JP6260933B2 - Emulsifier for emulsion polymerization - Google Patents
Emulsifier for emulsion polymerization Download PDFInfo
- Publication number
- JP6260933B2 JP6260933B2 JP2013271346A JP2013271346A JP6260933B2 JP 6260933 B2 JP6260933 B2 JP 6260933B2 JP 2013271346 A JP2013271346 A JP 2013271346A JP 2013271346 A JP2013271346 A JP 2013271346A JP 6260933 B2 JP6260933 B2 JP 6260933B2
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- JP
- Japan
- Prior art keywords
- formula
- group
- polymerization
- compound represented
- emulsion
- 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 description 18
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 47
- -1 oxypropylene group Chemical group 0.000 claims description 28
- 125000006353 oxyethylene group Chemical group 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 description 53
- 229920000642 polymer Polymers 0.000 description 41
- 238000006116 polymerization reaction Methods 0.000 description 37
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 25
- 238000005187 foaming Methods 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000001804 emulsifying effect Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical group COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000004439 Isononyl alcohol Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-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
- CDDDRVNOHLVEED-UHFFFAOYSA-N 1-cyclohexyl-3-[1-[[1-(cyclohexylcarbamoylamino)cyclohexyl]diazenyl]cyclohexyl]urea Chemical compound C1CCCCC1(N=NC1(CCCCC1)NC(=O)NC1CCCCC1)NC(=O)NC1CCCCC1 CDDDRVNOHLVEED-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-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
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- BODRLKRKPXBDBN-UHFFFAOYSA-N 3,5,5-Trimethyl-1-hexanol Chemical compound OCCC(C)CC(C)(C)C BODRLKRKPXBDBN-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
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 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
- 229940126062 Compound A Drugs 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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GQRHBOUXZFMQCJ-UHFFFAOYSA-N N(=NC(CCC(=O)O)(C)C#N)C(CCC(=O)O)(C)C#N.Cl.Cl.N(=NC(C(=N)N)(C)C)C(C(=N)N)(C)C Chemical compound N(=NC(CCC(=O)O)(C)C#N)C(CCC(=O)O)(C)C#N.Cl.Cl.N(=NC(C(=N)N)(C)C)C(C(=N)N)(C)C GQRHBOUXZFMQCJ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ALBJGICXDBJZGK-UHFFFAOYSA-N [1-[(1-acetyloxy-1-phenylethyl)diazenyl]-1-phenylethyl] acetate Chemical compound C=1C=CC=CC=1C(C)(OC(=O)C)N=NC(C)(OC(C)=O)C1=CC=CC=C1 ALBJGICXDBJZGK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical group C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- HJUGFYREWKUQJT-UHFFFAOYSA-N carbon tetrabromide Natural products BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 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
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 239000000123 paper Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 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 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
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- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明は、重合時の乳化安定性、及び得られるポリマーエマルジョンの低泡性や濡れ性に優れた乳化重合用乳化剤に関するものである。 The present invention relates to an emulsifier for emulsion polymerization, which is excellent in emulsion stability during polymerization, and excellent in low foamability and wettability of the resulting polymer emulsion.
ゴム・プラスチック工業製品に代表される合成樹脂の分野では、近年の環境負荷低減のニーズより、溶剤系から水系ポリマーエマルジョン化への移行が進んでいる。ポリマーエマルジョンは、塗料、接着剤、土木、繊維等の幅広い分野で利用されており、ポリマーエマルジョンを製造する際に用いられる乳化重合用乳化剤は重要な役割を担っている。 In the field of synthetic resins represented by rubber and plastic industrial products, the shift from solvent-based to water-based polymer emulsion is progressing due to the recent needs for reducing environmental impact. Polymer emulsions are used in a wide range of fields such as paints, adhesives, civil engineering, and fibers, and an emulsifier for emulsion polymerization used in producing polymer emulsions plays an important role.
従来より、乳化重合用乳化剤として様々な非イオン性界面活性剤が単独あるいは2種類以上併用されて用いられている。例えば、アルキルフェニルエーテルにエチレンオキシド等のアルキレンオキシドを付加したアルキルフェニルエーテル型の界面活性剤として、HLBが8〜12及び12を超え16までのノニルフェノールのエチレンオキサイド付加物を併用することが提案されている(特許文献1)。一般的にオクチルフェノールやノニルフェノール等を用いたアルキルフェニルエーテル型の界面活性剤は乳化性に優れる、樹脂の重合に悪影響を及ぼさない、低価格等の特長から、広く用いられてきた。しかし、生物や環境への影響への懸念から、アルキルフェノールを使用せずに脂肪族アルコールへと移行しつつある。また、アルキルフェニルエーテル型の界面活性剤は起泡しやすい問題があった。例えば塗料として用いる場合は、得られるポリマーエマルジョンが起泡しやすいと塗布面にピンホール等の欠陥が生じ、均一な塗膜が得られず塗装面の外観を損ねる原因となる。 Conventionally, various nonionic surfactants are used alone or in combination of two or more as emulsifiers for emulsion polymerization. For example, as an alkylphenyl ether type surfactant in which an alkylene oxide such as ethylene oxide is added to an alkylphenyl ether, it is proposed to use an ethylene oxide adduct of nonylphenol having an HLB of more than 8-12 and up to 12 to 16. (Patent Document 1). In general, alkylphenyl ether type surfactants using octylphenol, nonylphenol and the like have been widely used because of their excellent emulsifiability, no adverse effects on resin polymerization, and low cost. However, due to concerns about impacts on living organisms and the environment, they are shifting to aliphatic alcohols without using alkylphenols. In addition, alkylphenyl ether type surfactants have a problem of easily foaming. For example, when it is used as a paint, if the resulting polymer emulsion tends to foam, defects such as pinholes occur on the coated surface, and a uniform coating film cannot be obtained, causing the appearance of the painted surface to be impaired.
アルキルフェニルエーテル型の界面活性剤の代替としては、少なくとも3個のメチル基を有する炭素数10のアルコールを用い、これにエチレンオキシド付加した化合物や、さらに硫酸エステル化した化合物を乳化重合用乳化剤として用いることが提案されている(特許文献2)。この化合物は、アルキルフェニルエーテル型の界面活性剤と同等の重合時における乳化性を有している。しかし、得られるポリマーエマルジョンは依然として起泡しやすい問題があった。 As an alternative to the alkylphenyl ether type surfactant, a C10 alcohol having at least 3 methyl groups is used, and a compound obtained by adding ethylene oxide or a sulfated compound is used as an emulsifier for emulsion polymerization. (Patent Document 2). This compound has an emulsifying property during polymerization equivalent to that of an alkylphenyl ether type surfactant. However, the obtained polymer emulsion still has a problem of easily foaming.
また、例えば電子部品用の接着剤として用いる場合、塗布する基材の小型化に伴い、より微細に均一に塗布することのできるポリマーエマルジョンが求められている。そのため、ポリマーエマルジョンに求められる性能として、低泡性のみでなく濡れ性に優れるものが求められている。接着剤が起泡しやすかったり濡れ性が不十分だったりすると、接着剤の塗布されない部分が発生することで、接着強度の低下を引き起こす原因となる。 For example, when it is used as an adhesive for electronic parts, a polymer emulsion that can be applied more finely and uniformly is demanded as the substrate to be applied is downsized. Therefore, as the performance required for the polymer emulsion, not only low foamability but also excellent wettability is required. If the adhesive is liable to foam or if the wettability is insufficient, a portion where the adhesive is not applied is generated, which causes a decrease in adhesive strength.
そこで、分岐度が1.8〜2.4の炭素数が10のアルコールを用い、これにプロピレンオキサイドやエチレンオキサイドを付加した多分散度が1.10〜1.20の非イオン活性剤を乳化重合用乳化剤として用いることが提案されている(特許文献3)。この化合物は、重合時の乳化安定性に優れるのみでなく、低泡性を有するポリマーエマルジョンを得ることができる。しかし、低泡性は不十分であり、加えて、濡れ性に劣るという問題があった。 Therefore, a nonionic active agent having a polydispersity of 1.10 to 1.20 obtained by adding propylene oxide or ethylene oxide to an alcohol having a branching degree of 1.8 to 2.4 and having 10 carbon atoms is emulsified. It has been proposed to use as an emulsifier for polymerization (Patent Document 3). This compound is not only excellent in emulsion stability during polymerization, but also can provide a polymer emulsion having low foaming properties. However, the low foaming property is insufficient, and in addition, there is a problem that the wettability is inferior.
したがって、重合時の乳化安定性、及び得られるポリマーエマルジョンの低泡性や濡れ性のいずれにも優れる乳化重合用乳化剤が望まれていた。 Therefore, an emulsifier for emulsion polymerization that is excellent in both the emulsion stability during polymerization and the low foamability and wettability of the resulting polymer emulsion has been desired.
本発明の課題は、重合時の乳化安定性、及び得られるポリマーエマルジョンの低泡性や濡れ性のいずれにも優れる乳化重合用乳化剤を提供することである。 The subject of this invention is providing the emulsifier for emulsion polymerization which is excellent in both the emulsion stability at the time of superposition | polymerization, and the low-foaming property and wettability of the polymer emulsion obtained.
上記目的を達成するために鋭意検討を重ねた結果、特定のアルコールにオキシエチレン基やオキシプロピレン基を特定の割合で付加させた構造の化合物を用いることで、重合時の乳化安定性に優れ、且つ、得られるポリマーエマルジョンは低泡性や濡れ性に優れることを見出し、本発明に至ったものである。 As a result of intensive studies in order to achieve the above object, as a result of using a compound having a structure in which an oxyethylene group or an oxypropylene group is added to a specific alcohol at a specific ratio, the emulsion stability during polymerization is excellent. In addition, the polymer emulsion obtained has been found to be excellent in low-foaming property and wettability, leading to the present invention.
すなわち本発明に係る乳化重合用乳化剤は、式(1)で表される化合物100重量部に対し、式(2)で表される化合物を20〜110重量部添加してなることを特徴とする。
R1O−(AO)a−(PO)b−H (1)
(式(1)中、R1は炭素数9のアルキル基であり、AOはオキシエチレン基またはオキシプロピレン基であり、aはAOの平均付加モル数の合計であって、a=10〜35であり、(AO)a中の70重量%以上はオキシエチレン基が占めており、POはオキシプロピレン基であり、bはPOの平均付加モル数であってb=3〜5であり、a/b=3〜12である。)
R2O−(EO)c−(PO)d−H (2)
(式(2)中、R2は炭素数9のアルキル基であり、EOはオキシエチレン基であり、POはオキシプロピレン基であり、cはEOの平均付加モル数であってc=2〜9であり、dはPOの平均付加モル数であってd=2〜4であり、c/d=0.6〜3である。)
That is, the emulsifier for emulsion polymerization according to the present invention is obtained by adding 20 to 110 parts by weight of the compound represented by the formula (2) to 100 parts by weight of the compound represented by the formula (1). .
R 1 O- (AO) a - (PO) b -H (1)
(In the formula (1), R 1 is an alkyl group having 9 carbon atoms, AO is an oxyethylene group or an oxypropylene group, a is the sum of the average added moles of AO, and a = 10 to 35 (AO) 70% by weight or more of (AO) a is occupied by oxyethylene groups, PO is an oxypropylene group, b is the average number of moles of PO added, and b = 3 to 5, / B = 3-12.)
R 2 O- (EO) c - (PO) d -H (2)
(In the formula (2), R 2 is an alkyl group having 9 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, c is an average added mole number of EO, and c = 2 to 2. 9 and d is the average number of moles of PO added, d = 2-4, and c / d = 0.6-3.)
また、式(1)で表される化合物のAOがオキシエチレン基であることを特長とする、乳化重合用乳化剤である。 The emulsifier for emulsion polymerization is characterized in that AO of the compound represented by the formula (1) is an oxyethylene group.
本発明により、重合時の乳化安定性、及び得られるポリマーエマルジョンの低泡性や濡れ性のいずれにも優れる乳化重合用乳化剤を提供できるため、大変有用である。 According to the present invention, an emulsifier for emulsion polymerization which is excellent in both the emulsion stability during polymerization and the low foamability and wettability of the resulting polymer emulsion is very useful.
(式(1)で表される化合物)
R1は、炭素数9のアルキル基であり、また、直鎖または分岐の炭素数9のアルコールから水酸基を除いた残基である。具体的には、直鎖であるn−ノナノール由来のn−ノニル基や、n−ブテンやイソブチレンを原料としてオキソ法により得られるメチル分岐を有したイソノニルアルコール由来のイソノニル基や3,5,5−トリメチル−1−ヘキサノール由来の3,5,5−トリメチルヘキシル基が挙げられる。炭素数9のアルキル基のうち、メチル分岐を有するイソノニル基や3,5,5−トリメチルヘキシル基が好ましく、特に、重合時の乳化安定性や、得られるポリマーエマルジョンの低泡性や濡れ性の観点から、3個のメチル分岐を有する3,5,5−トリメチルヘキシル基が最も好ましい。
(Compound represented by Formula (1))
R 1 is an alkyl group having 9 carbon atoms, and is a residue obtained by removing a hydroxyl group from a linear or branched alcohol having 9 carbon atoms. Specifically, a linear n-nonyl group derived from n-nonanol, an isononyl group derived from isononyl alcohol having a methyl branch obtained by an oxo method using n-butene or isobutylene as a raw material, Examples include 3,5,5-trimethylhexyl group derived from 5-trimethyl-1-hexanol. Of the alkyl groups having 9 carbon atoms, isononyl groups having a methyl branch and 3,5,5-trimethylhexyl groups are preferred. In particular, the emulsion stability during polymerization and the low foamability and wettability of the resulting polymer emulsion From the viewpoint, a 3,5,5-trimethylhexyl group having three methyl branches is most preferable.
R1の炭素数が8以下の場合、重合時の乳化安定性や、得られるポリマーエマルジョンの濡れ性が劣るため好ましくない。 When R 1 has 8 or less carbon atoms, the emulsion stability during polymerization and the wettability of the resulting polymer emulsion are inferior.
AOは、オキシエチレン基またはオキシプロピレン基である。AOにおいて、オキシエチレン基とオキシプロピレン基とは併用してもよく、オキシエチレン基のみからなっていてもよい。 AO is an oxyethylene group or an oxypropylene group. In AO, the oxyethylene group and the oxypropylene group may be used in combination, or may be composed of only the oxyethylene group.
オキシエチレン基とオキシプロピレン基とを併用する場合は、ブロック付加物でもランダム付加物でも良い。オキシエチレン基とオキシプロピレン基とを併用する場合は、式(1)で表される化合物の凝固点を低下させてハンドリング性を向上させる観点から、ランダム付加物が特に好ましい。 When an oxyethylene group and an oxypropylene group are used in combination, a block adduct or a random adduct may be used. When an oxyethylene group and an oxypropylene group are used in combination, a random adduct is particularly preferable from the viewpoint of improving the handling property by lowering the freezing point of the compound represented by the formula (1).
また、オキシエチレン基とオキシプロピレン基とを併用する場合は、(AO)a部分のオキシエチレン基の割合は、70重量%以上である。オキシエチレン基の割合が70重量%未満では乳化性が低下し、重合時に固形分の析出やゲル化を引き起こしやすくなる。この観点からは、(AO)a部分のオキシエチレン基の割合は、70〜90重量%が好ましく、70〜85重量%がより好ましい。 Moreover, when using together an oxyethylene group and an oxypropylene group, the ratio of the oxyethylene group of (AO) a part is 70 weight% or more. When the proportion of oxyethylene groups is less than 70% by weight, the emulsifying properties are lowered, and solids are liable to precipitate or gel during polymerization. From this viewpoint, the proportion of the oxyethylene group in the (AO) a portion is preferably 70 to 90% by weight, and more preferably 70 to 85% by weight.
オキシプロピレン基は、プロピレンオキシド由来のオキシプロピレン基(メチルオキシエチレン基)である。 The oxypropylene group is a propylene oxide-derived oxypropylene group (methyloxyethylene group).
aは、AO(オキシエチレン基またはオキシプロピレン基)の平均付加モル数である。AOがオキシエチレン基とオキシプロピレン基との両方を含む場合は、aは、それぞれの平均付加モル数の合計を示す。 a is the average added mole number of AO (oxyethylene group or oxypropylene group). When AO contains both an oxyethylene group and an oxypropylene group, a shows the sum total of each average addition mole number.
aは、10〜35とする。aが10未満の場合、乳化性が低下し、重合時に固形分の析出やゲル化を引き起こしやすくなる。また、式(1)で表される化合物の凝固点を低下させてハンドリング性を向上させる観点から、aは、12以上が更に好ましく、15以上が一層好ましい。また、aが35を超えると、粘度の上昇や凝固点の影響によりハンドリング性が低下するため、aは30以下が好ましく、20以下がより好ましい。 a is 10 to 35. When a is less than 10, the emulsifying property is lowered, and it becomes easy to cause precipitation and gelation of solids during polymerization. From the viewpoint of reducing the freezing point of the compound represented by the formula (1) and improving the handleability, a is more preferably 12 or more, and more preferably 15 or more. Further, when a exceeds 35, the handling property is lowered due to an increase in viscosity or the influence of the freezing point, and therefore a is preferably 30 or less, and more preferably 20 or less.
POは、オキシプロピレン基であり、プロピレンオキシド由来のオキシプロピレン基(メチルオキシエチレン基)である。bは、オキシプロピレン基の平均付加モル数であり、3〜5であり、3〜4がより好ましい。bが3より小さい場合は、得られるポリマーエマルジョンの低起泡性や濡れ性に劣るため好ましくない。また、bが5より大きい場合は、乳化性が低下し、重合時に固形分の析出やゲル化を引き起こしやすくなるため好ましくない。 PO is an oxypropylene group and is an oxypropylene group (methyloxyethylene group) derived from propylene oxide. b is an average addition mole number of an oxypropylene group, is 3-5, and 3-4 are more preferable. When b is smaller than 3, the resulting polymer emulsion is inferior in low foaming property and wettability, which is not preferable. On the other hand, when b is larger than 5, the emulsifying property is lowered, and it is easy to cause precipitation or gelation of solids during polymerization, which is not preferable.
a/bは、AOの平均付加モル数aのPOの平均付加モル数bに対する比であり、3〜12である。a/bが3より小さい場合、乳化性が低下し、重合時に固形分の析出やゲル化を引き起こしやすくなる。この観点からは、a/bは、5以上がさらに好ましい。また、a/bが12より大きい場合、得られるポリマーエマルジョンの低泡性やレベリング性に劣るため好ましくない。この観点からは、a/bは12以下であるが、10以下がより好ましい。 a / b is a ratio of the average added mole number a of AO to the average added mole number b of PO, and is 3-12. When a / b is smaller than 3, the emulsifying property is lowered, and it becomes easy to cause precipitation and gelation of solids during polymerization. From this viewpoint, a / b is more preferably 5 or more. Moreover, when a / b is larger than 12, it is not preferable because the resulting polymer emulsion is inferior in low foaming property and leveling property. From this viewpoint, a / b is 12 or less, but 10 or less is more preferable.
なお、式(1)で表される化合物は、単独で使用しても、2種類以上を併用しても良い。 In addition, the compound represented by Formula (1) may be used independently, or may use 2 or more types together.
(式(2)で表される化合物)
R2は、炭素数9のアルキル基であり、直鎖または分岐の炭素数9のアルコールから水酸基を除いた残基である。具体的には、直鎖であるn−ノナノール由来のn−ノニル基や、n−ブテンやイソブチレンを原料としてオキソ法により得られるメチル分岐を有したイソノニルアルコール由来のイソノニル基や3,5,5−トリメチル−1−ヘキサノール由来の3,5,5−トリメチルヘキシルが挙げられる。炭素数9のアルキル基のうち、メチル分岐を有するイソノニル基や3,5,5−トリメチルヘキシル基が好ましく、特に、重合時の乳化安定性や、得られるポリマーエマルジョンの低泡性や濡れ性の観点から、3個のメチル分岐を有する3,5,5−トリメチルヘキシル基が最も好ましい。
(Compound represented by Formula (2))
R 2 is an alkyl group having 9 carbon atoms, and is a residue obtained by removing a hydroxyl group from a linear or branched alcohol having 9 carbon atoms. Specifically, a linear n-nonyl group derived from n-nonanol, an isononyl group derived from isononyl alcohol having a methyl branch obtained by an oxo method using n-butene or isobutylene as a raw material, Examples include 3,5,5-trimethylhexyl derived from 5-trimethyl-1-hexanol. Of the alkyl groups having 9 carbon atoms, isononyl groups having a methyl branch and 3,5,5-trimethylhexyl groups are preferred. In particular, the emulsion stability during polymerization and the low foamability and wettability of the resulting polymer emulsion From the viewpoint, a 3,5,5-trimethylhexyl group having three methyl branches is most preferable.
R2が炭素数8以下の場合、重合時の乳化安定性や、得られるポリマーエマルジョンの濡れ性が劣るため好ましくない。 When R 2 is 8 or less carbon atoms, emulsion stability and the time of polymerization is not preferable because the wettability of the resulting polymer emulsion is poor.
EOは、オキシエチレン基である。cはオキシエチレン基の平均付加モル数であり、2〜9とする。cが9より大きい場合、得られるポリマーエマルジョンの低泡性や濡れ性が低下するため好ましくない。cは、2〜8が好ましく、2〜5がより好ましい。 EO is an oxyethylene group. c is an average addition mole number of an oxyethylene group, and is set to 2-9. When c is larger than 9, it is not preferable because low foamability and wettability of the polymer emulsion to be obtained are lowered. c is preferably from 2 to 8, and more preferably from 2 to 5.
POは、オキシプロピレン基であり、プロピレンオキシド由来のオキシプロピレン基(メチルオキシエチレン基)である。dは、POの平均付加モル数であり、2〜4とする。dが2より小さい場合は、得られるポリマーエマルジョンの低起泡性や濡れ性に劣るため好ましくない。また、dが4より大きい場合は、乳化性が低下して重合時に固形分の析出やゲル化を引き起こしやすくなる。dは、3〜4がより好ましい。 PO is an oxypropylene group and is an oxypropylene group (methyloxyethylene group) derived from propylene oxide. d is the average number of moles of PO added and is 2-4. When d is smaller than 2, it is not preferable because the resulting polymer emulsion is inferior in low foaming property and wettability. On the other hand, when d is larger than 4, the emulsifiability is lowered, and it is easy to cause solid precipitation or gelation during polymerization. As for d, 3-4 are more preferable.
c/dは、EOの平均付加モル数cのPOの平均付加モル数dに対する比であり、0.6〜3である。これが0.6より小さい場合、乳化性が低下し、重合時に固形分の析出やゲル化を引き起こしやすくなるため好ましくない。この観点からは、c/dは0.6以上とするが、0.8以上がさらに好ましい。また、c/dが3より大きい場合、得られるポリマーエマルジョンの低泡性や濡れ性に劣るため好ましくない。この観点からは、c/dは、2以下がより好ましい。 c / d is the ratio of the average added mole number c of EO to the average added mole number d of PO, and is 0.6-3. When this is smaller than 0.6, the emulsifying property is lowered, and it is not preferable because solid content is easily precipitated and gelled during polymerization. From this viewpoint, c / d is set to 0.6 or more, and more preferably 0.8 or more. Moreover, when c / d is larger than 3, it is not preferable because the resulting polymer emulsion is inferior in low-foaming property and wettability. From this viewpoint, c / d is more preferably 2 or less.
なお、式(2)で表される化合物は、単独で使用しても、2種類以上を併用しても良い。 In addition, the compound represented by Formula (2) may be used independently, or may use 2 or more types together.
式(2)で表される化合物の添加量は、式(1)で表される化合物100重量部に対して、20〜110重量部とする。式(2)で表される化合物の添加量が20重量部より低い場合は、得られるポリマーエマルジョンの低起泡性やレベリング性に劣る。この観点からは、式(2)で表される化合物の添加量を20重量部以上とする。また、式(2)で表される化合物の添加量が110重量部より多い場合は、乳化性が低下し、重合時の固形分の析出やゲル化を引き起こしやすくなる。この観点から式(2)で表される化合物の添加量は、110重量部以下とするが、100重量部以下が更に好ましい。 The addition amount of the compound represented by the formula (2) is 20 to 110 parts by weight with respect to 100 parts by weight of the compound represented by the formula (1). When the amount of the compound represented by the formula (2) is lower than 20 parts by weight, the resulting polymer emulsion is inferior in low foaming property and leveling property. From this point of view, the addition amount of the compound represented by formula (2) and 20 parts by weight or more. Moreover, when there are more addition amounts of the compound represented by Formula (2) than 110 weight part, emulsification property will fall and it will become easy to cause precipitation and gelatinization of the solid content at the time of superposition | polymerization. From this viewpoint, the addition amount of the compound represented by the formula (2) is 110 parts by weight or less, and more preferably 100 parts by weight or less.
本発明の乳化剤組成物は、式(1)の化合物と式(2)の化合物からなり、その使用量の合計は、通常、後述のモノマーに対して0.1〜20重量%であり、好ましくは1〜15重量%である。 The emulsifier composition of the present invention consists of the compound of formula (1) and the compound of formula (2), and the total amount used is usually 0.1 to 20% by weight, preferably based on the monomers described below. Is 1 to 15% by weight.
本発明の乳化剤は、各種モノマーの乳化重合に適用することができ、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、アルキル基の水素原子の一部または全てがフッ素原子に置換された炭素数1〜6のアルキル基であるポリフルオロ基と炭素−炭素不飽和二重結合などの不飽和基を1個以上有するフッ素樹脂モノマー等が挙げられる。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 of the present invention can be applied to emulsion polymerization of various monomers, and the type of monomer is not particularly limited. Examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid. Acid methyl, butyl methacrylate, glycidyl methacrylate, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, acrylamide, methacrylamide, hydroxyethyl ester acrylate, hydroxyethyl ester methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid, Acrylic monomers such as methacrylic acid, aromatic monomers such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, divinylbenzene, vinyl acetate, etc. Ester ester monomers, halogenated olefin monomers such as vinyl chloride and vinylidene chloride, conjugated diolefin monomers such as butadiene, isoprene and chloroprene, and others, ethylene, itaconic acid, fumaric acid, maleic acid, methyl maleate, alkyl groups Fluoropolymer monomer having at least one polyfluoro group which is an alkyl group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms and one or more unsaturated groups such as carbon-carbon unsaturated double bonds Etc. These monomers can be used alone or in combination of two or more.
本発明の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、ベンジルパーオキシド、ラウリルパーオキシド、スクシニルパーオキシド、tert−ブチルパーピバレート、2,2’−アゾビス−2−メチルブチロニトリル、2,2’−アゾビスイソブチロニトリル、2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]、2,2’−アゾビス(4−メトキシ−2,4−ジメチルバレロニトリル)、1,1’−アゾビス(2−シクロヘキサン−1−カルボニトリル)、2,2’−アゾビス(2,4−ジメチルバレロニトリル)、1,1’−アゾビス(1−アセトキシ−1−フェニルエタン)、ジメチルアゾビスイソブチレート、4,4’−アゾビス(4−シアノ吉草酸)、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。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。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。 For emulsion polymerization using the emulsifier of the present invention, conventionally known polymerization initiators can be used without particular limitation. Representative examples include hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl peroxide, benzyl peroxide, lauryl peroxide, succinyl peroxide, tert-butyl perpivalate, 2,2′- Azobis-2-methylbutyronitrile, 2,2′-azobisisobutyronitrile, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis (4 -Methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis (2-cyclohexane-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'- Azobis (1-acetoxy-1-phenylethane), dimethylazobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid) 2,2'-azobis (2-amidinopropane) dihydrochloride, and the like. Redox polymerization can also be performed using sodium hydrogen sulfite, ferrous ammonium sulfate, or the like as a polymerization accelerator. 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.
また、重合の際には溶媒を添加することができる。例えば、水、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、2−ブタノール、tert−ブタノール、アセトン、メチルエチルケトン、メチルイロブチルケトン、ジメチルホルムアミド、ジメチルアセトアミド、ベンゼン、トルエン、キシレン、酢酸エチル等が挙げられる。 Moreover, a solvent can be added in the case of superposition | polymerization. For example, water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, tert-butanol, acetone, methyl ethyl ketone, methyl butyl ketone, dimethylformamide, dimethylacetamide, benzene, toluene, xylene, ethyl acetate, etc. Can be mentioned.
乳化重合の方法は、バッチ式重合法、連続式重合法等、通常用いられるいずれの方法でも良い。バッチ式重合法の場合、溶媒、乳化剤、モノマー、開始剤を一括に仕込んでも、モノマーや開始剤を滴下しても良い。重合温度や重合時間は、モノマーの重合性や開始剤によるが、通常は20〜130℃、好ましくは30〜100℃である。 The emulsion polymerization method may be any commonly used method such as a batch polymerization method or a continuous polymerization method. In the case of a batch polymerization method, a solvent, an emulsifier, a monomer and an initiator may be charged all at once, or a monomer and an initiator may be dropped. The polymerization temperature and polymerization time depend on the polymerizability of the monomer and the initiator, but are usually 20 to 130 ° C, preferably 30 to 100 ° C.
上記の方法で得られたポリマーエマルジョンに、その他成分としてエマルジョンの安定化のための安定化剤や増粘剤、腐敗防止のための防腐剤を添加しても良い。これらは、乳化重合前に添加しても重合後に添加しても良い。さらに、各種陽イオン性、陰イオン性、非イオン性界面活性剤や式(1)や式(2)で表される化合物を添加してもよい。 To the polymer emulsion obtained by the above method, stabilizers and thickeners for stabilizing the emulsion and preservatives for preventing spoilage may be added as other components. These may be added before emulsion polymerization or after polymerization. Further, various cationic, anionic, and nonionic surfactants and compounds represented by formula (1) and formula (2) may be added.
本発明の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)、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、ガラス、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 of the present invention is, for example, as a printing ink, paint (for construction, household use, can use, electrodeposition coating, etc.), adhesive, pressure-sensitive adhesive, coating agent, impregnation reinforcing agent, etc. It can be applied to wood, metal, paper, cloth, plastic, glass, ceramic, and other concrete.
以下に、実施例を挙げて本発明をさらに詳細に説明する。
本発明にかかる式(1)で表される化合物の合成例を示す。また、表1に合成した化合物及び用いた化合物を示す。
Hereinafter, the present invention will be described in more detail with reference to examples.
The synthesis example of the compound represented by Formula (1) concerning this invention is shown. Table 1 shows the synthesized compounds and the compounds used.
(合成例1(化合物1))
5Lオートクレーブに、3,5,5−トリメチル−1−ヘキサノール(商品名:ノナノール、KHネオケム(株)製)433g(3mol)および水酸化カリウム5gを仕込み、窒素置換後、撹拌しながら120℃に昇温した。次に滴下装置によりエチレンオキシド2114g(48mol)を滴下し、1時間反応させた。続いて滴下装置によりプロピレンオキシド523g(9mol)を滴下し、2時間反応させた。その後、オートクレーブ内から、反応物を取り出し、塩酸で中和して、pH6〜7とし、含有する水分を除去するため、100℃、1時間、減圧処理を行い、最後に濾過により塩を除去して、3,5,5−トリメチルヘキシル−O−(EO)16−(PO)3−Hで表される化合物2917gを得た。
(Synthesis Example 1 (Compound 1))
Into a 5 L autoclave, 433 g (3 mol) of 3,5,5-trimethyl-1-hexanol (trade name: Nonanol, manufactured by KH Neochem Co., Ltd.) and 5 g of potassium hydroxide were charged. The temperature rose. Next, 2114 g (48 mol) of ethylene oxide was added dropwise with a dropping device and reacted for 1 hour. Subsequently, 523 g (9 mol) of propylene oxide was dropped with a dropping device and reacted for 2 hours. Thereafter, the reaction product is taken out from the autoclave, neutralized with hydrochloric acid to pH 6-7, and subjected to reduced pressure treatment at 100 ° C. for 1 hour to remove the contained water, and finally the salt is removed by filtration. Thus, 2917 g of a compound represented by 3,5,5-trimethylhexyl-O— (EO) 16- (PO) 3 —H was obtained.
上記合成例1に準じて、表1に示す各化合物を合成した。表2に組成を示し、表3に結果を示す。 Each compound shown in Table 1 was synthesized according to Synthesis Example 1. Table 2 shows the composition, and Table 3 shows the result.
(ポリマーエマルジョンの調製と乳化重合方法、及び乳化性の確認)
(実施例1)
撹拌羽根、窒素吹き込み管、熱電対、冷却管の接続された300mL4つ口フラスコに、イオン交換水:90.0g、3,5,5−トリメチルヘキシル−O−(EO)16−(PO)3−Hで表される化合物:2.0g、3,5,5−トリメチルヘキシル−O−(EO)4−(PO)3−Hで表される化合物:2.0gを仕込み、均一に溶解させた。これに、アクリル酸2−エチルヘキシル:40.0g、過硫酸カリウム0.3gを仕込み、撹拌して均一に乳化した。これを撹拌しながら窒素雰囲気下に40℃に昇温し、4時間重合を行い、ポリマーエマルジョンを得た。
(Preparation of polymer emulsion, emulsion polymerization method, and confirmation of emulsification)
Example 1
In a 300 mL four-necked flask connected with a stirring blade, a nitrogen blowing tube, a thermocouple, and a cooling tube, ion-exchanged water: 90.0 g, 3,5,5-trimethylhexyl-O- (EO) 16- (PO) 3 represented by -H compound: 2.0 g, 3,5,5-trimethyl-hexyl -O- (EO) 4 - (PO ) 3 represented by -H compounds: charged 2.0 g, uniformly dissolved It was. To this, 2-ethylhexyl acrylate: 40.0 g and potassium persulfate 0.3 g were charged and stirred to uniformly emulsify. While stirring this, the temperature was raised to 40 ° C. in a nitrogen atmosphere and polymerization was carried out for 4 hours to obtain a polymer emulsion.
上記実施例1に準じて、表2に記載された重量の化合物A、化合物B、アクリル酸2−エチルヘキシル、過硫酸カリウム、イオン交換水を仕込み、乳化重合を行った。 In accordance with Example 1 above, emulsion A was prepared by charging Compound A, Compound B, 2-ethylhexyl acrylate, potassium persulfate, and ion-exchanged water in the weights listed in Table 2.
重合時に均一に乳化しているものが優れた乳化性を有している事を表し、均一に乳化したポリマーエマルジョンが得られたものを○、重合時に固形分が析出したりゲル化したりして均一なポリマーエマルジョンが得られなかったものを×で示す。 It means that what is uniformly emulsified at the time of polymerization has excellent emulsifiability, and ○ that obtained a polymer emulsion that was uniformly emulsified, solids precipitated or gelled at the time of polymerization The case where a uniform polymer emulsion was not obtained is indicated by x.
(起泡試験)
得られたポリマーエマルジョンを50mLスクリュー管に30mL充填し、室温で蓋をして4回/秒の速さで20回上下に振とうし、振とう終了後から1分経過後の液面からの泡の高さを測定した。発生した気泡の高さが低い程、ポリマーエマルジョンが低泡性であることを表し、15mm以下で優れていることを示す。
(Foaming test)
Fill the resulting polymer emulsion with 30 mL into a 50 mL screw tube, cap at room temperature, shake up and down 20 times at a rate of 4 times / second, and remove from the liquid level after 1 minute from the end of shaking. The height of the foam was measured. The lower the height of the generated bubbles, the lower the polymer emulsion, and the better it is at 15 mm or less.
(濡れ性)
得られたポリマーエマルジョンをガラス製パスツールピペットに採取し、ポリエステルフィルム(東洋紡(株)製コスモシャインA4300)、及びガラス板(松浪硝子工業(株)製S9224)上に1滴落とし、乾燥後にできた跡の面積を測定した。乾燥後の面積が大きい程、ポリマーエマルジョンが濡れ性に優れて均一に塗布しやすいことを表し、40.0mm2以上で優れている事を示す。
(Wettability)
The obtained polymer emulsion was collected in a glass Pasteur pipette, dropped on a polyester film (Toyobo Co., Ltd. Cosmo Shine A4300) and a glass plate (S9224, Matsunami Glass Industrial Co., Ltd.), and dried. The area of the trace was measured. The larger the area after drying, the better the polymer emulsion and the easier it is to apply uniformly, indicating that it is better at 40.0 mm 2 or more.
本発明の式(1)及び式(2)で表される化合物を用いた実施例1〜4は、いずれも均一に乳化されており固形分の析出やゲル化することもなく、得られたポリマーエマルジョンは低起泡性、濡れ性に優れていた。 Examples 1 to 4 using the compounds represented by the formulas (1) and (2) of the present invention were all uniformly emulsified and obtained without precipitation or gelation of solids. The polymer emulsion was excellent in low foaming property and wettability.
比較例1は、式(1)で表される化合物を用いなかったため、重合時にゲル化した。
比較例2及び比較例3は、式(2)で表される化合物を用いなかったため、得られたポリマーエマルジョンは濡れ性に劣っていた。
比較例4は、式(1)で表される化合物のオキシプロピレン基が付加されていない化合物を用い、加えて式(2)で表される化合物を用いなかったため、得られたポリマーエマルジョンは濡れ性に劣っていた。
Since Comparative Example 1 did not use the compound represented by Formula (1), it gelled during polymerization.
Since the comparative example 2 and the comparative example 3 did not use the compound represented by Formula (2), the obtained polymer emulsion was inferior in wettability.
In Comparative Example 4, since the compound represented by the formula (1) in which the oxypropylene group was not added was used and the compound represented by the formula (2) was not used, the obtained polymer emulsion was wet. It was inferior.
比較例5は、式(1)で表される化合物のオキシプロピレン基が付加されていないため、得られたポリマーエマルジョンは濡れ性に劣っていた。
比較例6は、式(1)で表される化合物を用いなかったため、重合時にゲル化した。
比較例7は、式(2)で表される化合物を用いなかったため、重合時に固形分が析出して均一なポリマーエマルジョンが得られなかった。
In Comparative Example 5, since the oxypropylene group of the compound represented by the formula (1) was not added, the obtained polymer emulsion was inferior in wettability.
Since Comparative Example 6 did not use the compound represented by Formula (1), it gelled during polymerization.
In Comparative Example 7, since the compound represented by the formula (2) was not used, a solid content was precipitated during the polymerization, and a uniform polymer emulsion could not be obtained.
比較例8は、式(1)で表される化合物のアルキル基が異なり、加えて式(2)で表される化合物を用いなかったため、重合時にゲル化した。
比較例9は、式(1)で表される化合物のアルキル基が異なるため、重合時に固形分が析出して均一なポリマーエマルジョンが得られなかった。
In Comparative Example 8, the alkyl group of the compound represented by the formula (1) was different and, in addition, the compound represented by the formula (2) was not used, and thus gelled at the time of polymerization.
In Comparative Example 9, since the alkyl group of the compound represented by the formula (1) is different, a solid content was precipitated during the polymerization, and a uniform polymer emulsion was not obtained.
比較例10及び比較例11は、式(1)及び式(2)で表される化合物を用いなかったため、得られたポリマーエマルジョンは低泡性や濡れ性に劣っていた。
比較例12は、式(1)及び式(2)で表される化合物を用いなかったため、重合時に固形分が析出して均一なポリマーエマルジョンが得られなかった。
Since the comparative example 10 and the comparative example 11 did not use the compound represented by Formula (1) and Formula (2), the obtained polymer emulsion was inferior to low-foaming property or wettability.
Since Comparative Example 12 did not use the compounds represented by Formula (1) and Formula (2), solid content was precipitated during polymerization, and a uniform polymer emulsion could not be obtained.
Claims (2)
R1O−(AO)a−(PO)b−H (1)
(式(1)中、R1は炭素数9のアルキル基であり、AOはオキシエチレン基またはオキシプロピレン基であり、aはAOの平均付加モル数の合計であって、a=10〜35であり、(AO)a中の70重量%以上はオキシエチレン基が占めており、POはオキシプロピレン基であり、bはPOの平均付加モル数であってb=3〜5であり、a/b=3〜12である。)
R2O−(EO)c−(PO)d−H (2)
(式(2)中、R2は炭素数9のアルキル基であり、EOはオキシエチレン基であり、POはオキシプロピレン基であり、cはEOの平均付加モル数であってc=2〜9であり、dはPOの平均付加モル数であってd=2〜4であり、c/d=0.6〜3である。) An emulsifier for emulsion polymerization, comprising 20 to 110 parts by weight of a compound represented by formula (2) to 100 parts by weight of a compound represented by formula (1).
R 1 O- (AO) a - (PO) b -H (1)
(In the formula (1), R 1 is an alkyl group having 9 carbon atoms, AO is an oxyethylene group or an oxypropylene group, a is the sum of the average added moles of AO, and a = 10 to 35 (AO) 70% by weight or more of (AO) a is occupied by oxyethylene groups, PO is an oxypropylene group, b is the average number of moles of PO added, and b = 3 to 5, / B = 3-12.)
R 2 O- (EO) c - (PO) d -H (2)
(In the formula (2), R 2 is an alkyl group having 9 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, c is an average added mole number of EO, and c = 2 to 2. 9 and d is the average number of moles of PO added, d = 2-4, and c / d = 0.6-3.)
The emulsifier for emulsion polymerization according to claim 1, wherein AO of the compound represented by formula (1) is an oxyethylene group.
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