飽和基を有し、親水基にポリオキシアルキレン鎖を導入した反応性乳化重合用乳化剤が数多く提案されている。例えば、特開平８−４１１１２号公報、特開平４−５０２０４号公報、特開昭６３−３１９０３５号公報、特開昭６２−１０４８０２号公報などがあり、各種モノマーについて乳化重合が試みられている。これらの反応性乳化剤を乳化剤として使用したエマルションは重合時の安定性が良く、また、該エマルションから得られたポリマーフィルムは耐水性、接着性、耐熱性、耐候性において優れた性能を示すものである。 From this viewpoint, in order to improve the problems of conventional emulsifiers, many reactive emulsion polymerization emulsifiers having a copolymerizable unsaturated group as a reactive group and a polyoxyalkylene chain introduced into a hydrophilic group have been proposed. ing. For example, JP-A-8-41112, JP-A-4-50204, JP-A-63-319035, JP-A-62-2104802 and the like have attempted emulsion polymerization of various monomers. Emulsions using these reactive emulsifiers as emulsifiers have good stability during polymerization, and polymer films obtained from the emulsions exhibit excellent performance in water resistance, adhesiveness, heat resistance, and weather resistance. is there.
しかしながら、このようなアルキレンオキサイドから誘導される反応性乳化重合用乳化剤の問題点として、未反応のアルキレンオキサイドが製品中に残存すること、副生成物として発がん性や刺激性の高い物質が発生することが挙げられる。例えば、合成時の有害なジオキサンの生成や、アルキレンオキサイド鎖の酸化分解により有害性のアルデヒド類を生成することが知られており、シックハウス症候群やＶＯＣ問題が騒がれる近年、アルデヒド等を含む乳化剤をエマルションの製造に用いるのは好ましくない。 However, as a problem of such an emulsifier for reactive emulsion polymerization derived from alkylene oxide, unreacted alkylene oxide remains in the product, and a substance with high carcinogenicity and irritation is generated as a by-product. Can be mentioned. For example, it is known that harmful dioxane is generated during synthesis and toxic aldehydes are generated by oxidative degradation of alkylene oxide chains. It is not preferable to use it for the production of an emulsion.
これに対し、アルキレンオキサイドから誘導されないノニオン性乳化重合用乳化剤として、アルキルポリグリコシドを用いた乳化重合用乳化剤が開示されている（例えば、特許文献１）。
アルキルポリグルコシドは、ポリオキシアルキレンアルキルエーテルのように有害なジオキサンやホルムアルデヒドが発生せず、またアルキレンオキサイドを出発原料としていないため高い安全性を持ち、また生分解性にも優れているため自然環境に排出された際も自然環境に対する負荷の少ない乳化重合用乳化剤であるが、重合時の安定性、ポリマーエマルションの安定性、また得られたポリマーフィルムの性質は必ずしも満足するものではなく、解決すべき問題点が多く残されている。 Alkylpolyglucoside does not generate harmful dioxane or formaldehyde like polyoxyalkylene alkyl ether, and has high safety because it does not use alkylene oxide as a starting material. Although it is an emulsifier for emulsion polymerization that has a low impact on the natural environment even when discharged into the water, the stability during polymerization, the stability of the polymer emulsion, and the properties of the resulting polymer film are not always satisfactory and can be solved. There are many problems to be solved.
本発明は、上記実情に鑑みてなされたものであって、その目的は親水基としてポリオキシアルキレン鎖を持たず、乳化重合時の安定性を良好なものとし、ポリマー及びポリマーフィルムの耐水性、接着性、耐熱性、耐候性等の諸特性が著しく改善された反応性乳化重合用乳化剤を提供することにある。 The present invention has been made in view of the above circumstances, and its purpose is not to have a polyoxyalkylene chain as a hydrophilic group, to improve the stability during emulsion polymerization, and to improve the water resistance of polymers and polymer films, An object of the present invention is to provide an emulsifier for reactive emulsion polymerization in which various properties such as adhesion, heat resistance and weather resistance are remarkably improved.
本発明者らは、上記課題を解決するため鋭意研究を重ねた結果、共重合性の不飽和基を有し、親水基部分がポリグルコシドである乳化重合用乳化剤が適していることを見出し、本発明に到達したものである。 As a result of intensive studies to solve the above problems, the present inventors have found that an emulsifier for emulsion polymerization having a copolymerizable unsaturated group and having a hydrophilic group portion of polyglucoside is suitable. The present invention has been achieved.
即ち、本発明は、下記一般式（１）で表されることを特徴とする乳化重合用乳化剤である。
（式中、Ｒ１は炭化水素基である。Ｒ２及びＲ３はアルケニル基または水素原子であり、Ｒ２及びＲ３は一方又は両方がアルケニル基である。また、Ｒ２及びＲ３は異なるアルケニル基でも良い。Ｇは単糖類の残基を表す。ｎは１〜３０である。） (Wherein R 1 is a hydrocarbon group, R 2 and R 3 are alkenyl groups or hydrogen atoms, one or both of R 2 and R 3 are alkenyl groups, and R 2 and R 3 are Different alkenyl groups may be used, G represents a monosaccharide residue, and n is 1 to 30.)
本発明の乳化重合用乳化剤は、上記一般式（１）において、前記アルケニル基が下記一般式（２）〜（４）で表されるアルケニル基であることが好ましい。
また、本発明のポリマーエマルションの製造方法は、モノマーに対して上記の乳化重合用乳化剤を０．１〜２０重量％の量で使用し、水性媒体中で前記モノマーを重合させる、または前記モノマー重合後のポリマーに添加することにある。 In addition, the method for producing a polymer emulsion of the present invention uses the above-mentioned emulsifier for emulsion polymerization in an amount of 0.1 to 20% by weight with respect to the monomer, and polymerizes the monomer in an aqueous medium, or the monomer polymerization. It is to be added to the later polymer.
そして、本発明のポリマーエマルションは、上記ポリマーエマルションの製造方法により得られるものである。 And the polymer emulsion of this invention is obtained by the manufacturing method of the said polymer emulsion.
本発明の乳化重合用乳化剤によれば、その分子中の疎水基部分に共重合性の不飽和基を有し、重合性モノマーとの共重合性に優れ、ポリマー組成に取り込まれやすい。そのため、共重合性の反応性乳化重合用乳化剤として有用であり、本発明の乳化重合用乳化剤を使用し重合されたポリマーエマルションから得られたポリマーフィルム中に遊離した状態で存在する乳化剤量が減少しフィルムの耐水性、接着性、耐熱性、耐候性向上に極めて優れた効果を発揮する。かつポリマーエマルションの泡立ち、機械安定性等が著しく改善される。更に、ジオキサンやアルデヒド類などの有害物質を大幅に低減したポリマーエマルションを得ることができる。 The emulsifier for emulsion polymerization according to the present invention has a copolymerizable unsaturated group in the hydrophobic part of the molecule, is excellent in copolymerizability with a polymerizable monomer, and is easily incorporated into a polymer composition. Therefore, it is useful as an emulsifier for copolymerizable reactive emulsion polymerization, and the amount of emulsifier present in a free state in a polymer film obtained from a polymer emulsion obtained by polymerization using the emulsifier for emulsion polymerization of the present invention is reduced. The film exhibits excellent effects in improving the water resistance, adhesiveness, heat resistance, and weather resistance of the film. In addition, foaming and mechanical stability of the polymer emulsion are remarkably improved. Furthermore, a polymer emulsion in which harmful substances such as dioxane and aldehydes are greatly reduced can be obtained.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
本発明の乳化重合用乳化剤は、上記一般式（１）の化合物において、式中Ｒ１は炭化水素基を表す。炭化水素基としては、例えば、アルキル基、アルケニル基、アリール基、シクロアルキル基、シクロアルケニル基等が挙げられる。 The emulsifier for emulsion polymerization of the present invention is a compound of the above general formula (1), wherein R 1 represents a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, a cycloalkenyl group, and the like.
アルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、２級ブチル、ターシャリブチル、ペンチル、イソペンチル、２級ペンチル、ネオペンチル、ターシャリペンチル、ヘキシル、２級ヘキシル、ヘプチル、２級ヘプチル、オクチル、２−エチルヘキシル、２級オクチル、ノニル、２級ノニル、デシル、２級デシル、ウンデシル、２級ウンデシル、ドデシル、２級ドデシル、トリデシル、イソトリデシル、２級トリデシル、テトラデシル、２級テトラデシル、ヘキサデシル、２級ヘキサデシル、ステアリル、イコシル、ドコシル、テトラコシル、トリアコンチル、２−ブチルオクチル、２−ブチルデシル、２−ヘキシルオクチル、２−ヘキシルデシル、２−オクチルデシル、２−ヘキシルドデシル、２−オクチルドデシル、２−デシルテトラデシル、２−ドデシルヘキサデシル、２−ヘキサデシルオクタデシル、２−テトラデシルオクタデシル、モノメチル分枝−イソステアリル基等が挙げられる。 Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, secondary pentyl, neopentyl, tertiary pentyl, hexyl, secondary hexyl, heptyl, 2 Secondary heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl, decyl, secondary decyl, undecyl, secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl , Hexadecyl, secondary hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldecyl, - octyldodecyl, 2-decyltetradecyl, 2-dodecyl-hexadecyl, 2-hexadecyl octadecyl, 2-tetradecyl-octadecyl, monomethyl branched - and the like isostearyl group.
アルケニル基としては、例えば、ビニル、アリル、プロペニル、イソプロペニル、ブテニル、イソブテニル、ペンテニル、イソペンテニル、ヘキセニル、ヘプテニル、オクテニル、ノネニル、デセニル、ウンデセニル、ドデセニル、テトラデセニル、オレイル等が挙げられる。 Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.
アリール基としては、例えば、フェニル、トルイル、キシリル、クメニル、メシチル、ベンジル、フェネチル、スチリル、シンナミル、ベンズヒドリル、トリチル、エチルフェニル、プロピルフェニル、ブチルフェニル、ペンチルフェニル、ヘキシルフェニル、ヘプチルフェニル、オクチルフェニル、ノニルフェニル、デシルフェニル、ウンデシルフェニル、ドデシルフェニル、フェニルフェニル、ベンジルフェニル、スチレン化フェニル、クミルフェニル、スチレン化クレシル、ベンジルキシリル、α−ナフチル、β−ナフチル基等が挙げられる。 As an aryl group, for example, phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, Nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, styrenated phenyl, cumylphenyl, styrenated cresyl, benzylxylyl, α-naphthyl, β-naphthyl groups and the like can be mentioned.
シクロアルキル基、シクロアルケニル基としては、例えば、シクロペンチル、シクロヘキシル、シクロヘプチル、メチルシクロペンチル、メチルシクロヘキシル、メチルシクロヘプチル、シクロペンテニル、シクロヘキセニル、シクロヘプテニル、メチルシクロペンテニル、メチルシクロヘキセニル、メチルシクロヘプテニル基等が挙げられる。 Examples of the cycloalkyl group and cycloalkenyl group include a cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcycloheptenyl group. Etc.
また、Ｒ１は上記に記載の炭化水素基を２種類以上含んでいても良い。 R 1 may contain two or more types of the hydrocarbon groups described above.
一般式（１）において、Ｒ１は炭素数６から３０のアルキル基またはアルケニル基であることが好ましい。 In the general formula (1), R 1 is preferably an alkyl group or alkenyl group having 6 to 30 carbon atoms.
通常、Ｒ１はα−オレフィンエポキサイドからエポキシド部分を除いた残基である。工業的に製造されるα−オレフィンエポキサイドとしては、ダイセル化学工業（株）製のＡＯＥシリーズ、大日本インキ化学工業（株）製のエポサイザーシリーズ、ＡＲＫＥＭＡ社製のＶｉｋｏｌｏｘシリーズなどがある。これらは商業生産上好適に使用できる原料の一例である。また、これらを２種類以上配合して使用することも可能である。 R 1 is usually a residue obtained by removing an epoxide moiety from an α-olefin epoxide. Industrially produced α-olefin epoxides include AOE series manufactured by Daicel Chemical Industries, Ltd., Eposizer series manufactured by Dainippon Ink and Chemicals, and Vikolox series manufactured by ARKEMA. These are examples of raw materials that can be suitably used for commercial production. Moreover, it is also possible to mix and use two or more of these.
一般式（１）において、Ｒ２及びＲ３は一方または両方がアルケニル基である。Ｒ２及びＲ３は同一でも異なるアルケニル基でも良い。 In general formula (1), one or both of R 2 and R 3 is an alkenyl group. R 2 and R 3 may be the same or different alkenyl groups.
アルケニル基としては、例えば、ビニル基、１−プロペニル基、２−プロペニル基、イソプロペニル基、１−メチル−１−プロペニル基、２−メチル−１−プロペニル基、２−メチル−２−プロペニル基、３−メチル−２−プロペニル基、１−ブテニル基、２−ブテニル基、３−ブテニル基等が挙げられる。 Examples of the alkenyl group include a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group, and 2-methyl-2-propenyl group. , 3-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like.
一般式（１）において、Ｒ２及びＲ３は下記一般式（２）〜（４）で表されるアルケニル基であることが好ましい。 In the general formula (1), R 2 and R 3 are preferably alkenyl groups represented by the following general formulas (2) to (4).
一般式（１）において、ｎは１〜３０で、好ましくは１〜１０である。 In General formula (1), n is 1-30, Preferably it is 1-10.
［合成方法］
本発明の乳化重合用乳化剤を得るための反応条件は特に限定されるものではなく、例えば、α−オレフィンエポキシドとアルケニルフェノールを触媒存在下反応させた後、得られた反応組成物にポリグルコシド部分を導入して、本発明の乳化重合用乳化剤を得ることができる。また、必要に応じ精製を行っても良い。
[Synthesis method]
The reaction conditions for obtaining the emulsifier for emulsion polymerization of the present invention are not particularly limited. For example, after reacting an α-olefin epoxide and an alkenylphenol in the presence of a catalyst, a polyglucoside moiety is added to the obtained reaction composition. Can be introduced to obtain the emulsifier for emulsion polymerization of the present invention. Moreover, you may refine | purify as needed.
反応性基を持った疎水基部分へのポリグルコシドの導入は、アルキルポリグルコシドの公知の製造方法を適用することにより可能である。アルキルポリグルコシドの製造方法は、例えば、特開２００１−２７８８９１号公報、特開平１１−２０９３９１号公報、特開平８−２６９１０３号公報、特開昭６４−４７７９６号公報、特開昭６２−２９２７８９号公報等において開示されている。 Polyglucoside can be introduced into the hydrophobic group having a reactive group by applying a known production method of alkylpolyglucoside. Examples of the method for producing alkyl polyglucoside include, for example, JP-A No. 2001-278891, JP-A No. 11-209391, JP-A No. 8-269103, JP-A No. 64-47796, and JP-A No. 62-292789. It is disclosed in publications and the like.
一般的に用いられるアルキルポリグルコシドの製造方法としては、糖と脂肪アルコールを酸触媒下で反応させアルキルポリグルコシドを得る方法、または糖とブタノールを酸触媒下で反応させブチルポリグルコシドにした後、脂肪アルコールと交換反応させて二段階でアルキルポリグルコシドを得る方法がある。 As a generally used method for producing an alkylpolyglucoside, a method of obtaining an alkylpolyglucoside by reacting a sugar and a fatty alcohol in the presence of an acid catalyst, or a reaction of sugar and butanol in the presence of an acid catalyst to form a butylpolyglucoside, There is a method of obtaining an alkylpolyglucoside in two stages by exchange reaction with a fatty alcohol.
ポリグルコシド化合物の製造に使用される糖としては、単糖、単糖誘導体、またはオリゴ糖がある。単糖ではヘキソース類として、グルコース、マンノース、アロース、アルトロース、ガラクトース、タロース、グロース、イドース、フルクトース、プシコース、タガトース、ソルボース等がある。ペントース類として、リボース、アラビノース、キシルロース、リキソース、リブロース等がある。 Examples of the sugar used for the production of the polyglucoside compound include a monosaccharide, a monosaccharide derivative, and an oligosaccharide. Monosaccharides include hexoses such as glucose, mannose, allose, altrose, galactose, talose, growth, idose, fructose, psicose, tagatose, sorbose and the like. Examples of pentoses include ribose, arabinose, xylulose, lyxose and ribulose.
単糖誘導体では、デオキシ糖として、ラムノース、フコース等がある。ウロン酸として、グルクロン酸、ガラクチュロン酸、マンヌロン酸等がある。また、アミノ糖としてグルコサミン、コンドロサミン等がある。 Monosaccharide derivatives include rhamnose, fucose and the like as deoxy sugars. Examples of uronic acid include glucuronic acid, galacturonic acid, mannuronic acid and the like. Examples of amino sugars include glucosamine and chondrosamine.
オリゴ糖としては、重合度が２〜１０のマルトオリゴ糖、セロオリゴ糖、マンノオリゴ糖、ガラクトオリゴ糖等が挙げられる。 Examples of the oligosaccharide include malto-oligosaccharides, cellooligosaccharides, manno-oligosaccharides, galactooligosaccharides and the like having a degree of polymerization of 2 to 10.
また、上記に記載の単糖、単糖誘導体またはオリゴ糖を２種類以上配合して使用することもできる。 Further, two or more kinds of the monosaccharides, monosaccharide derivatives or oligosaccharides described above can be blended and used.
［乳化重合用モノマー］
本発明の乳化重合用乳化剤を用いた乳化重合に適用されうるモノマーとしては各種のものを挙げることができ、例えば、アクリル酸、アクリル酸メチル、アクリル酸ブチル、アクリル酸２−エチルヘキシル、メタクリル酸メチル、アクリロニトリル、アクリルアミド、アクリル酸ヒドロキシエステル等のアクリル系モノマー、例えば、スチレン、ジビニルベンゼン等の芳香族モノマー、酢酸ビニル等のビニルエステル系モノマー、塩化ビニル、塩化ビニリデン等のハロゲン化オレフィンモノマー、ブタジエン、イソプレン、クロロプレン等の共役系ジオレフィン系モノマー等の他、エチレン、無水マレイン酸、マレイン酸メチル等がある。本発明の乳化剤は、上記モノマーの１種または２種以上の乳化重合または懸濁重合に利用できる。
[Emulsion polymerization monomer]
Examples of the monomer that can be applied to the emulsion polymerization using the emulsifier for emulsion polymerization of the present invention include various monomers such as acrylic acid, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate. Acrylic monomers such as acrylonitrile, acrylamide, and acrylic acid hydroxy ester, aromatic monomers such as styrene and divinylbenzene, vinyl ester monomers such as vinyl acetate, halogenated olefin monomers such as vinyl chloride and vinylidene chloride, butadiene, In addition to conjugated diolefin monomers such as isoprene and chloroprene, there are ethylene, maleic anhydride, methyl maleate and the like. The emulsifier of the present invention can be used for emulsion polymerization or suspension polymerization of one or more of the above monomers.
［重合条件］
本発明の乳化重合用乳化剤を使用した乳化重合反応に使用される重合開始剤は従来公知のものでよく、例えば、過酸化水素、過硫酸カリウム、アゾビスイソブチロニトリル、ベンゾイルパーオキサイド等が利用できる。重合促進剤としては、亜硫酸水素ナトリウム、硫酸第１鉄アンモニウム等が使用できる。また、連鎖移動剤として、α−メチルスチレンダイマー、ｎ−ブチルメルカプタン、ｔ−ドデシルメルカプタンなどのメルカプタン類、四塩化炭素、四臭化炭素などのハロゲン化炭化水素などを用いてもよい。
[Polymerization conditions]
The polymerization initiator used in the emulsion polymerization reaction using the emulsifier for emulsion polymerization of the present invention may be a conventionally known one, such as hydrogen peroxide, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, etc. Available. As the polymerization accelerator, sodium bisulfite, ferrous ammonium sulfate, and the like can be used. Further, as a chain transfer agent, mercaptans such as α-methylstyrene dimer, n-butyl mercaptan, t-dodecyl mercaptan, halogenated hydrocarbons such as carbon tetrachloride and carbon tetrabromide may be used.
本発明の乳化重合用乳化剤の使用量は、通常、全モノマーに対して０．１〜２０．０％が適当である。なお、より好ましくは、０．２〜１０．０％が適当である。 The use amount of the emulsifier for emulsion polymerization of the present invention is usually suitably 0.1 to 20.0% with respect to all monomers. In addition, 0.2 to 10.0% is more preferable.
本発明の乳化重合用乳化剤は、それ単独でも乳化重合は良好に完結しうるが、さらにアニオン界面活性剤またはカチオン界面活性剤または／及び他のノニオン界面活性剤を併用してもよく、これにより乳化重合時の重合安定性が向上し、また後工程における処理特性を向上させることができる。 The emulsifier for emulsion polymerization of the present invention alone can complete emulsion polymerization satisfactorily. However, an anionic surfactant or a cationic surfactant or / and other nonionic surfactants may be used in combination. Polymerization stability at the time of emulsion polymerization can be improved, and processing characteristics in the subsequent process can be improved.
かかるアニオン界面活性剤、カチオン界面活性剤及びノニオン界面活性剤としては特に限定されないが、例えば、アニオン界面活性剤としては、脂肪酸セッケン、ロジン酸セッケン、アルキルスルホン酸塩、アルキルアリールスルホン酸塩、アルキルスルホコハク酸塩、ポオキシアルキレンアルキル硫酸塩、ポリオキシアルキレンアリール硫酸塩などが挙げられ、カチオン界面活性剤としてはステアリルトリメチルアンモニウム、セチルトリメチルアンモニウム、ラウリルトリメチルアンモニウムなどが挙げられ、ノニオン界面活性剤としては、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシアルキレンアルキルエーテル、アルキルポリグルコシド、ポリグリセリンアルキルエーテル、ポリオキシアルキレン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エステルなどが挙げられる。 The anionic surfactant, the cationic surfactant and the nonionic surfactant are not particularly limited. For example, examples of the anionic surfactant include fatty acid soap, rosin acid soap, alkyl sulfonate, alkyl aryl sulfonate, alkyl Examples include sulfosuccinate, polyoxyalkylene aryl sulfate, and polyoxyalkylene aryl sulfate. Examples of cationic surfactants include stearyl trimethyl ammonium, cetyl trimethyl ammonium, and lauryl trimethyl ammonium. Nonionic surfactants include , Polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, alkyl polyglucoside, polyglycerin alkyl ether, polyoxyalkylene fatty acid ester, Li glycerin fatty acid ester, and the like sorbitan fatty acid ester.
これらの界面活性剤の使用量としては、本発明の乳化重合用乳化剤１００部に対して、０．５〜１００重量部含まれることが好ましく、より好ましくは５〜６０重量部である。さらに好ましくは１０〜３０重量部である。 The amount of these surfactants to be used is preferably 0.5 to 100 parts by weight, more preferably 5 to 60 parts by weight, with respect to 100 parts by weight of the emulsifier for emulsion polymerization of the present invention. More preferably, it is 10-30 weight part.
また、乳化重合時の重合安定性を向上させる目的で公知の保護コロイド剤を併用することができる。併用できる保護コロイド剤としては、完全けん化ポリビニルアルコール（ＰＶＡ）、部分けん化ＰＶＡ、ヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルセルロース、ポリアクリル酸、アラビアゴムなどがある。 Moreover, a well-known protective colloid agent can be used together in order to improve the polymerization stability at the time of emulsion polymerization. Examples of protective colloid agents that can be used in combination include fully saponified polyvinyl alcohol (PVA), partially saponified PVA, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyacrylic acid, and gum arabic.
本発明の乳化重合用乳化剤の他の使用方法としては、ポリマーエマルションの安定性を改善するために、重合終了後のポリマーに添加し使用することができる。 As another method of using the emulsifier for emulsion polymerization of the present invention, it can be added to the polymer after completion of polymerization in order to improve the stability of the polymer emulsion.
［作用、その他］
本発明の乳化重合用乳化剤はその分子中の疎水基部分に共重合性の不飽和基を有し、重合性モノマー、殊にビニル系モノマー等との共重合性に優れ、ポリマー組成に組み込まれやすい。そのため、共重合性の反応性乳化剤として、ポリマーエマルションから得られたポリマーフィルム中に遊離した状態で存在する乳化剤量が著しく減少し、フィルムの耐水性、接着性、耐熱性、耐候性向上に極めて優れた効果を発揮する。かつポリマーエマルションの泡立ち、機械安定性等が著しく改善される。
[Action, other]
The emulsifier for emulsion polymerization of the present invention has a copolymerizable unsaturated group in the hydrophobic group portion of the molecule, is excellent in copolymerizability with polymerizable monomers, particularly vinyl monomers, and is incorporated into the polymer composition. Cheap. Therefore, as a copolymerizable reactive emulsifier, the amount of the emulsifier present in the polymer film obtained from the polymer emulsion is remarkably reduced, and the water resistance, adhesiveness, heat resistance and weather resistance of the film are greatly improved. Exhibits excellent effects. In addition, foaming and mechanical stability of the polymer emulsion are remarkably improved.
さらに、ジオキサンやアルデヒド類などの有害物質を大幅に低減したポリマーエマルションを得ることができる。 Furthermore, a polymer emulsion in which harmful substances such as dioxane and aldehydes are greatly reduced can be obtained.
本発明の乳化重合用乳化剤を添加して得られるポリマーエマルションは、例えば接着剤、被覆剤、含浸補強剤等として、木材、金属、紙、布、その他コンクリートなどに適用することができる。また、エマルションあるいはラテックスから取り出したポリマーは樹脂、ゴム、ポリマーの改質剤等に使用することができる。 The polymer emulsion obtained by adding the emulsifier for emulsion polymerization of the present invention can be applied to wood, metal, paper, cloth, other concrete, etc. as, for example, an adhesive, a coating agent, and an impregnation reinforcing agent. The polymer taken out from the emulsion or latex can be used as a resin, rubber, polymer modifier or the like.
以下、実施例および比較例により本発明をより詳細に説明するが、本発明はこれらの例により限定されることはない。なお、文中「部」は特に記載がない限り質量基準である。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited by these examples. In the text, “part” is based on mass unless otherwise specified.
〈製造例１〉
撹拌機、窒素導入管、及び温度計を備えた反応器に１−プロペニルフェノール１３４部、触媒として三フッ化ホウ素エーテル錯体を仕込み、炭素数１２、１４のα−オレフィンエポキシド（ＡＯＥ Ｘ２４、ダイセル化学工業（株）製）１９６部を滴下し、８０℃にて５時間撹拌反応を行った後、精製して中間体Ａを得た。
<Production Example 1>
A reactor equipped with a stirrer, a nitrogen inlet tube, and a thermometer was charged with 134 parts of 1-propenylphenol and a boron trifluoride ether complex as a catalyst, and an α-olefin epoxide having 12 or 14 carbon atoms (AOE X24, Daicel Chemical). 196 parts (manufactured by Kogyo Co., Ltd.) was added dropwise, followed by stirring reaction at 80 ° C. for 5 hours, followed by purification to obtain Intermediate A.
中間体Ａに触媒としてｐ−トルエンスルホン酸、そしてブチルグルコシド４０部を加えた後、１３０℃に昇温して３時間反応を行った。そのとき、反応器内を１０ミリバールに減圧して副生物であるブタノールを留去した。次に、水酸化ナトリウムを用いて中和を行った後、過剰の中間体Ａを除去して中間体Ａのポリグルコシド化合物を得た。これを精製して本発明品の乳化重合用乳化剤Ａとした。 After adding p-toluenesulfonic acid and 40 parts of butyl glucoside as catalysts to Intermediate A, the temperature was raised to 130 ° C. and the reaction was carried out for 3 hours. At that time, the pressure in the reactor was reduced to 10 mbar to distill off butanol as a by-product. Next, after neutralizing with sodium hydroxide, excess intermediate A was removed to obtain a polyglucoside compound of intermediate A. This was refine | purified and it was set as the emulsifier A for emulsion polymerization of this invention product.
〈製造例２〉
撹拌機、窒素導入管、及び温度計を備えた反応器に２−プロペニルフェノール１３４部、触媒として水酸化ナトリウムを仕込み、炭素数１２、１４のα−オレフィンエポキシド１９６部を滴下し、８０℃にて５時間撹拌反応を行った後、精製して中間体Ｂを得た。
<Production Example 2>
A reactor equipped with a stirrer, a nitrogen inlet tube, and a thermometer was charged with 134 parts of 2-propenylphenol and sodium hydroxide as a catalyst, and 196 parts of an α-olefin epoxide having 12 and 14 carbon atoms was added dropwise to 80 ° C. Then, the mixture was stirred for 5 hours and purified to obtain Intermediate B.
中間体Ｂに触媒としてアルキルベンゼンスルホン酸、そしてグルコース５５部を加えた後１３０℃に昇温して３時間反応を行った。そのとき、反応器内を１０ミリバールに減圧して副生物である水を留去した。次に、水酸化ナトリウムを用いて中和を行った後、過剰の中間体Ｂを除去して中間体Ｂのポリグルコシド化合物を得た。これを精製して本発明品の乳化重合用乳化剤Ｂとした。 After adding alkylbenzene sulfonic acid as a catalyst and 55 parts of glucose to Intermediate B, the temperature was raised to 130 ° C. and the reaction was carried out for 3 hours. At that time, the pressure in the reactor was reduced to 10 mbar, and water as a by-product was distilled off. Next, after neutralizing with sodium hydroxide, excess intermediate B was removed to obtain a polyglucoside compound of intermediate B. This was refine | purified and it was set as the emulsifier B for emulsion polymerization of this invention product.
〈製造例３〉
撹拌機、窒素導入管、及び温度計を備えた反応器にビニルフェノール１２０部、触媒として四塩化スズ、重合禁止剤としてハイドロキノンを加え、５０℃までの温度で炭素数１２、１４のα−オレフィンエポキシド（エポサイザーＭ−２４、大日本インキ化学工業（株）製）を１９６部を滴下し、６０℃で５時間反応を行った後、精製して中間体Ｃを得た。
<Production Example 3>
120 parts of vinylphenol, tin tetrachloride as a catalyst, and hydroquinone as a polymerization inhibitor are added to a reactor equipped with a stirrer, a nitrogen introduction tube, and a thermometer, and an α-olefin having 12 and 14 carbon atoms at a temperature up to 50 ° C. 196 parts of epoxide (Eposizer M-24, manufactured by Dainippon Ink & Chemicals, Inc.) was added dropwise, reacted at 60 ° C. for 5 hours, and then purified to obtain Intermediate C.
触媒としてアルキルベンゼンスルホン酸、重合禁止剤としてハイドロキノン、そしてブチルグルコシド３５部を加えた後、少量の空気を導入しながら１１０℃に昇温して４時間反応を行った。そのとき、反応器内を１０ミリバールに減圧して副生物であるブタノールを留去した。次に、水酸化ナトリウムを用いて中和を行った後、過剰の中間体Ｃを除去して中間体Ｃのポリグルコシド化合物を得た。これを精製して本発明品の乳化重合用乳化剤Ｃとした。 After adding alkylbenzene sulfonic acid as a catalyst, hydroquinone as a polymerization inhibitor, and 35 parts of butyl glucoside, the temperature was raised to 110 ° C. and a reaction was carried out for 4 hours while introducing a small amount of air. At that time, the pressure in the reactor was reduced to 10 mbar to distill off butanol as a by-product. Next, after neutralizing with sodium hydroxide, excess intermediate C was removed to obtain a polyglucoside compound of intermediate C. This was refine | purified and it was set as the emulsifier C for emulsion polymerization of this invention product.
〈製造例４〉
製造例１の方法に準じて、炭素数１２、１４のα−オレフィンエポキシドの代わりに、炭素数１２のα−オレフィンエポキシド（Ｖｉｋｏｌｏｘ１２、ＡＲＫＥＭＡ社製）１８４部として中間体Ｄを得た。またブチルグルコシドを３５部として本発明品の乳化重合用乳化剤Ｄを得た。
<Production Example 4>
In accordance with the method of Production Example 1, Intermediate D was obtained as 184 parts of an α-olefin epoxide having 12 carbon atoms (Vikolox 12, manufactured by ARKEMA) instead of the α-olefin epoxide having 12 carbon atoms and 14 carbon atoms. Moreover, the emulsifier D for emulsion polymerization of this invention product was obtained by using 35 parts of butyl glucoside.
〈製造例５〉
製造例３の方法に準じて、炭素数１２、１４のα−オレフィンエポキシド及びビニルフェノールの代わりに、炭素数１２のα−オレフィンエポキシドを１８４部及び１−メチルビニルフェノールを１３４部として中間体Ｅを得た。またブチルグルコシドを７５部として本発明品の乳化重合用乳化剤Ｅを得た。
<Production Example 5>
According to the method of Production Example 3, instead of α-olefin epoxide having 12 and 14 carbon atoms and vinylphenol, 184 parts of α-olefin epoxide having 12 carbon atoms and 134 parts of 1-methylvinylphenol were used as intermediate E. Got. Moreover, the emulsifier E for emulsion polymerization of this invention product was obtained for 75 parts of butyl glucoside.
〈製造例６〉
製造例１の方法に準じて、炭素数１２、１４のα−オレフィンエポキシド及び１−プロペニルフェノールの代わりに、炭素数１４のα−オレフィンエポキシド（Ｖｉｋｏｌｏｘ１４、ＡＲＫＥＭＡ社製）を２１２部及び２−メチルー２−プロペニルフェノールを１４８部として中間体Ｆを得た。またブチルグルコシドを７０部として本発明品の乳化重合用乳化剤Ｆを得た。
<Production Example 6>
According to the method of Production Example 1, instead of α-olefin epoxide having 12 and 14 carbon atoms and 1-propenylphenol, 212 parts of α-olefin epoxide having 14 carbon atoms (Vikolox14, manufactured by ARKEMA) and 2-methyl- Intermediate F was obtained using 148 parts of 2-propenylphenol. Further, the emulsifier F for emulsion polymerization of the present invention was obtained with 70 parts of butyl glucoside.
〈製造例７〉
製造例２の方法に準じて、炭素数１２、１４のα−オレフィンエポキシドの代わりに、炭素数１２の分岐型α−オレフィンエポキシドを１８４部として中間体Ｇを得た。また、グルコースを４０部として本発明品の乳化重合用乳化剤Ｇを得た。
<Production Example 7>
According to the method of Production Example 2, Intermediate G was obtained using 184 parts of a branched α-olefin epoxide having 12 carbon atoms instead of the α-olefin epoxide having 12 or 14 carbon atoms. Moreover, the emulsifier G for emulsion polymerization of this invention product was obtained by making glucose into 40 parts.
〈製造例８〉
製造例１の方法に準じて、炭素数１２、１４のα−オレフィンエポキシドの代わりに、炭素数１４の分岐型α−オレフィンエポキシドを２１２部として中間体Ｈを得た。また、ブチルグルコシドを３５部として本発明品の乳化重合用乳化剤Ｈを得た。
<Production Example 8>
In accordance with the method of Production Example 1, Intermediate H was obtained using 212 parts of branched α-olefin epoxide having 14 carbon atoms instead of α-olefin epoxide having 12 or 14 carbon atoms. Moreover, the emulsifier H for emulsion polymerization of this invention product was obtained by using 35 parts of butyl glucoside.
〈製造例９〉
製造例２の方法に準じて、炭素数１２、１４のα−オレフィンエポキシドの代わりに、炭素数１６の分岐型α−オレフィンエポキシドを２４０部として中間体Ｉを得た。また、グルコースを３０部として本発明品の乳化重合用乳化剤Ｉを得た。
<Production Example 9>
According to the method of Production Example 2, Intermediate I was obtained using 240 parts of a branched α-olefin epoxide having 16 carbon atoms instead of the α-olefin epoxide having 12 or 14 carbon atoms. Moreover, the emulsifier I for emulsion polymerization of this invention product was obtained by making glucose into 30 parts.
〈製造例１０〉
製造例１の方法に準じて、炭素数１２、１４のα−オレフィンエポキシド及び１−プロペニルフェノールの代わりに、１６、１８のα−オレフィンエポキシド（エポサイザーＭ−６８、大日本インキ化学工業（株）製）を２５２部及び２−メチルー２−プロペニルフェノールを１４８部として中間体Ｊを得た。またブチルグルコシドを６０部として本発明品の乳化重合用乳化剤Ｊを得た。
<Production Example 10>
In accordance with the method of Production Example 1, instead of α-olefin epoxide having 12 or 14 carbon atoms and 1-propenylphenol, α-olefin epoxide having 16 or 18 (Eposizer M-68, Dainippon Ink & Chemicals, Inc.) Product) and 148 parts of 2-methyl-2-propenylphenol. Moreover, the emulsifier J for emulsion polymerization of this invention product was obtained by using 60 parts of butyl glucoside.
〈製造例１１〉
製造例１の方法に準じて、炭素数１２、１４のα−オレフィンエポキシドの代わりに、炭素数１６、１８のα−オレフィンエポキシド（ＡＯＥ Ｘ６８、ダイセル化学工業（株）製）を２５２部として中間体Ｋを得た。また、ブチルグルコシドの代わりにマルトースとマルトトリオースの混合物を１００部として本発明品の乳化重合用乳化剤Ｋを得た。
<Production Example 11>
According to the method of Production Example 1, instead of the α-olefin epoxide having 12 or 14 carbon atoms, 252 parts of an α-olefin epoxide having 16 or 18 carbon atoms (AOE X68, manufactured by Daicel Chemical Industries, Ltd.) is used as an intermediate. Body K was obtained. Moreover, the emulsifier K for emulsion polymerization of the present invention was obtained using 100 parts of a mixture of maltose and maltotriose instead of butyl glucoside.
〈実施例及び比較例〉
実施例及び比較例に用いた乳化重合用乳化剤は表１の通りである。
<Examples and Comparative Examples>
Table 1 shows emulsifiers for emulsion polymerization used in Examples and Comparative Examples.
〈使用例１〉
アクリル酸ブチル１００部、スチレン１００部、イオン交換水２９０部および乳化重合用乳化剤１０部を混合して混合モノマー乳濁液を調製し、窒素ガスにて溶存酸素を除去した。次に攪拌機、還流冷却器、温度計および滴下漏斗を備えた反応器に、上記混合モノマー乳濁液を１００部仕込み、８０℃に昇温し、過硫酸カリウム０．５部を加えて先行重合させた。次いで、重合開始１０分後より３時間かけて残りの混合モノマー乳濁液４００部を滴下して重合させた。さらに、続けて重合温度にて２時間熟成した後、冷却してポリマーエマルションを得た。
<Usage example 1>
A mixed monomer emulsion was prepared by mixing 100 parts of butyl acrylate, 100 parts of styrene, 290 parts of ion-exchanged water and 10 parts of an emulsifier for emulsion polymerization, and dissolved oxygen was removed with nitrogen gas. Next, a reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel was charged with 100 parts of the above mixed monomer emulsion, heated to 80 ° C., and 0.5 parts of potassium persulfate was added for prepolymerization. I let you. Next, 400 parts of the remaining mixed monomer emulsion was dropped over 3 hours from 10 minutes after the start of polymerization, and polymerization was performed. Further, after aging for 2 hours at the polymerization temperature, the mixture was cooled to obtain a polymer emulsion.
使用した乳化重合用乳化剤は表２に示す通りである。また、併用アニオン性乳化剤としてラウリル硫酸エステルナトリウム塩を乳化重合用乳化剤の内１０重量％使用した。 The emulsifiers for emulsion polymerization used are as shown in Table 2. Moreover, 10% by weight of an emulsifier for emulsion polymerization was used as a combined anionic emulsifier.
使用した乳化重合用乳化剤のジオキサン及びホルムアルデヒドの含有量及び、得られたポリマーエマルションについて、重合安定性、機械安定性、粒子径、起泡性、フィルムの光沢性をそれぞれ評価した。評価方法は以下の通りである。結果は表２に示す。 The contents of dioxane and formaldehyde of the emulsifier for emulsion polymerization used, and the obtained polymer emulsion were evaluated for polymerization stability, mechanical stability, particle diameter, foamability, and gloss of the film. The evaluation method is as follows. The results are shown in Table 2.
［ジオキサン及びホルムアルデヒドの含有量］
乳化重合用乳化剤に含まれるジオキサンをＧＣ、ホルムアルデヒドをアセチルアセトン法を用い吸光光度法で定量を行った。その結果を、ジオキサン量が１ｐｐｍ未満：○、１〜１０ｐｐｍ：△、１０ｐｐｍ以上：×、ホルムアルデヒド量が１ｐｐｍ未満：○、１〜１０ｐｐｍ：△、１０ｐｐｍ以上：×、として示す。
[Contents of dioxane and formaldehyde]
The dioxane contained in the emulsifier for emulsion polymerization was determined by spectrophotometry using GC and formaldehyde using the acetylacetone method. The results are shown as dioxane content less than 1 ppm: ◯, 1-10 ppm: Δ, 10 ppm or more: x, formaldehyde content less than 1 ppm: ◯, 1-10 ppm: Δ, 10 ppm or more: x.
［重合安定性］
重合後のポリマーエマルションを８０メッシュのろ布を用いてろ過し、ろ布上の残渣を水洗後、乾燥し、その重量をエマルションの固形分に対し％で示す。
[Polymerization stability]
The polymer emulsion after polymerization is filtered using an 80-mesh filter cloth, and the residue on the filter cloth is washed with water and dried, and the weight is expressed in% with respect to the solid content of the emulsion.
［機械安定性］
ポリマーエマルション５０ｇをマーロン型試験器にて荷重１０ｋｇ、回転数１０００ｒｐｍで５分間撹拌し、生成した凝集物を８０メッシュの金網でろ過し、残渣を水洗後、乾燥し、その重量をエマルションの固形分に対し％で示す。
[Machine stability]
50 g of the polymer emulsion was stirred with a Marlon tester at a load of 10 kg and a rotational speed of 1000 rpm for 5 minutes, the resulting aggregate was filtered through an 80 mesh wire mesh, the residue was washed with water and dried, and its weight was determined as the solid content of the emulsion. In%.
［粒子径］
動的光散乱式粒度分布測定装置（日機装製 ＭＩＣＲＯＴＲＡＣ ＵＰＡ９３４０）にて測定し、μｍで示す。
[Particle size]
It is measured with a dynamic light scattering type particle size distribution analyzer (MICROTRAC UPA9340 manufactured by Nikkiso), and is shown in μm.
［起泡性］
エマルションを水で２倍希釈し、１００ｍｌネスラー管に３０ｃｃ入れ、３０回倒立させてから静置５分後における泡の量（ｍｌ）を測定した。
[Foaming]
The emulsion was diluted 2-fold with water, put in 30 cc in a 100 ml Nessler tube, inverted 30 times, and then the amount of foam (ml) after 5 minutes of standing was measured.
［フィルムの光沢性］
ガラスプレート上に０．５ｍｍ（ｗｅｔ）のエマルション膜を作り、室温で２４時間放置してフィルムを作成した。このフィルムの光沢性を目視にて観察し３段階で評価した。その結果を、優れる：○、可：△、不可：×、として示す。
[Glossiness of film]
A 0.5 mm (wet) emulsion film was formed on a glass plate and allowed to stand at room temperature for 24 hours to prepare a film. The glossiness of this film was visually observed and evaluated in three stages. The results are shown as excellent: ◯, acceptable: Δ, impossible: x.
〈使用例２〉
攪拌機、還流冷却器、温度計および滴下漏斗を備えた反応器に、イオン交換水１３５部、緩衝剤として炭酸水素ナトリウム０．５部を仕込み、８０℃まで昇温させ、窒素ガスにて水中の溶存酸素を除去した。これとは別にメタクリル酸メチル７５部、アクリル酸エチル１７１部、アクリル酸４部、乳化重合用乳化剤８部、イオン交換水１１０部とを混合して、モノマーエマルションを調製した。次に、上記で調製したモノマーエマルション４０部を一括して上記反応器に添加し、１０分間撹拌後、重合開始剤である過硫酸アンモニウム０．５部を加え、１０分間撹拌した。次に残りのモノマーエマルションを３時間かけて滴下して重合反応を行い、４０℃まで冷却後、アンモニア水でｐＨ８〜９に調整してポリマーエマルションを得た。
<Usage example 2>
A reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel was charged with 135 parts of ion-exchanged water and 0.5 part of sodium bicarbonate as a buffering agent, heated to 80 ° C. Dissolved oxygen was removed. Separately, 75 parts of methyl methacrylate, 171 parts of ethyl acrylate, 4 parts of acrylic acid, 8 parts of an emulsifier for emulsion polymerization, and 110 parts of ion-exchanged water were mixed to prepare a monomer emulsion. Next, 40 parts of the monomer emulsion prepared above were added all at once to the reactor, and after stirring for 10 minutes, 0.5 part of ammonium persulfate as a polymerization initiator was added and stirred for 10 minutes. Next, the remaining monomer emulsion was added dropwise over 3 hours to conduct a polymerization reaction, cooled to 40 ° C., and adjusted to pH 8-9 with aqueous ammonia to obtain a polymer emulsion.
使用した乳化重合用乳化剤は表３に示す通りである。また、併用アニオン性乳化剤として直鎖アルキルベンゼンスルホン酸ナトリウム塩を乳化重合用乳化剤の内１０重量％使用した。 The emulsifiers for emulsion polymerization used are as shown in Table 3. Further, as a combined anionic emulsifier, linear alkylbenzene sulfonic acid sodium salt was used in an amount of 10% by weight of the emulsion polymerization emulsifier.
得られたポリマーエマルションについて、重合安定性、粒子径、ＶＯＣ量、未反応乳化剤量、耐水性をそれぞれ評価した。重合安定性、粒子径の評価方法は上記の評価方法と同様である。ＶＯＣ量、未反応乳化剤量、耐水性評価方法は以下の通りである。結果は表３に示す。 The obtained polymer emulsion was evaluated for polymerization stability, particle diameter, VOC amount, unreacted emulsifier amount, and water resistance. The evaluation method of polymerization stability and particle diameter is the same as the above evaluation method. The amount of VOC, the amount of unreacted emulsifier, and the water resistance evaluation method are as follows. The results are shown in Table 3.
［ＶＯＣ量］
ポリマーエマルションに含まれるＶＯＣ量をヘッドスペースＧＣにより測定を行った。その結果を、１０ｐｐｍ未満：○、１０〜５０ｐｐｍ：△、５０ｐｐｍ以上：×、として示す。
[VOC amount]
The amount of VOC contained in the polymer emulsion was measured by headspace GC. The results are shown as less than 10 ppm: ◯, 10-50 ppm: Δ, 50 ppm or more: x.
［未反応乳化剤量］
ポリマーエマルションにメタノールを加えて、ポリマーを凝固し、遠心分離処理後、その上澄みを用い、ＨＰＬＣ−ＭＳ法にて未反応乳化剤量を測定し、％で示す。
[Unreacted emulsifier amount]
Methanol is added to the polymer emulsion to solidify the polymer, and after centrifugation, the amount of unreacted emulsifier is measured by the HPLC-MS method using the supernatant, and is shown in%.
［耐水性試験］
ガラス板上に０．５ｍｍ厚のポリマーフィルムを作製し、これを水に浸漬し、前記ポリマーフィルムを透して４．５ポイント文字が読めなくなるまでの時間を測定した。その結果を、３００時間以上：○、３００〜２００時間：△、２００時間未満：×、として示す。
[Water resistance test]
A polymer film having a thickness of 0.5 mm was prepared on a glass plate, immersed in water, and the time until 4.5 point characters could not be read through the polymer film was measured. The results are shown as 300 hours or more: ◯, 300 to 200 hours: Δ, less than 200 hours: x.
〈使用例３〉
攪拌機、還流冷却器、温度計および滴下漏斗を備えた反応器に、イオン交換水２５０部を仕込み、８０℃まで昇温させ、窒素ガスにて水中の溶存酸素を除去した。次にアクリル酸ブチル１２５部とアクリル酸２−エチルヘキシル１２５部に乳化重合用乳化剤５部を溶解させた混合モノマー液のうち５０部を反応器に仕込み、次いで過硫酸アンモニウム０．５部を加えて先行重合させ、重合開始１０分後より３時間かけて残りの混合モノマー液２０５部を滴下して重合させた。続けて重合温度にてさらに２時間熟成した後、４０℃まで冷却後、アンモニア水でｐＨ８〜９に調整してポリマーエマルションを得た。
<Usage example 3>
A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was charged with 250 parts of ion-exchanged water, heated to 80 ° C., and dissolved oxygen in water was removed with nitrogen gas. Next, 50 parts of a mixed monomer solution prepared by dissolving 5 parts of an emulsifier for emulsion polymerization in 125 parts of butyl acrylate and 125 parts of 2-ethylhexyl acrylate was charged into the reactor, and then 0.5 part of ammonium persulfate was added to the reactor. Polymerization was performed, and the remaining 205 parts of the mixed monomer solution was added dropwise over 3 hours from 10 minutes after the start of the polymerization. Subsequently, the mixture was further aged for 2 hours at the polymerization temperature, cooled to 40 ° C., and adjusted to pH 8-9 with aqueous ammonia to obtain a polymer emulsion.
使用した乳化重合用乳化剤は表４に示す通りである。また、併用アニオン性乳化剤としてポリオキシエチレンスチレン化フェニルエーテルリン酸エステル（ＥＯ８モル付加体）を乳化重合用乳化剤の内１０重量％使用した。 The emulsifiers for emulsion polymerization used are as shown in Table 4. Further, 10% by weight of an emulsifier for emulsion polymerization was used as a combined anionic emulsifier, polyoxyethylene styrenated phenyl ether phosphate ester (EO 8 mol adduct).
得られたポリマーエマルションについて、重合安定性、機械安定性、未反応乳化剤量、耐熱着色性、接着性をそれぞれ評価した。重合安定性、機械安定性、未反応乳化剤量の評価方法は上記と同様である。耐熱着色性、接着性の評価方法は以下の通りである。結果は表４に示す。 About the obtained polymer emulsion, polymerization stability, mechanical stability, the amount of unreacted emulsifier, heat-resistant coloring property, and adhesiveness were evaluated, respectively. The evaluation methods for polymerization stability, mechanical stability, and amount of unreacted emulsifier are the same as described above. The evaluation methods for heat resistant colorability and adhesiveness are as follows. The results are shown in Table 4.
［耐熱着色性］
ガラス板上に０．５ｍｍ厚のポリマーフィルムを作製し、２００℃に調整した熱風乾燥器内で３０分間熱処理して、ポリマーフィルムの着色を目視で観察した。その結果を、全く着色が認められない：○、淡い黄色に着色している：△、濃い褐色に着色している：×、として示す。
[Heat resistant coloring]
A polymer film having a thickness of 0.5 mm was prepared on a glass plate, heat-treated for 30 minutes in a hot air drier adjusted to 200 ° C., and coloring of the polymer film was visually observed. The results are shown as no coloring at all: ◯, pale yellow: Δ, dark brown: x.
［接着性］
５ｃｍ幅に切ったＰＥＴフィルム上にエマルションを２５μｍ（ｄｒｙ）の厚さに塗工し、熱処理した後ＳＵＳ板に貼り付け、ローラ圧着する。接着面が５ｃｍ×５ｃｍとなるようにフィルムを剥がし、フィルムの端に２００ｇの重りを吊り下げて剥がれるまでの時間（秒）を測定した。
[Adhesiveness]
The emulsion is applied to a thickness of 25 μm (dry) on a PET film cut to a width of 5 cm, heat-treated, then attached to a SUS plate, and roller-pressed. The film was peeled off so that the adhesive surface was 5 cm × 5 cm, and a time (second) until the film was peeled off by hanging a weight of 200 g on the edge of the film was measured.
〈使用例４〉
攪拌機、還流冷却器、温度計および滴下漏斗を備えた反応器に、イオン交換水１３１部、緩衝剤として炭酸水素ナトリウム０．５部を仕込み、７０℃まで昇温させ、窒素ガスにて水中の溶存酸素を除去した。これとは別に酢酸ビニル２５０部、乳化重合用乳化剤８部、イオン交換水１１０部とを混合して、モノマーエマルションを調製した。次に、上記で調製したモノマーエマルション４０部を一括して上記反応容器に添加し、１０分間撹拌後、重合開始剤である過硫酸アンモニウム０．５部を加え、１０分間撹拌した。次に残りのモノマーエマルションを３時間かけて滴下して重合反応を行い、４０℃まで冷却後、アンモニア水でｐＨ８〜９に調整してポリマーエマルションを得た。
<Usage example 4>
A reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel was charged with 131 parts of ion-exchanged water and 0.5 part of sodium bicarbonate as a buffering agent, heated to 70 ° C. Dissolved oxygen was removed. Separately, 250 parts of vinyl acetate, 8 parts of an emulsifier for emulsion polymerization, and 110 parts of ion-exchanged water were mixed to prepare a monomer emulsion. Next, 40 parts of the monomer emulsion prepared above were added all at once to the reaction vessel, and after stirring for 10 minutes, 0.5 part of ammonium persulfate as a polymerization initiator was added and stirred for 10 minutes. Next, the remaining monomer emulsion was added dropwise over 3 hours to conduct a polymerization reaction, cooled to 40 ° C., and adjusted to pH 8-9 with aqueous ammonia to obtain a polymer emulsion.
使用した乳化重合用乳化剤は表５に示す通りである。 The emulsifiers for emulsion polymerization used are as shown in Table 5.
得られたポリマーエマルションについて、重合安定性、粒子径、接着性をそれぞれ評価した。重合安定性、粒子径評価方法は上記の評価方法と同様である。接着性の評価方法は以下の通りである。結果を表５に示す。 The obtained polymer emulsion was evaluated for polymerization stability, particle diameter, and adhesiveness. The polymerization stability and particle size evaluation method is the same as the above evaluation method. The evaluation method of adhesiveness is as follows. The results are shown in Table 5.
［接着性］
５ｃｍ幅に切った合板上にエマルションを２５μｍ（ｄｒｙ）の厚さに塗工し、熱処理した後５ｃｍ幅の綿製の布を貼り付け、ローラ圧着する。接着面が５ｃｍ×５ｃｍとなるように布を剥がし、はがした布の端に１Ｋｇの重りを吊り下げて剥がれるまでの時間（秒）を測定した。
[Adhesiveness]
The emulsion is coated on a plywood cut to a width of 5 cm to a thickness of 25 μm (dry), heat-treated, and then a 5 cm wide cotton cloth is affixed and roller-pressed. The cloth was peeled off so that the adhesive surface was 5 cm × 5 cm, and a time (second) until the piece was peeled off by hanging a 1 kg weight on the edge of the peeled cloth was measured.
表２〜表５から、本発明にかかる乳化重合用乳化剤は、エマルションの重合安定性、機械安定性が良好で、乳化剤に含まれるアルデヒドやジオキサンの生成量が極めて少量であり、エマルション中のＶＯＣ量を大幅に低減できる。また、未反応の乳化剤量が少なく得られたポリマーエマルションのフィルム光沢性、耐水性、接着性、耐熱性などの諸特性が従来の乳化重合用乳化剤を用いたものより優れることが明らかである。 From Table 2 to Table 5, the emulsifier for emulsion polymerization according to the present invention has good polymerization stability and mechanical stability of the emulsion, and the amount of aldehyde and dioxane contained in the emulsifier is extremely small, and the VOC in the emulsion The amount can be greatly reduced. It is also clear that the polymer emulsion obtained with a small amount of unreacted emulsifier is superior in properties such as film gloss, water resistance, adhesiveness, heat resistance and the like using conventional emulsifiers for emulsion polymerization.
本発明の乳化重合用乳化剤を添加して得られるポリマーエマルションは、例えば接着剤、被覆剤、含浸補強剤等として、木材、金属、紙、布、その他コンクリートなどに適用することができる。また、エマルションあるいはラテックスから取り出したポリマーは樹脂、ゴム、ポリマーの改質剤等に使用することができる。
The polymer emulsion obtained by adding the emulsifier for emulsion polymerization of the present invention can be applied to wood, metal, paper, cloth, other concrete, etc. as, for example, an adhesive, a coating agent, and an impregnation reinforcing agent. The polymer taken out from the emulsion or latex can be used as a resin, rubber, polymer modifier or the like.
Claims (4)
A polymer emulsion obtained by the method for producing a polymer emulsion according to claim 3.
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| CN103797034B (en) * | 2012-01-16 | 2015-03-04 | 第一工业制药株式会社 | Emulsifying agent for emulsion polymerization |
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