JP2006273882A - Emulsifying agent for emulsion polymerization - Google Patents
Emulsifying agent for emulsion polymerization Download PDFInfo
- Publication number
- JP2006273882A JP2006273882A JP2005090279A JP2005090279A JP2006273882A JP 2006273882 A JP2006273882 A JP 2006273882A JP 2005090279 A JP2005090279 A JP 2005090279A JP 2005090279 A JP2005090279 A JP 2005090279A JP 2006273882 A JP2006273882 A JP 2006273882A
- Authority
- JP
- Japan
- Prior art keywords
- emulsion polymerization
- raw material
- emulsifier
- general formula
- parts
- 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.)
- Pending
Links
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims abstract description 42
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 42
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 38
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000000129 anionic group Chemical group 0.000 claims abstract description 7
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 37
- 229920000642 polymer Polymers 0.000 abstract description 30
- 238000006116 polymerization reaction Methods 0.000 abstract description 16
- 238000005187 foaming Methods 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000000178 monomer Substances 0.000 description 17
- -1 alkylphenyl ether Chemical compound 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000002245 particle Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 238000009826 distribution Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 125000001165 hydrophobic group Chemical group 0.000 description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000004094 surface-active agent Substances 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
- 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 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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-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
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- CCTFAOUOYLVUFG-UHFFFAOYSA-N 2-(1-amino-1-imino-2-methylpropan-2-yl)azo-2-methylpropanimidamide Chemical compound NC(=N)C(C)(C)N=NC(C)(C)C(N)=N CCTFAOUOYLVUFG-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-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
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 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
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
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- 239000000919 ceramic Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
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- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
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- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 238000000034 method Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- 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に関する。 The present invention relates to an emulsifier for emulsion polymerization used in emulsion polymerization.
従来、乳化重合用乳化剤としては、ノニルフェノール、オクチルフェノール等のアルキルフェノールにエチレンオキサイド等のアルキレンオキサイドを付加してなるアルキルフェニルエーテル型の非イオン性界面活性剤や、これを硫酸エステル化したアニオン界面活性剤が広く用いられていた。しかし、近年、アルキルフェノールは難生分解性であるため、環境に対する負荷が大きいという問題が指摘されている。そのため、乳化重合用乳化剤の疎水基原料としても、アルキルフェノールから脂肪族アルコールへ移行してきている。 Conventionally, as an emulsifier for emulsion polymerization, an alkylphenyl ether type nonionic surfactant obtained by adding an alkylene oxide such as ethylene oxide to an alkylphenol such as nonylphenol or octylphenol, or an anionic surfactant obtained by sulfate conversion of this Was widely used. However, in recent years, since alkylphenol is hardly biodegradable, it has been pointed out that the burden on the environment is large. For this reason, as a hydrophobic group raw material for emulsifiers for emulsion polymerization, alkylphenols have been shifted to aliphatic alcohols.
これに対し、下記特許文献１には、疎水基が脂肪族アルコール残基である乳化重合用乳化剤として、オキソ法によって合成された炭素数１３のアルコールに、アルキレンオキサイドを付加してなるエーテル型の非イオン又はアニオン界面活性剤が開示されている。
乳化重合用乳化剤に要求される性能としては、重合時の乳化安定性、得られるポリマーエマルジョンの機械安定性等があり、上記特許文献１に開示された乳化重合用乳化剤であると、これらの改善効果が認められるものの、なお不十分であった。また、得られるポリマーエマルジョンを塗料用途に用いる場合には、ポリマーエマルジョンの泡立ちが少ないこと、また該エマルジョンから形成されるフィルムの光沢性に優れることが求められるが、上記従来の乳化重合用乳化剤で重合したポリマーエマルジョンはこれらの点でも不十分なものであった。 The performance required for the emulsion polymerization emulsifier includes emulsion stability during polymerization, mechanical stability of the resulting polymer emulsion, and the like. Although the effect was recognized, it was still insufficient. In addition, when the obtained polymer emulsion is used for coating applications, it is required that the polymer emulsion has less foaming and that the film formed from the emulsion is excellent in glossiness. The polymer emulsion polymerized was insufficient in these respects.
本発明は、以上の点に鑑みてなされたものであり、重合時の乳化安定性、得られるポリマーエマルジョンの機械安定性に優れるとともに、泡立ちが少なく、更にフィルムの光沢性に優れるポリマーエマルジョンが得られる乳化重合用乳化剤を提供することを目的とする。 The present invention has been made in view of the above points, and provides a polymer emulsion having excellent emulsion stability during polymerization, mechanical stability of the resulting polymer emulsion, less foaming, and excellent film gloss. An object of the present invention is to provide an emulsifier for emulsion polymerization.
本発明者らは、上記の点に鑑み鋭意検討していく中で、疎水基原料として特定範囲の分岐度の脂肪族アルコールを用いるとともに、原料非イオン界面活性剤の多分散度を特定の範囲内に設定することにより、上記の課題が解決されることを見い出し、本発明を完成するに至った。 In the course of diligent investigations in view of the above points, the present inventors use aliphatic alcohols having a specific range of branching degree as the hydrophobic group raw material, and the polydispersity of the raw material nonionic surfactant within a specific range. It has been found that the above-mentioned problems can be solved by setting the value within the range, and the present invention has been completed.
すなわち、本発明に係る乳化重合用乳化剤は、下記一般式（１）で表されるアニオン界面活性剤であって、原料非イオン界面活性剤の多分散度Ｍｗ／Ｍｎが１．１０〜１．２０、分岐度が０．８〜２．５であるアニオン界面活性剤を含有するものである。 That is, the emulsifier for emulsion polymerization according to the present invention is an anionic surfactant represented by the following general formula (1), and the polydispersity Mw / Mn of the raw material nonionic surfactant is 1.10-1. 20. An anionic surfactant having a branching degree of 0.8 to 2.5 is contained.
Ｒ１−Ｏ−（ＡＯ）ｚ−Ｘ （１）
（式中、Ｒ１は、炭素数が１２〜１４であるアルキル基を表し、ＡＯはオキシアルキレン基を表し、ｚは１〜５０の整数であり、Ｘはアニオン性親水基を表す。ＡＯの付加形態はランダム付加、ブロック付加又はこれらの混合付加である。）
R 1 -O- (AO) z- X (1)
(In the formula, R 1 represents an alkyl group having 12 to 14 carbon atoms, AO represents an oxyalkylene group, z represents an integer of 1 to 50, and X represents an anionic hydrophilic group. (The addition form is random addition, block addition, or mixed addition thereof.)
本発明の乳化重合用乳化剤は、上記一般式（１）において、Ｒ１がブテントリマーのオキソ反応から得られたアルコールから誘導されたものである。 The emulsifier for emulsion polymerization of the present invention is one in which R 1 is derived from an alcohol obtained from an oxo reaction of a butene trimer in the above general formula (1).
また、本発明の乳化重合用乳化剤は、上記一般式（１）において、Ｒ１がゲルベ反応から得られたアルコールから誘導されたものでもよい。 Moreover, the emulsifier for emulsion polymerization of the present invention may be one in which R 1 is derived from an alcohol obtained from the Gerve reaction in the above general formula (1).
また、本発明の乳化重合用乳化剤においては、上記一般式（１）において、Ｘが、下記一般式（２）〜（６）のいずれかで表される基であることが好ましい。 In the emulsifier for emulsion polymerization of the present invention, in the general formula (1), X is preferably a group represented by any one of the following general formulas (2) to (6).
Ｘ：−ＳＯ３Ｍ （２）
−ＰＯ３Ｍ２ （３）
−Ｐ（Ｒ２）Ｏ２Ｍ （４）
−ＣＨ２ＣＯＯＭ （５）
−ＣＯ−ＣＨ２−ＣＨ（ＳＯ３Ｍ）ＣＯＯＭ （６）
（式中、Ｍはそれぞれ独立に水素、アルカリ金属、ＮＨ４又はアルカノールアミン残基であり、Ｒ２は上記一般式（１）のＸ以外の残基である。）
X: -SO 3 M (2)
-PO 3 M 2 (3)
-P (R 2) O 2 M (4)
—CH 2 COOM (5)
-CO-CH 2 -CH (SO 3 M) COOM (6)
(In the formula, each M is independently a hydrogen, alkali metal, NH 4 or alkanolamine residue, and R 2 is a residue other than X in the general formula (1).)
本発明の乳化重合用乳化剤であると、重合安定性、機械安定性が良好であり、泡立ちの少ないポリマーエマルジョンが得られる。また、得られるポリマーエマルジョンの粒子径分布が狭く、塗料用途に用いた場合に良好な光沢を有するフィルムを得ることができる。 With the emulsifier for emulsion polymerization of the present invention, a polymer emulsion having good polymerization stability and mechanical stability and less foaming can be obtained. Moreover, the particle diameter distribution of the obtained polymer emulsion is narrow, and a film having good gloss when used for coatings can be obtained.
上記一般式（１）において、Ｒ１は、炭素数が１２〜１４のアルキル基を表し、本発明では炭素数１２〜１４の分岐脂肪族アルコールを疎水基の原料アルコールとして用いる。ここで、Ｒ１は、炭素数１２〜１４のアルキル基を表し、具体的にはイソドデシル基、イソトリデシル基、イソテトラデシル基が挙げられる。好ましくはイソトリデシル基である。特に限定はしないが、疎水基原料がイソトリデシルアルコールと他のアルコールとの混合物であってもよい。この場合の他のアルコールとしては、上記した炭素数１２〜１４の分岐脂肪族アルコールを用いることが好ましいが、本発明の効果を損なわない範囲内で炭素数が１２〜１４でない分岐脂肪族アルコールを用いることもできる。炭素数が１２〜１４でない分岐脂肪族アルコールを混合する場合、その比率は１０重量％以下であることが好ましい。 In the general formula (1), R 1 represents an alkyl group having 12 to 14 carbon atoms. In the present invention, a branched aliphatic alcohol having 12 to 14 carbon atoms is used as a raw material alcohol for a hydrophobic group. Here, R 1 represents an alkyl group having 12 to 14 carbon atoms, and specific examples include an isododecyl group, an isotridecyl group, and an isotetradecyl group. An isotridecyl group is preferable. Although not particularly limited, the hydrophobic group raw material may be a mixture of isotridecyl alcohol and another alcohol. As the other alcohol in this case, the above-mentioned branched aliphatic alcohol having 12 to 14 carbon atoms is preferably used. However, a branched aliphatic alcohol having 12 to 14 carbon atoms within the range not impairing the effects of the present invention. It can also be used. When the branched aliphatic alcohol having 12 to 14 carbon atoms is mixed, the ratio is preferably 10% by weight or less.
一般式（１）において、（ＡＯ）ｚは、上記した原料アルコールに、プロピレンオキサイドとエチレンオキサイドを付加重合させることにより形成されるポリオキシアルキレン部分であり、ＰＯがオキシプロピレン基を、ＥＯがオキシエチレン基をそれぞれ表す。プロピレンオキサイドとエチレンオキサイドの付加形態は、ランダム重合鎖でも、ブロック重合鎖でも、又はこれらの組み合わせでもよい。より好ましくは、アルコール残基側がオキシプロピレン基部分となるように、原料アルコールに対して、まずプロピレンオキサイドを付加し、次いでエチレンオキサイドをブロック付加することである。すなわち、上記アニオン界面活性剤は下記一般式（７）で表されることがより好ましい。このようなブロック付加形態を採用することにより、乳化重合時の重合安定性が良好で、得られるポリマーエマルジョンの機械安定性やフィルムの光沢性が良好なものとなる。 In the general formula (1), (AO) z is a polyoxyalkylene moiety formed by addition polymerization of propylene oxide and ethylene oxide to the raw material alcohol described above, PO being an oxypropylene group, EO being an oxy Each represents an ethylene group. The addition form of propylene oxide and ethylene oxide may be a random polymer chain, a block polymer chain, or a combination thereof. More preferably, propylene oxide is first added to the raw material alcohol, and then ethylene oxide is block-added so that the alcohol residue side becomes an oxypropylene group portion. That is, the anionic surfactant is more preferably represented by the following general formula (7). By adopting such a block addition form, the polymerization stability during emulsion polymerization is good, and the mechanical stability of the resulting polymer emulsion and the gloss of the film are good.
Ｒ１−Ｏ−（ＰＯ）ｍ（ＥＯ）ｎ−Ｘ （７）
ここで、式中、Ｒ１は、炭素数が１２〜１４であるアルキル基を表し、ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表し、ｍは０〜４、ｎは１〜５０の整数である。
R 1 —O— (PO) m (EO) n —X (7)
Here, in the formula, R 1 represents an alkyl group having 12 to 14 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, m is an integer of 0 to 4, and n is an integer of 1 to 50. It is.
上記アルキル部分において、分岐度は０．８〜２．５の範囲である。分岐度が０．８未満では、得られるポリマーエマルジョンの泡立ちが多くなる。逆に、分岐度が２．５より大きい場合、得られるポリマーエマルジョンの粒子径分布が粗くなり、塗料用途に用いた場合に良好な光沢を有するフィルムが得られない。一方、ＥＯの付加モル数ｎは１〜５０であり、より好ましくは３〜３０である。 In the alkyl moiety, the degree of branching is in the range of 0.8 to 2.5. When the degree of branching is less than 0.8, foaming of the resulting polymer emulsion increases. On the other hand, when the degree of branching is greater than 2.5, the particle size distribution of the resulting polymer emulsion becomes coarse, and a film having good gloss cannot be obtained when used for coating applications. On the other hand, the added mole number n of EO is 1-50, more preferably 3-30.
上記一般式（１）で表されるアニオン界面活性剤は、下記一般式（８）で表される非イオン界面活性剤を原料として合成されるものであり、即ち、この原料非イオン界面活性剤の水酸基の水素原子Ｈをアニオン性親水基Ｘで置換してなるものである。 The anionic surfactant represented by the general formula (1) is synthesized using a nonionic surfactant represented by the following general formula (8) as a raw material, that is, this raw material nonionic surfactant. The hydrogen atom H of the hydroxyl group is substituted with an anionic hydrophilic group X.
Ｒ１−Ｏ−（ＰＯ）ｍ（ＥＯ）ｎ−Ｈ （８）
ここで、式中のＲ１、ＰＯ、ＥＯ、ｍ、ｎは上記一般式（７）と同じである。
R 1 —O— (PO) m (EO) n —H (8)
Here, R 1 , PO, EO, m, and n in the formula are the same as those in the general formula (7).
上記アニオン性親水基Ｘとしては、下記一般式（２）〜（６）のいずれかで表される基が好ましい例として挙げられる。 As said anionic hydrophilic group X, group represented by either of the following general formula (2)-(6) is mentioned as a preferable example.
Ｘ：−ＳＯ３Ｍ （２）
−ＰＯ３Ｍ２ （３）
−Ｐ（Ｒ２）Ｏ２Ｍ （４）
−ＣＨ２ＣＯＯＭ （５）
−ＣＯ−ＣＨ２−ＣＨ（ＳＯ３Ｍ）ＣＯＯＭ （６）
ここで、式中のＭは、それぞれ独立に、水素、リチウム，ナトリウム，カリウム等のアルカリ金属、ＮＨ４、又はエタノールアミン，ジエタノールアミン，プロパノールアミン等のアルカノールアミンの残基を表す。また、Ｒ２は上記一般式（１）のＸ以外の残基であり、従って、上記式（３）はリン酸モノエステルを、上記式（４）はリン酸ジエステルをそれぞれ示す。
X: -SO 3 M (2)
-PO 3 M 2 (3)
-P (R 2) O 2 M (4)
—CH 2 COOM (5)
-CO-CH 2 -CH (SO 3 M) COOM (6)
Here, M in the formula independently represents an alkali metal such as hydrogen, lithium, sodium or potassium, NH 4 , or an alkanolamine residue such as ethanolamine, diethanolamine or propanolamine. R 2 is a residue other than X in the general formula (1). Therefore, the above formula (3) represents a phosphoric acid monoester, and the above formula (4) represents a phosphoric acid diester.
本発明では、上記原料非イオン界面活性剤として、平均分子量（Ｍｎ）に対する重量平均分子量（Ｍｗ）の比で表される多分散度（Ｍｗ／Ｍｎ）が１．１０〜１．２０の範囲内にあるものを用いる。多分散度Ｍｗ／Ｍｎが１．２０より大きいと、得られるポリマーエマルジョンの粒子径分布が粗くなり、塗料用途に用いた場合に良好な光沢を有するフィルムが得られない。逆に、多分散度Ｍｗ／Ｍｎが１．１０より小さいと、乳化重合に使用できるモノマーが限定されるだけでなく、乳化力不足のために重合安定性が不十分になる。 In the present invention, as the raw material nonionic surfactant, the polydispersity (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the average molecular weight (Mn) is in the range of 1.10 to 1.20. Use what is in If the polydispersity Mw / Mn is greater than 1.20, the particle size distribution of the resulting polymer emulsion becomes coarse, and a film having good gloss cannot be obtained when used for coating applications. Conversely, when the polydispersity Mw / Mn is less than 1.10, not only the monomers that can be used for emulsion polymerization are limited, but also the polymerization stability becomes insufficient due to insufficient emulsification power.
ここで、原料非イオン界面活性剤の多分散度はアルキレンオキサイドの付加重合による分布に基づくものであるため、該非イオン界面活性剤にアニオン性親水基を導入して得られるアニオン界面活性剤でも基本的には同様の多分散度となるが、アニオン性親水基の分子量の大小による影響を排除するため、本発明では原料非イオン界面活性剤の多分散度として規定している。なお、この多分散度を上記範囲内に設定するためには、疎水基原料であるアルコールにアルキレンオキサイドを付加させる際の触媒の種類及び量、並びに反応温度等の反応条件を調整すればよい。 Here, since the polydispersity of the raw material nonionic surfactant is based on the distribution by addition polymerization of the alkylene oxide, an anionic surfactant obtained by introducing an anionic hydrophilic group into the nonionic surfactant is also basically used. However, in order to eliminate the influence of the molecular weight of the anionic hydrophilic group, the polydispersity of the raw material nonionic surfactant is specified in the present invention. In order to set the polydispersity within the above range, the reaction conditions such as the type and amount of the catalyst and the reaction temperature when the alkylene oxide is added to the alcohol as the hydrophobic group raw material may be adjusted.
本発明の乳化重合用乳化剤は、上記した一般式（１）で表されるアニオン界面活性剤からなるものであり、この乳化重合用乳化剤は各種モノマーの乳化重合に適用することができる。適用可能なモノマーの種類は特に限定されないが、例としては、アクリル酸メチル、アクリル酸エチル、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、メタクリル酸ブチル、メタクリル酸グリシジル、アクリロニトリル、メタクリロニトリル、α−クロルアクリロニトリル、アクリルアミド、メタクリルアミド、アクリル酸ヒドロキシエチルエステル、メタクリル酸ヒドロキシエチルエステル、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、アクリル酸、メタクリル酸等のアクリル系モノマー、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−メチルスチレン、ジビニルベンゼン等の芳香族系モノマー、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系モノマー、ブタジエン、イソプレン、クロロプレン等の共役ジオレフィン系モノマー等、その他、エチレン、イタコン酸、フマル酸、マレイン酸、マレイン酸メチル等が挙げられる。これらのモノマーは、１種または２種以上を用いることができる。 The emulsifier for emulsion polymerization of the present invention comprises the anionic surfactant represented by the above general formula (1), and this emulsifier for emulsion polymerization can be applied to emulsion polymerization of various monomers. Although the kind of applicable monomer is not particularly limited, examples include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, glycidyl methacrylate, acrylonitrile, methacrylo Nitrile, α-chloroacrylonitrile, acrylamide, methacrylamide, acrylic acid hydroxyethyl ester, methacrylic acid hydroxyethyl ester, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid, methacrylic acid and other acrylic monomers, styrene, α-methylstyrene, Aromatic monomers such as vinyl toluene, p-methylstyrene, divinylbenzene, vinyl ester monomers such as vinyl acetate, vinyl chloride, vinylidene chloride, etc. Examples thereof include halogenated olefin monomers, conjugated diolefin monomers such as butadiene, isoprene and chloroprene, and others, ethylene, itaconic acid, fumaric acid, maleic acid, methyl maleate and the like. These monomers can be used alone or in combination of two or more.
本発明の乳化重合用乳化剤は、通常、モノマー総量に対して０．１〜２０重量％、好ましくは、０．２〜５重量％で使用する。 The emulsifier for emulsion polymerization of the present invention is usually used in an amount of 0.1 to 20% by weight, preferably 0.2 to 5% by weight, based on the total amount of monomers.
本発明の乳化重合用乳化剤を用いる乳化重合には、従来公知の重合開始剤が特に制限なく使用できる。代表的な例としては、過酸化水素、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化ベンゾイル、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩等が挙げられる。 For emulsion polymerization using the emulsifier for emulsion polymerization of the present invention, a conventionally known polymerization initiator can be used without particular limitation. Representative examples include hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane). And dihydrochloride.
また、重合促進剤として、亜硫酸水素ナトリウム、硫酸第１鉄アンモニウム等を用い、レドックス重合を行うこともできる。 Further, redox polymerization can be performed using sodium bisulfite, ferrous ammonium sulfate, or the like as a polymerization accelerator.
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、ｎ−オクチルメルカプタン、ｎ−ラウリルメルカプタン、ｎ−ドデシルメルカプタン、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類などを用いてもよい。 Further, as chain transfer agents, mercaptans such as α-methylstyrene dimer, n-butyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, carbon tetrachloride, carbon tetrabromide Halogenated hydrocarbons such as may be used.
本発明の乳化重合用乳化剤は、他の界面活性剤と併用することもでき、そのような他の界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンポリオキシプロピレンブロックポリマー等の非イオン界面活性剤、アルキルベンゼンスルホン酸塩等の他のアニオン界面活性剤などが挙げられる。 The emulsifier for emulsion polymerization of the present invention can be used in combination with other surfactants. Examples of such other surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters. And nonionic surfactants such as polyoxyethylene polyoxypropylene block polymers, and other anionic surfactants such as alkylbenzene sulfonates.
本発明の乳化重合用乳化剤を用いて得られるポリマーエマルジョンは、例えば、印刷インキ、塗料（建築用、家庭用、缶用、電着塗装用等）等のバインダー、インクジェット用メディアのバインダー、接着剤、粘着剤、被覆剤、含浸補強剤等として、木材、金属、紙、布、プラスチック、セラミック、その他コンクリート等に適用することができる。 The polymer emulsion obtained using the emulsifier for emulsion polymerization of the present invention includes, for example, binders for printing inks, paints (for construction, household use, cans, electrodeposition coating, etc.), binders for inkjet media, and adhesives. It can be applied to wood, metal, paper, cloth, plastic, ceramic, other concrete, etc. as an adhesive, a coating agent, an impregnation reinforcing agent and the like.
以下、本発明を実施例により具体的に説明するが、本発明の範囲はこれに限定されるものではない。なお、以下の実施例中、「部」は特に記載がない限り質量基準である。 Hereinafter, the present invention will be specifically described by way of examples, but the scope of the present invention is not limited thereto. In the following examples, “part” is based on mass unless otherwise specified.
原料非イオン界面活性剤の合成
下記表１に示す原料非イオン界面活性剤［Ａ］〜［Ｋ］を次のようにして合成した。表において、（ＥＯ）はエチレンオキサイド、（ＰＯ）はプロピレンオキサイドの略である。
Synthesis of Raw Material Nonionic Surfactant Raw material nonionic surfactants [A] to [K] shown in Table 1 below were synthesized as follows. In the table, (EO) is an abbreviation for ethylene oxide and (PO) is an abbreviation for propylene oxide.
＜製造例１＞
オートクレーブに、イソトリデシルアルコール（分岐度２．１）２００部（１モル）と水酸化カリウム０．４２部（０．００７モル、対粗製物あたり０．１％）を仕込み、オートクレーブ内を窒素置換した後、撹拌しながら７０℃で減圧して、反応器内の内圧が２．７ｋＰａ到達後、引き続き３０分間減圧脱水を継続した。次に、温度１２０℃、反応圧０．２５ＭＰａでエチレンオキサイド２２０部（５モル）を導入した後、反応温度を維持しつつ、内圧が低下して一定になるまで熟成させた。その後、反応液を７０℃まで冷却した後、氷酢酸０．４９部（０．００８モル、対水酸化カリウムあたり１．１モル等量）で中和して、原料非イオン界面活性剤［Ａ］を得た。
<Production Example 1>
An autoclave was charged with 200 parts (1 mol) of isotridecyl alcohol (branch degree 2.1) and 0.42 parts of potassium hydroxide (0.007 mol, 0.1% per crude product), and the autoclave was filled with nitrogen. After the replacement, the pressure was reduced at 70 ° C. while stirring. After the internal pressure in the reactor reached 2.7 kPa, dehydration under reduced pressure was continued for 30 minutes. Next, after introducing 220 parts (5 moles) of ethylene oxide at a temperature of 120 ° C. and a reaction pressure of 0.25 MPa, the reaction temperature was maintained and aging was performed until the internal pressure decreased and became constant. Thereafter, the reaction solution was cooled to 70 ° C., and then neutralized with 0.49 part of glacial acetic acid (0.008 mol, 1.1 mol equivalent to potassium hydroxide), and the raw material nonionic surfactant [A ] Was obtained.
＜製造例２＞
エチレンオキサイドの導入量を６６０部（１５モル）に変更し、それに合わせて触媒量も変更した（対粗製物あたり０．１％）という以外は製造例１と同様にして、原料非イオン界面活性剤［Ｂ］を得た。
<Production Example 2>
The raw material nonionic surface activity was changed in the same manner as in Production Example 1 except that the amount of ethylene oxide introduced was changed to 660 parts (15 mol), and the amount of catalyst was changed accordingly (0.1% per crude product). Agent [B] was obtained.
＜製造例３＞
オートクレーブに、イソトリデシルアルコール（分岐度２．１）２００部（１モル）と水酸化カリウム０．９２部（０．０１６モル、対粗製物あたり０．１％）を仕込み、オートクレーブ内を窒素置換した後、撹拌しながら７０℃で減圧して、反応器内の内圧が２．７ｋＰａ到達後、引き続き３０分間減圧脱水を継続した。ついで１１０℃まで昇温した後、反応圧０．２０ＭＰａでプロピレンオキサイド５８部（１モル）を導入した。プロピレンオキサイドの導入後、反応温度を維持して、内圧が低下して一定になるまで熟成させた。次に、温度１２０℃、反応圧０．２５ＭＰａでエチレンオキサイド６６０部（１５モル）を導入した後、反応温度を維持しつつ、内圧が低下して一定になるまで熟成させた。その後、反応液を７０℃まで冷却した後、８５重量％乳酸１．９１部（０．０１８モル、対水酸化カリウムあたり１．１モル等量）で中和して、原料非イオン界面活性剤［Ｃ］を得た。
<Production Example 3>
An autoclave was charged with 200 parts (1 mol) of isotridecyl alcohol (branch degree 2.1) and 0.92 parts of potassium hydroxide (0.016 mol, 0.1% per crude product), and nitrogen was added to the autoclave. After the replacement, the pressure was reduced at 70 ° C. while stirring. After the internal pressure in the reactor reached 2.7 kPa, dehydration under reduced pressure was continued for 30 minutes. Subsequently, after raising the temperature to 110 ° C., 58 parts (1 mol) of propylene oxide was introduced at a reaction pressure of 0.20 MPa. After the introduction of propylene oxide, the reaction temperature was maintained, and aging was performed until the internal pressure decreased and became constant. Next, after introducing 660 parts (15 moles) of ethylene oxide at a temperature of 120 ° C. and a reaction pressure of 0.25 MPa, the reaction temperature was maintained and aging was performed until the internal pressure decreased and became constant. Thereafter, the reaction solution was cooled to 70 ° C. and then neutralized with 1.91 parts of 85% by weight of lactic acid (0.018 mol, 1.1 mol equivalent to potassium hydroxide) to obtain a raw material nonionic surfactant. [C] was obtained.
＜製造例４＞
イソトリデシルアルコール（分岐度２．１）を下記表１に記載のアルコールに変更し、エチレンオキサイドの導入量を下記表１に記載の割合に変更し、それに合わせて触媒量も変更した（対粗製物あたり０．１％）以外は製造例２と同様にして原料非イオン界面活性剤［Ｄ］［Ｇ］［Ｉ］〜［Ｋ］を得た。
<Production Example 4>
Isotridecyl alcohol (branch degree 2.1) was changed to the alcohol shown in Table 1 below, the amount of ethylene oxide introduced was changed to the ratio shown in Table 1 below, and the catalyst amount was changed accordingly (as opposed to Except for 0.1% per crude product), raw material nonionic surfactants [D] [G] [I] to [K] were obtained in the same manner as in Production Example 2.
＜製造例５＞
オートクレーブに、イソトリデシルアルコール（分岐度２．１）２００部（１モル）と三フッ化ホウ素０．４２部（０．００６モル、対粗製物あたり０．１％）を仕込み、オートクレーブ内を窒素置換した。次に、温度７０℃、反応圧０．２５ＭＰａでエチレンオキサイド２２０部（５モル）を導入した後、反応温度を維持しつつ、内圧が低下して一定になるまで熟成させた。その後、反応液を６０℃まで冷却し、原料非イオン界面活性剤［Ｅ］を得た。
<Production Example 5>
An autoclave was charged with 200 parts (1 mole) of isotridecyl alcohol (branching degree 2.1) and 0.42 part of boron trifluoride (0.006 moles, 0.1% per crude product). Replaced with nitrogen. Next, after introducing 220 parts (5 moles) of ethylene oxide at a temperature of 70 ° C. and a reaction pressure of 0.25 MPa, the reaction temperature was maintained and aging was performed until the internal pressure decreased and became constant. Thereafter, the reaction solution was cooled to 60 ° C. to obtain a raw material nonionic surfactant [E].
＜製造例６＞
オートクレーブに、イソトリデシルアルコール（分岐度２．１）２００（１モル）と水酸化カリウム０．８６部（０．０１５モル、対粗製物あたり０．１％）を仕込み、オートクレーブ内を窒素置換した後、撹拌しながら７０℃で減圧して、反応器内の内圧が２．７ｋＰａ到達後、引き続き３０分間減圧脱水を継続した。次に、温度１７０℃、反応圧０．２５ＭＰａでエチレンオキサイド６６０部（１５モル）を導入した後、反応温度を維持しつつ、内圧が低下して一定になるまで熟成させた。その後、反応液を７０℃まで冷却した後、氷酢酸１．０１部（０．０１７モル、対水酸化カリウムあたり１．１モル等量）で中和して、原料非イオン界面活性剤［Ｆ］を得た。
<Production Example 6>
An autoclave is charged with 200 (1 mol) of isotridecyl alcohol (branch degree 2.1) and 0.86 parts of potassium hydroxide (0.015 mol, 0.1% per crude product), and the inside of the autoclave is purged with nitrogen Then, the pressure was reduced at 70 ° C. with stirring, and after the internal pressure in the reactor reached 2.7 kPa, dehydration under reduced pressure was continued for 30 minutes. Next, after introducing 660 parts (15 moles) of ethylene oxide at a temperature of 170 ° C. and a reaction pressure of 0.25 MPa, the reaction temperature was maintained and aging was performed until the internal pressure decreased and became constant. Thereafter, the reaction solution was cooled to 70 ° C., and then neutralized with 1.01 part of glacial acetic acid (0.017 mol, 1.1 mol equivalent to potassium hydroxide), and the raw material nonionic surfactant [F ] Was obtained.
＜製造例７＞
イソトリデシルアルコール（分岐度２．１）をイソトリデシルアルコール（分岐度２．９）に変更した以外は製造例３と同様にして原料非イオン界面活性剤［Ｈ］を得た。
<Production Example 7>
A raw material nonionic surfactant [H] was obtained in the same manner as in Production Example 3, except that isotridecyl alcohol (branch degree 2.1) was changed to isotridecyl alcohol (branch degree 2.9).
［多分散度測定］
次の条件によるＧＰＣ測定を行うことにより、界面活性剤の分子量分布の広狭の程度である多分散度Ｍｗ／Ｍｎを求めた。
カラム：Megapak GEL 201FP×1＋Megapak GEL 201F×２（ともに日本分光（株）製）
移動相：ＴＨＦ（３ｍＬ／分）
カラム温度：４０℃
検出器：ＲＩ
サンプル注入：５重量％溶液１００μＬ
[Polydispersity measurement]
By performing GPC measurement under the following conditions, the polydispersity Mw / Mn, which is the extent of the molecular weight distribution of the surfactant, was determined.
Column: Megapak GEL 201FP x 1 + Megapak GEL 201F x 2 (both manufactured by JASCO Corporation)
Mobile phase: THF (3 mL / min)
Column temperature: 40 ° C
Detector: RI
Sample injection: 5% by weight solution 100 μL
［分岐度］
Ｈ１−ＮＭＲ測定によりメチル基数を求め、末端メチル基部位相当の１を引いて得た数値である。
[Degree of branching]
It is a numerical value obtained by obtaining the number of methyl groups by H 1 -NMR measurement and subtracting 1 corresponding to the terminal methyl group site.
乳化重合用乳化剤の合成
上記で得られた原料非イオン界面活性剤を用いて、下記表２に示す乳化重合用乳化剤である本発明品［１］〜［７］と比較品［１］〜［１０］を次のようにして合成した。
Synthesis of Emulsifier for Emulsion Polymerization Using the raw material nonionic surfactant obtained above, the present invention products [1] to [7] and the comparative products [1] to [1] which are emulsifiers for emulsion polymerization shown in Table 2 below. 10] was synthesized as follows.
＜製造例８＞
原料非イオン界面活性剤［Ａ］４２０部（１モル）とスルファミン酸９７．１部（１モル）を１２０℃、５時間の条件にて反応させ、本発明品［１］を得た。
<Production Example 8>
420 parts (1 mol) of raw material nonionic surfactant [A] and 97.1 parts (1 mol) of sulfamic acid were reacted under the conditions of 120 ° C. and 5 hours to obtain the product [1] of the present invention.
＜製造例９＞
２０℃に冷却した原料非イオン界面活性剤［Ａ］４２０部（１モル）にクロロスルホン酸１１７部（１モル）を滴下した。滴下後、反応により発生するＨＣｌを真空ポンプで吸引し、水酸化ナトリウム水溶液で中和して、本発明品［２］を得た。
<Production Example 9>
117 parts (1 mol) of chlorosulfonic acid was added dropwise to 420 parts (1 mol) of the raw material nonionic surfactant [A] cooled to 20 ° C. After the dropping, HCl generated by the reaction was sucked with a vacuum pump and neutralized with an aqueous sodium hydroxide solution to obtain the product [2] of the present invention.
＜製造例１０＞
原料非イオン界面活性剤［Ａ］を下記表２に記載の原料非イオン界面活性剤に変更した以外は製造例８と同様にして、本発明品［３］〜［４］、比較品［１］［３］〜［６］を得た。
<Production Example 10>
Except for changing the raw material nonionic surfactant [A] to the raw material nonionic surfactant shown in Table 2 below, the products [3] to [4] of the present invention and the comparative product [1] were prepared in the same manner as in Production Example 8. ] [3] to [6] were obtained.
＜製造例１１＞
原料非イオン界面活性剤［Ａ］４２０部（１モル）と無水マレイン酸９８部（１モル）を８０℃で２時間反応させた後、水３０００部を投入し、３０℃以下にて水酸化ナトリウム水溶液により中和した。次に亜硫酸水素ナトリウム１０４部（１．１モル）を仕込み、７０℃で３時間反応を行い、本発明品［５］を得た。
<Production Example 11>
After reacting 420 parts (1 mol) of raw material nonionic surfactant [A] and 98 parts (1 mol) of maleic anhydride at 80 ° C. for 2 hours, 3000 parts of water was added and hydroxylated at 30 ° C. or less. Neutralized with aqueous sodium solution. Next, 104 parts (1.1 mol) of sodium hydrogen sulfite was added and reacted at 70 ° C. for 3 hours to obtain the product [5] of the present invention.
＜製造例１２＞
原料非イオン界面活性剤［Ｂ］８６０部（１モル）とモノクロル酢酸ナトリウム１１７部（１モル）を室温で３０分かけて混合し、反応容器内を４０℃に保ち水酸化ナトリウム４４部（１．１モル）を３時間かけて添加し、さらに４０℃にて１７時間反応させた。次に７５重量％リン酸で中和した後、塩化メチレン４００ｍＬと水２００ｍＬを加え、水洗を行った。更に水２００ｍＬを使用した水洗を２回行った後、有機層の塩化メチレンを留去した。その後、水酸化ナトリウム水溶液でｐＨ８まで中和して、本発明品［６］を得た。
<Production Example 12>
860 parts (1 mole) of raw material nonionic surfactant [B] and 117 parts (1 mole) sodium monochloroacetate were mixed at room temperature over 30 minutes, and the reaction vessel was kept at 40 ° C. to 44 parts of sodium hydroxide (1 0.1 mol) was added over 3 hours, and the mixture was further reacted at 40 ° C. for 17 hours. Next, after neutralizing with 75 wt% phosphoric acid, 400 mL of methylene chloride and 200 mL of water were added and washed with water. Further, after washing with 200 mL of water twice, methylene chloride in the organic layer was distilled off. Then, it neutralized to pH 8 with sodium hydroxide aqueous solution, and this invention product [6] was obtained.
＜製造例１３＞
原料非イオン界面活性剤［Ａ］１０５０部（２．５モル）と無水リン酸１４２部（１モル）を８０℃で５時間反応させた後、水酸化ナトリウム水溶液により中和して、本発明品［７］を得た。
<Production Example 13>
1050 parts (2.5 mol) of raw material nonionic surfactant [A] and 142 parts (1 mol) of phosphoric anhydride were reacted at 80 ° C. for 5 hours, and then neutralized with an aqueous sodium hydroxide solution. Product [7] was obtained.
＜製造例１４＞
原料非イオン界面活性剤［Ａ］を原料非イオン界面活性剤［Ｅ］に変更した以外は製造例９と同様にして、比較品［２］を得た。
<Production Example 14>
A comparative product [2] was obtained in the same manner as in Production Example 9 except that the raw material nonionic surfactant [A] was changed to the raw material nonionic surfactant [E].
＜製造例１５＞
原料非イオン界面活性剤［Ａ］を原料非イオン界面活性剤［Ｉ］に変更した以外は製造例１１と同様にして、比較品［７］を得た。
<Production Example 15>
A comparative product [7] was obtained in the same manner as in Production Example 11 except that the raw material nonionic surfactant [A] was changed to the raw material nonionic surfactant [I].
＜製造例１６＞
原料非イオン界面活性剤［Ｂ］を原料非イオン界面活性剤［Ｋ］に変更した以外は製造例１２と同様にして、比較品［８］を得た。
<Production Example 16>
A comparative product [8] was obtained in the same manner as in Production Example 12 except that the raw material nonionic surfactant [B] was changed to the raw material nonionic surfactant [K].
＜製造例１７＞
原料非イオン界面活性剤［Ａ］を原料非イオン界面活性剤［Ｊ］に変更した以外は製造例１３と同様にして、比較品［９］を得た。
<Production Example 17>
A comparative product [9] was obtained in the same manner as in Production Example 13 except that the raw material nonionic surfactant [A] was changed to the raw material nonionic surfactant [J].
＜製造例１８＞
原料非イオン界面活性剤［Ａ］をラウリルアルコールに変更した以外は製造例９と同様にして、比較品［１０］を得た。
<Production Example 18>
A comparative product [10] was obtained in the same manner as in Production Example 9 except that the raw material nonionic surfactant [A] was changed to lauryl alcohol.
＜実施例１〜３及び比較例１〜４＞
撹拌機、還流冷却機、温度計及び滴下漏斗を備えた反応容器に蒸留水１３４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、窒素ガスにて溶存酸素を除去した。これとは別にスチレン７５部、メタクリル酸メチル５０部、アクリル酸ブチル１２１部、アクリル酸４部、乳化重合用乳化剤５部、蒸留水１１０部とを混合して、モノマーエマルジョンを調製した。次に、上記で調製したモノマーエマルジョン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ジョンを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ジョンを得た。使用した乳化重合用乳化剤は下記表３に示す通りである。
<Examples 1-3 and Comparative Examples 1-4>
A reaction vessel equipped with a stirrer, reflux condenser, thermometer and dropping funnel was charged with 134 parts of distilled water and 0.5 part of sodium bicarbonate as a buffering agent, heated to 80 ° C., and dissolved oxygen was added with nitrogen gas. Removed. Separately, 75 parts of styrene, 50 parts of methyl methacrylate, 121 parts of butyl acrylate, 4 parts of acrylic acid, 5 parts of an emulsifier for emulsion polymerization, and 110 parts of distilled 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. 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. The emulsifiers for emulsion polymerization used are as shown in Table 3 below.
得られたポリマーエマルジョンについて、重合安定性、機械安定性、粒子径、粒子径分布、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り、結果を表３に示す。 The resulting polymer emulsion was evaluated for polymerization stability, mechanical stability, particle size, particle size distribution, and film gloss. The evaluation method is as follows, and the results are shown in Table 3.
［重合安定性］
重合後のポリマーエマルジョンを８０メッシュの濾布を用いて濾過し、濾布上の残渣を水洗後、１０５℃×３時間で乾燥した。乾燥後の残渣の重量を測定し、全固形分に対する重量比率（％）で表示した。
[Polymerization stability]
The polymer emulsion after polymerization was filtered using an 80 mesh filter cloth, and the residue on the filter cloth was washed with water and dried at 105 ° C. for 3 hours. The weight of the residue after drying was measured and expressed as a weight ratio (%) to the total solid content.
［機械安定性］
ポリマーエマルジョン５０ｇをマーロン型試験機（荷重：１０ｋｇ、回転数：１０００ｒｐｍ、時間：５分）にて測定した。発生した凝集物を８０メッシュの金網で濾過し、残渣を水洗後、１０５℃×３時間で乾燥させ、その重量を全固形分に対する重量比率（％）で表示した。
[Machine stability]
50 g of the polymer emulsion was measured with a Marlon tester (load: 10 kg, rotation speed: 1000 rpm, time: 5 minutes). The generated agglomerates were filtered through an 80-mesh wire mesh, and the residue was washed with water and dried at 105 ° C. for 3 hours. The weight was expressed as a weight ratio (%) to the total solid content.
［粒子径］
動的光散乱式粒度分布測定装置（日機装製 MICROTRAC UPA 9340）にて測定し、μｍで表示した。
[Particle size]
The particle size distribution was measured with a dynamic light scattering particle size distribution analyzer (MICROTRAC UPA 9340 manufactured by Nikkiso) and displayed in μm.
［粒子径分布］
動的光散乱式粒度分布測定にて得られた粒子径分布から標準偏差を求め、それをメディアン径で割った値、つまり相対標準偏差（％）で表示した。
[Particle size distribution]
The standard deviation was obtained from the particle size distribution obtained by the dynamic light scattering particle size distribution measurement, and was expressed as a value obtained by dividing the standard deviation by the median diameter, that is, relative standard deviation (%).
［フィルムの光沢性］
ガラスプレート上に０．５ｍｍ（ｗｅｔ）のエマルジョン膜を作り、室温で１８〜２０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、○（優）、△（可）、×（不可）の３段階で評価した。
[Glossiness of film]
A 0.5 mm (wet) emulsion film was formed on a glass plate and allowed to stand at room temperature for 18 to 20 hours to prepare a film. The glossiness of this film was visually evaluated in three stages: ○ (excellent), Δ (possible), and × (impossible).
＜実施例４〜５及び比較例５〜７＞
撹拌機、還流冷却機、温度計及び滴下漏斗を備えた反応容器に蒸留水１３４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、窒素ガスにて溶存酸素を除去した。これとは別にアクリル酸２−エチルヘキシル１７１部、アクリル酸エチル７５部、アクリル酸４部、乳化重合用乳化剤５部、蒸留水１１０部とを混合し、乳化重合用乳化剤を含むモノマーエマルジョンを調製した。次に、上記で調製したモノマーエマルジョン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カリウム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ジョンを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ジョンを得た。使用した乳化重合用乳化剤は下記表４に示す通りである。
<Examples 4-5 and Comparative Examples 5-7>
A reaction vessel equipped with a stirrer, reflux condenser, thermometer and dropping funnel was charged with 134 parts of distilled water and 0.5 part of sodium bicarbonate as a buffering agent, heated to 80 ° C., and dissolved oxygen was added with nitrogen gas. Removed. Separately, 171 parts of 2-ethylhexyl acrylate, 75 parts of ethyl acrylate, 4 parts of acrylic acid, 5 parts of an emulsifier for emulsion polymerization, and 110 parts of distilled water were mixed to prepare a monomer emulsion containing an emulsifier for emulsion polymerization. . 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 potassium 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. The emulsifier for emulsion polymerization used is as shown in Table 4 below.
得られたポリマーエマルジョンについて、重合安定性、粒子径、泡立ち性をそれぞれ評価した。泡立ち性の評価方法は以下の通りであり、それ以外の評価方法は上記実施例と同じである。結果を表４に示す。 The resulting polymer emulsion was evaluated for polymerization stability, particle size, and foamability. The evaluation method of foamability is as follows, and the other evaluation methods are the same as those in the above examples. The results are shown in Table 4.
［泡立ち］
室温でポリマーエマルジョン２０ｍＬと水１０ｍＬを１００ｍＬネスラー管に入れ、振盪（１５回；１回／２秒）により起泡させ、２分間静置した後の泡量（ｍＬ）で表示した。
[Bubbling]
At room temperature, 20 mL of polymer emulsion and 10 mL of water were placed in a 100 mL Nessler tube, foamed by shaking (15 times; once / 2 seconds), and expressed as the amount of foam (mL) after standing for 2 minutes.
＜実施例６〜８及び比較例８〜１０＞
オートクレーブに蒸留水２３８部、過硫酸アンモニウム１部、乳化重合用乳化剤６部、α−メチルスチレンダイマー３部、ｔ−ドデシルメルカプタン１部、炭酸水素ナトリウム１部を仕込み、７０℃まで昇温させ、窒素ガスにて溶存酸素を除去した。次に反応液を７０℃に保ちつつブタジエン９０部、スチレン１２０部、アクリロニトリル３５部、イタコン酸５部を３時間かけて別々に導入し、導入終了後も３時間反応を行った。その後、４０℃まで冷却し、水酸化ナトリウム水溶液でｐＨ８〜９に調整してポリマーエマルジョンを得た。使用した乳化重合用乳化剤は下記表５に示す通りである。
<Examples 6-8 and Comparative Examples 8-10>
An autoclave is charged with 238 parts of distilled water, 1 part of ammonium persulfate, 6 parts of an emulsifier for emulsion polymerization, 3 parts of α-methylstyrene dimer, 1 part of t-dodecyl mercaptan, and 1 part of sodium hydrogen carbonate, and the temperature is raised to 70 ° C. The dissolved oxygen was removed with gas. Next, 90 parts of butadiene, 120 parts of styrene, 35 parts of acrylonitrile and 5 parts of itaconic acid were separately introduced over 3 hours while maintaining the reaction solution at 70 ° C., and the reaction was carried out for 3 hours after the introduction was completed. Then, it cooled to 40 degreeC and adjusted to pH8-9 with the sodium hydroxide aqueous solution, and obtained the polymer emulsion. The emulsifiers for emulsion polymerization used are as shown in Table 5 below.
得られたポリマーエマルジョンについて、重合安定性、粒子径をそれぞれ評価した。評価方法は上記実施例と同じである。結果を表５に示す。 The resulting polymer emulsion was evaluated for polymerization stability and particle size. The evaluation method is the same as in the above example. The results are shown in Table 5.
上記実施例及び比較例により示されるように、本発明品の乳化重合用乳化剤は特に限定した範囲の分岐度でかつ特に限定したアルキレンオキサイド付加形態であるため、重合安定性、機械安定性が良好であり、泡立ちの少ないポリマーエマルジョンが得られた。また、フィルムの光沢性にも優れていた。 As shown in the above examples and comparative examples, the emulsion polymerization emulsifier of the present invention has a particularly limited range of branching and a particularly limited alkylene oxide addition form, so that the polymerization stability and mechanical stability are good. A polymer emulsion with less foaming was obtained. Moreover, the glossiness of the film was also excellent.
これに対し、分岐度が０．８未満の比較品［４］では、比較例５に示されるように、ポリマーエマルジョンの泡立ちが大きかった。また、分岐度が２．５より大きい比較品［５］では、比較例４に示されるようにフィルムの光沢性にも劣るものであった。多分散度が１．２０を越える比較品［３］では、比較例３に示されように、フィルムの光沢性に劣っていた。また、多分散度が１．１０未満の比較品［１］［２］では、比較例１，２に示されるように重合安定性及び機械安定性が不十分であった。 In contrast, in the comparative product [4] having a branching degree of less than 0.8, as shown in Comparative Example 5, the foaming of the polymer emulsion was large. Further, the comparative product [5] having a degree of branching greater than 2.5 was inferior in the gloss of the film as shown in Comparative Example 4. As shown in Comparative Example 3, the comparative product [3] having a polydispersity exceeding 1.20 was inferior in the glossiness of the film. In addition, the comparative products [1] and [2] having a polydispersity of less than 1.10 had insufficient polymerization stability and mechanical stability as shown in Comparative Examples 1 and 2.
本発明の乳化重合用乳化剤は、上記した優れた作用効果を有するものであるため、各種モノマーを乳化重合する際の乳化剤として好ましく使用することができ、特に泡立ちが少なく、またフィルムの光沢性に優れるポリマーエマルジョンを得ることができるため、塗料用途に用いるポリマーエマルジョンを乳化重合するための乳化剤として特に好ましく使用することができる。
Since the emulsifier for emulsion polymerization according to the present invention has the above-described excellent effects, it can be preferably used as an emulsifier for emulsion polymerization of various monomers, particularly with less foaming, and the gloss of the film. Since an excellent polymer emulsion can be obtained, it can be particularly preferably used as an emulsifier for emulsion polymerization of a polymer emulsion used for coating.
Claims (4)
Ｒ１−Ｏ−（ＡＯ）ｚ−Ｘ （１）
（式中、Ｒ１は、炭素数が１２〜１４であるアルキル基を表し、ＡＯは炭素数が２〜４のオキシアルキレン基を表しｚは１〜５０の整数であり、Ｘはアニオン性親水基を表す。ＡＯの付加形態はランダム付加、ブロック付加又はこれらの混合付加である。） An anionic surfactant represented by the following general formula (1), wherein the raw material nonionic surfactant has a polydispersity Mw / Mn of 1.10 to 1.20 and a branching degree of 0.8 to 2.5. An emulsifier for emulsion polymerization, comprising an anionic surfactant which is
R 1 -O- (AO) z- X (1)
(Wherein R 1 represents an alkyl group having 12 to 14 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, z is an integer of 1 to 50, and X is an anionic hydrophilic group) (The addition form of AO is random addition, block addition, or mixed addition thereof.)
Ｘ：−ＳＯ３Ｍ （２）
−ＰＯ３Ｍ２ （３）
−Ｐ（Ｒ２）Ｏ２Ｍ （４）
−ＣＨ２ＣＯＯＭ （５）
−ＣＯ−ＣＨ２−ＣＨ（ＳＯ３Ｍ）ＣＯＯＭ （６）
（式中、Ｍはそれぞれ独立に水素、アルカリ金属、ＮＨ４又はアルカノールアミン残基であり、Ｒ２は上記一般式（１）のＸ以外の残基である。）
The emulsifier for emulsion polymerization according to claim 1, wherein, in the general formula (1), X is a group represented by any one of the following general formulas (2) to (6).
X: -SO 3 M (2)
-PO 3 M 2 (3)
-P (R 2) O 2 M (4)
—CH 2 COOM (5)
-CO-CH 2 -CH (SO 3 M) COOM (6)
(In the formula, each M is independently a hydrogen, alkali metal, NH 4 or alkanolamine residue, and R 2 is a residue other than X in the general formula (1).)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108660805A (en) * | 2018-06-06 | 2018-10-16 | 苏州印丝特纺织数码科技有限公司 | A kind of ink-jet printed adhesive and preparation method thereof |
| CN114907238A (en) * | 2022-06-16 | 2022-08-16 | 淄博鲁瑞精细化工有限公司 | Alkyl alcohol polyoxyethylene ether sulfate salt for mercerizing penetrant and preparation method and application thereof |
-
2005
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108660805A (en) * | 2018-06-06 | 2018-10-16 | 苏州印丝特纺织数码科技有限公司 | A kind of ink-jet printed adhesive and preparation method thereof |
| CN114907238A (en) * | 2022-06-16 | 2022-08-16 | 淄博鲁瑞精细化工有限公司 | Alkyl alcohol polyoxyethylene ether sulfate salt for mercerizing penetrant and preparation method and application thereof |
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