JP2016069523A - Emulsifier for emulsion polymerization - Google Patents
Emulsifier for emulsion polymerization Download PDFInfo
- Publication number
- JP2016069523A JP2016069523A JP2014200433A JP2014200433A JP2016069523A JP 2016069523 A JP2016069523 A JP 2016069523A JP 2014200433 A JP2014200433 A JP 2014200433A JP 2014200433 A JP2014200433 A JP 2014200433A JP 2016069523 A JP2016069523 A JP 2016069523A
- Authority
- JP
- Japan
- Prior art keywords
- emulsifier
- emulsion polymerization
- anionic surfactant
- emulsion
- mol
- 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.)
- Granted
Links
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims abstract description 37
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 33
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 63
- -1 alkaline earth metal cation Chemical class 0.000 claims description 56
- 239000000839 emulsion Substances 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000012459 cleaning agent Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 20
- 238000000034 method Methods 0.000 description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 15
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 125000006353 oxyethylene group Chemical group 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 4
- 150000001896 cresols Chemical class 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000002904 solvent Chemical class 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 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 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001180 sulfating effect Effects 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
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 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
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 125000004806 1-methylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-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
- 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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004807 2-methylethylene group Chemical group [H]C([H])([H])C([H])([*:2])C([H])([H])[*:1] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 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 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical compound CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
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- 238000005755 formation reaction Methods 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
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- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229940006487 lithium cation Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium 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
- 238000005259 measurement Methods 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 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
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Detergent Compositions (AREA)
Abstract
Description
本発明は、乳化重合用乳化剤に関する。 The present invention relates to an emulsifier for emulsion polymerization.
従来、各種界面活性剤を用い、乳化重合法によってアクリル酸エステル系重合体、エチレン−酢酸ビニル共重合体、スチレン−ブタジエン共重合体、スチレン−アクリロニトリル共重合体等の重合体を製造する方法が提案されている。 Conventionally, a method for producing a polymer such as an acrylate polymer, an ethylene-vinyl acetate copolymer, a styrene-butadiene copolymer, a styrene-acrylonitrile copolymer by emulsion polymerization using various surfactants. Proposed.
例えば、長鎖アルキル硫酸塩、長鎖アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、アルキルジフェニルエーテルジスルホン酸塩等の陰イオン性界面活性剤、また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、プルロニック型界面活性剤等の非イオン界面活性剤を用いて乳化重合する方法が知られている。 For example, anionic surfactants such as long chain alkyl sulfates, long chain alkyl benzene sulfonates, polyoxyethylene alkyl phenyl ether sulfates, alkyl diphenyl ether disulfonates, or polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyls A method of emulsion polymerization using a nonionic surfactant such as ether, polyoxyethylene fatty acid ester, or pluronic surfactant is known.
本来、重合体エマルジョンの製造において使用される界面活性剤は、重合の開始反応、生成反応に関与するのみではなく、重合中の重合体エマルジョンの安定化、生成した重合体エマルジョンの機械的安定性や化学的安定性、凍結安定性、顔料混和性、貯蔵安定性などに深く関与している。 Originally, the surfactant used in the production of the polymer emulsion is not only involved in the initiation reaction and the formation reaction of the polymerization, but also stabilizes the polymer emulsion during the polymerization, and the mechanical stability of the produced polymer emulsion. And chemical stability, freeze stability, pigment miscibility, and storage stability.
また、界面活性剤はエマルジョンの粒子径、粘性、起泡性等の物性にも大きく影響するものであり、界面活性剤の選択ではその用途に適合した界面活性剤を選定することが肝要である。 In addition, surfactants greatly affect the physical properties of the emulsion, such as particle size, viscosity, and foaming properties, and it is important to select a surfactant that is suitable for the application. .
一般に非イオン性界面活性剤は、その構造から推察できるようにイオンの影響を受け難く、化学的安定性の良い重合体エマルジョンを得ることができる。しかしながら、重合中に発生する凝集物量は、陰イオン性界面活性剤と比べて比較的多く、安定なエマルジョンを得ることが難しいという問題がある。 In general, a nonionic surfactant is hardly affected by ions as can be inferred from its structure, and a polymer emulsion having good chemical stability can be obtained. However, the amount of agglomerates generated during the polymerization is relatively large compared to an anionic surfactant, and there is a problem that it is difficult to obtain a stable emulsion.
一方、陰イオン性界面活性剤は親水基に静電的反撥力の効果があるため、安定性良好な重合体エマルジョンを得ることができるが、使用される陰イオン性界面活性剤が本質的に泡立ちしやすい性質を有しているため、重合体エマルジョンの製造および使用工程において、種々障害をもたらす原因となっている。すなわち、重合体エマルジョンの製造工程に おいては、製造中の重合体エマルジョンが多くの泡を生じることにより、加熱や冷却の効率が低下したり、未反応単量体の回収および除去時に障害となったりする。また、使用工程では、例えば塗料用ビヒクルや紙加工または接着剤に用いる場合、重合体エマルジョンの発泡により、得られる皮膜に気泡やピンホールが残り、このために皮膜の耐水性や接着力の低下、および最終製品の仕上がりの不良につながる原因となっている。 On the other hand, since an anionic surfactant has an electrostatic repulsive effect on a hydrophilic group, a polymer emulsion with good stability can be obtained. However, the anionic surfactant used is essentially Since it has the property of easily foaming, it causes various obstacles in the production and use process of the polymer emulsion. That is, in the production process of the polymer emulsion, the polymer emulsion being produced produces a lot of bubbles, so that the efficiency of heating and cooling is reduced, and it is an obstacle when recovering and removing unreacted monomers. It becomes. Also, in the process of use, for example, when used for paint vehicles, paper processing or adhesives, bubbles and pinholes remain in the resulting film due to foaming of the polymer emulsion, which reduces the water resistance and adhesion of the film. , And the final product is poor.
このような、乳化重合用乳化剤として陰イオン性界面活性剤を用いる場合に生じる課題を解決することを目的として、例えば特許文献１では、スチレン化アルキルフェノール誘導体を乳化重合用乳化剤として用いる技術が提案されている。 For example, Patent Document 1 proposes a technique of using a styrenated alkylphenol derivative as an emulsifier for emulsion polymerization in order to solve such problems that occur when an anionic surfactant is used as an emulsifier for emulsion polymerization. ing.
特許文献１に記載されているようなスチレン化アルキルフェノール誘導体を用いることで、陰イオン性界面活性剤でありながら起泡性がある程度抑えられ、重合安定性についても従来の界面活性剤と比較すると改善されているとされている。 By using a styrenated alkylphenol derivative as described in Patent Document 1, foaming properties can be suppressed to some extent even though it is an anionic surfactant, and the polymerization stability is also improved compared to conventional surfactants. It is said that it has been.
しかしながら、本発明者らの検討によれば、特許文献１に開示された一般式（１）で表されるスチレン化アルキルフェノール誘導体を用いた場合であっても、必ずしも十分な重合安定性が達成できない場合があることが判明した。特に工業的用途では非常に高レベルの重合安定性が求められつつあり、このような高レベルの重合安定性を達成可能な乳化重合用乳化剤の開発に対する要求は非常に大きいものがある。 However, according to studies by the present inventors, even when the styrenated alkylphenol derivative represented by the general formula (1) disclosed in Patent Document 1 is used, sufficient polymerization stability cannot always be achieved. It turns out that there may be cases. Particularly for industrial applications, a very high level of polymerization stability is being demanded, and there is a great demand for the development of an emulsifier for emulsion polymerization that can achieve such a high level of polymerization stability.
そこで本発明は、陰イオン性界面活性剤を用いた乳化重合用乳化剤において、重合安定性をよりいっそう向上させうる手段を提供することを目的とする。 Accordingly, an object of the present invention is to provide a means capable of further improving the polymerization stability in an emulsifier for emulsion polymerization using an anionic surfactant.
本発明者らは上記課題を解決すべく鋭意検討を行った。その結果、特許文献１に開示された一般式（１）で表されるスチレン化アルキルフェノール誘導体におけるスチレンまたはメチルスチレンの２モル付加体の割合（モル比）を特定の範囲内の値に精密に制御することによって、上記課題を解決することが可能となることを見出し、本発明を完成させるに至った。 The present inventors have intensively studied to solve the above problems. As a result, the ratio (molar ratio) of 2-mole adduct of styrene or methylstyrene in the styrenated alkylphenol derivative represented by the general formula (1) disclosed in Patent Document 1 is precisely controlled to a value within a specific range. As a result, it has been found that the above problems can be solved, and the present invention has been completed.
すなわち、本発明の一形態によれば、下記一般式（１）： That is, according to one aspect of the present invention, the following general formula (1):
式中、Ｒ１は水素原子またはメチル基を表し、Ｒ２は水素原子または炭素数１〜４のアルキル基を表し、Ａは炭素数２〜４の直鎖状または分枝状のアルキレン基を表し、ｍはＡＯの平均付加モル数を表し１〜１５０の数であり、ｌは１〜３の整数であり、ｎはＱ＋の原子価を表し１または２であり、Ｑ＋はアルカリ金属カチオン、アルカリ土類金属カチオンまたは含窒素化合物カチオンを表す、
で表される陰イオン性界面活性剤を含む、乳化重合用乳化剤または洗浄剤が提供される。そして、当該剤は、陰イオン性界面活性剤１００モル％に占めるｌが２である２モル付加体の割合が６５．０〜８４．０モル％である点に特徴を有するものである。
In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A represents a linear or branched alkylene group having 2 to 4 carbon atoms. represents, m is the number of 1 to 150 represents an average addition mole number of AO, l is an integer of 1 to 3, n is 1 or 2 represents the valence of Q +, Q + is an alkali metal Represents a cation, an alkaline earth metal cation or a nitrogen-containing compound cation,
An emulsifier or a detergent for emulsion polymerization is provided, which comprises an anionic surfactant represented by the formula: And the said agent has the characteristics in the point that the ratio of 2 mol adduct whose 1 which occupies for 100 mol% of anionic surfactant is 2 is 65.0-84.0 mol%.
本発明によれば、陰イオン性界面活性剤を用いた乳化重合用乳化剤において、重合安定性をよりいっそう向上させることが可能となる。 According to the present invention, it is possible to further improve the polymerization stability in an emulsifier for emulsion polymerization using an anionic surfactant.
以下、本発明の実施形態を説明する。 Embodiments of the present invention will be described below.
本発明の一形態は、下記一般式（１）： One embodiment of the present invention is the following general formula (1):
で表される陰イオン性界面活性剤を含む、乳化重合用乳化剤または洗浄剤に関する。 The emulsifier for emulsion polymerization or the washing | cleaning agent containing the anionic surfactant represented by these.
一般式（１）において、Ｒ１は、水素原子またはメチル基を表す。 In the general formula (1), R 1 represents a hydrogen atom or a methyl group.
一般式（１）において、Ｒ２は、水素原子または炭素数１〜４のアルキル基を表す。炭素数１〜４のアルキル基としては、メチル基、エチル基、プロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基が挙げられる。なかでも、Ｒ２は好ましくは水素原子またはメチル基であり、より好ましくはメチル基である。 In general formula (1), R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. Among these, R 2 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
一般式（１）において、Ａは、炭素数２〜４の直鎖状または分枝状のアルキレン基を表す。炭素数２〜４の直鎖状または分枝状のアルキレン基としては、エチレン基、メチルメチレン基（−ＣＨ２ＣＨ２−）、トリメチレン基、１−メチルエチレン基、２−メチルエチレン基、テトラメチレン基、１−メチルトリメチレン基、２−メチルトリメチレン基、１，１−ジメチルジメチレン基、１，２−ジメチルジメチレン基が挙げられる。これらのアルキレン基は酸素原子とともにオキシアルキレン基を形成する。このオキシアルキレン基（ＡＯ基）は同一または異種の混合物（ブロックまたはランダム）でもよく、好ましくは、オキシエチレン基単独、オキシプロピレン基単独、またはオキシエチレン基とオキシプロピレン基との混合物（ブロックまたはランダム）であり、より好ましくはオキシエチレン基またはオキシプロピレン基であり、特に好ましくはオキシエチレン基（つまり、Ａはエチレン基）である。 In the general formula (1), A represents a linear or branched alkylene group having 2 to 4 carbon atoms. Examples of the linear or branched alkylene group having 2 to 4 carbon atoms include ethylene group, methylmethylene group (—CH 2 CH 2 —), trimethylene group, 1-methylethylene group, 2-methylethylene group, tetra Examples include a methylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethyldimethylene group, and 1,2-dimethyldimethylene group. These alkylene groups together with the oxygen atom form an oxyalkylene group. The oxyalkylene group (AO group) may be the same or different mixture (block or random), preferably oxyethylene group alone, oxypropylene group alone, or a mixture of oxyethylene group and oxypropylene group (block or random). More preferably an oxyethylene group or an oxypropylene group, and particularly preferably an oxyethylene group (that is, A is an ethylene group).
一般式（１）において、ｍはＡＯの平均付加モル数を表し、１〜１５０の数であり、好ましくは５〜１２０である。 In General formula (1), m represents the average addition mole number of AO, is the number of 1-150, Preferably it is 5-120.
一般式（１）において、ｌは１〜３の整数である。一般式（１）で表される陰イオン性界面活性剤は、ｌが１である化合物（本明細書中、「１モル付加体」とも称する）と、１が２である化合物（本明細書中、「２モル付加体」とも称する）と、ｌが３である化合物（本明細書中、「３モル付加体」とも称する）との混合物の形態として存在する。 In general formula (1), l is an integer of 1-3. The anionic surfactant represented by the general formula (1) includes a compound in which l is 1 (also referred to as “1 molar adduct” in this specification) and a compound in which 1 is 2 (in this specification). In the form of a mixture of a compound in which l is 3 (also referred to herein as a “3 molar adduct”).
一般式（１）において、ｎはＱ＋の原子価を表し、１または２である。つまり、Ｑ＋が１価のカチオンであればｎは１であり、Ｑ＋が２価のカチオンであればｎは２である。 In the general formula (1), n represents a valence of Q + and is 1 or 2. That is, if the Q + is a monovalent cation n is 1, if Q + is a divalent cation and n is 2.
一般式（１）において、Ｑ＋はアルカリ金属カチオン、アルカリ土類金属カチオンまたは含窒素化合物カチオンを表す。アルカリ金属カチオンとしては、例えば、ナトリウムカチオン、カリウムカチオン、リチウムカチオンなどが挙げられる。また、アルカリ土類金属カチオンとしては、カルシウムカチオン、マグネシウムカチオンなどが挙げられる。さらに、含窒素化合物カチオンとしては、アンモニウムイオン（ＮＨ４ ＋）または有機アミンカチオンが挙げられる。有機アミンカチオンとしては、例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン；モノエチルアミン、ジエチルアミン、トリエチルアミン等のアルキルアミン；エチレンジアミン、トリエチレンジアミン等のポリアミン等の、有機アミン由来のカチオンが挙げられる。 In the general formula (1), Q + represents an alkali metal cation, an alkaline earth metal cation or a nitrogen-containing compound cation. Examples of the alkali metal cation include a sodium cation, a potassium cation, and a lithium cation. Examples of alkaline earth metal cations include calcium cations and magnesium cations. Further, examples of the nitrogen-containing compound cation include ammonium ions (NH 4 + ) and organic amine cations. Examples of organic amine cations include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; alkylamines such as monoethylamine, diethylamine, and triethylamine; cations derived from organic amines such as polyamines such as ethylenediamine and triethylenediamine. It is done.
上述したような一般式（１）で表される陰イオン性界面活性剤の例としては、以下の化合物が挙げられる（いずれも、ｌが１〜３の混合物として例示される）。 Examples of the anionic surfactant represented by the general formula (1) as described above include the following compounds (all are exemplified as a mixture of 1 to 3).
１）ポリオキシエチレン（７）［スチレン化（メチルフェニルエーテル）］硫酸エステルアンモニウム塩
２）ポリオキシプロピレン（８）［スチレン化（メチルフェニルエーテル）］硫酸エステルアンモニウム塩
３）ポリオキシエチレン（３０）［スチレン化（メチルフェニルエーテル）］硫酸エステルアンモニウム塩
４）ポリオキシエチレン（１２）［スチレン化（ブチルフェニルエーテル）］硫酸エステルソーダ塩
５）ポリオキシエチレン（１０）［メチルスチレン化（メチルフェニルエーテル）］硫酸エステルソーダ塩
６）ポリオキシプロピレン（２０）［メチルスチレン化（メチルフェニルエーテル）］硫酸エステルソーダ塩
７）［ポリオキシプロピレン（５）ポリオキシエチレン（６）］ランダム［スチレン化（メチルフェニルエーテル）］硫酸エステルアンモニウム塩
８）［ポリオキシプロピレン（１０）ポリオキシエチレン（２０）］ブロック［スチレン化メチルフェニルエーテル）］硫酸エステルソーダ塩。
1) Polyoxyethylene (7) [styrenated (methylphenyl ether)] sulfate ammonium salt 2) Polyoxypropylene (8) [styrenated (methylphenyl ether)] sulfate ammonium salt 3) Polyoxyethylene (30) [Styrenated (methyl phenyl ether)] sulfate ammonium salt 4) Polyoxyethylene (12) [Styrenated (butyl phenyl ether)] sulfate soda salt 5) Polyoxyethylene (10) [Methyl styrenated (methyl phenyl ether) ] Sulfuric acid ester soda salt 6) Polyoxypropylene (20) [Methyl styrenated (methyl phenyl ether)] Sulfuric acid ester soda salt 7) [Polyoxypropylene (5) Polyoxyethylene (6)] Random [Styrenated (Methylpheny Ether) sulfate ammonium salt 8) [polyoxypropylene (10) polyoxyethylene (20)] block [styrenated-methylphenyl ether) sulfate sodium salt.
上記記載例において、ポリオキシエチレン（１２）はオキシエチレン基が平均１２モル付加していることを示し、ポリオキシプロピレン（８）はオキシプロピレン基が平均８モル付加していることを示し、他はこれに準ずる。 In the above described examples, polyoxyethylene (12) indicates that an average of 12 moles of oxyethylene groups are added, polyoxypropylene (8) indicates that an average of 8 moles of oxypropylene groups are added, and others Is equivalent to this.
本発明に係る乳化重合用乳化剤または洗浄剤は、上述した一般式（１）で表される陰イオン性界面活性剤を含むものであるが、当該陰イオン性界面活性剤１００モル％に占めるｌが２である化合物（２モル付加体）の割合が６５．０〜８４．０モル％である点に特徴がある。この割合は、より好ましくは７０．５〜８０．２モル％であり、さらに好ましくは７０．５〜７７．１モル％であり、特に好ましくは７２．０〜７７．１モル％である。陰イオン性界面活性剤に占める２モル付加体の割合がかような範囲内の値であれば、本発明に係る陰イオン性界面活性剤を乳化重合用乳化剤として用いた場合に、きわめて優れた重合安定性が達成される。また、陰イオン性界面活性剤に占める２モル付加体の割合がかような範囲内の値であれば、本発明に係る陰イオン性界面活性剤を洗浄剤として用いた場合にも、低泡性に優れるという効果が奏される。 The emulsifier for emulsion polymerization or the cleaning agent according to the present invention contains the anionic surfactant represented by the general formula (1) described above, but 1 in 100 mol% of the anionic surfactant is 2 The ratio of the compound (2 mol adduct) is 65.0 to 84.0 mol%. This ratio is more preferably 70.5 to 80.2 mol%, further preferably 70.5 to 77.1 mol%, and particularly preferably 72.0 to 77.1 mol%. If the ratio of the 2-mole adduct occupying the anionic surfactant is within such a range, the anionic surfactant according to the present invention is extremely excellent when used as an emulsifier for emulsion polymerization. Polymerization stability is achieved. In addition, if the ratio of the 2 mol adduct to the anionic surfactant is a value within such a range, even when the anionic surfactant according to the present invention is used as a cleaning agent, low foam The effect that it is excellent in property is produced.
一般式（Ｉ）で表される化合物（陰イオン性界面活性剤）は、炭素数１〜４のアルキル基（Ｒ２に対応）で置換されているフェノール化合物に、常法に従って、スチレンまたはメチルスチレンを反応させて得られるスチレン化アルキルフェノール誘導体を出発物質として、それ自体公知の方法に従って製造される。 The compound represented by the general formula (I) (anionic surfactant) is prepared by converting styrene or methyl into a phenol compound substituted with an alkyl group having 1 to 4 carbon atoms (corresponding to R 2 ) according to a conventional method. A styrenated alkylphenol derivative obtained by reacting styrene is used as a starting material and is produced according to a method known per se.
具体的には、まず、上記手法により得られるスチレン化アルキルフェノール誘導体のフェノール性水酸基に、例えば水酸化ナトリウムまたは水酸化カリウムなどの塩基触媒の存在下でアルキレンオキシドの所望のモル数を付加する。次いで、無水硫酸、クロロスルホン酸、スルファミン酸、硫酸等の硫酸化剤を用いて硫酸エステル化し、この硫酸エステル化体を塩基を用いて中和することによりカチオン（Ｑ＋）との塩に変換して、一般式（１）で表される化合物（陰イオン性界面活性剤）を得ることができる。 Specifically, first, the desired number of moles of alkylene oxide is added to the phenolic hydroxyl group of the styrenated alkylphenol derivative obtained by the above method in the presence of a base catalyst such as sodium hydroxide or potassium hydroxide. Next, it is sulfated using a sulfating agent such as sulfuric anhydride, chlorosulfonic acid, sulfamic acid, sulfuric acid, etc., and this sulfated ester is neutralized with a base to convert it to a salt with a cation (Q + ). Thus, the compound (anionic surfactant) represented by the general formula (1) can be obtained.
ここで、上述したように、本発明に係る乳化重合用乳化剤または洗浄剤は、陰イオン性界面活性剤１００モル％に占めるｌが２である化合物（２モル付加体）の割合が所定の範囲内の値に制御されている点に特徴を有しているが、この割合は、上記フェノール化合物にスチレンまたはメチルスチレンを反応させる際の反応系におけるスチレンまたはメチルスチレンの配合割合を変えることで制御可能である。なお、一般式（１）で表される陰イオン性界面活性剤における２モル付加体の割合の値は、当業者に周知の測定方法によって測定することが可能である。また、後述する実施例の欄に記載のように、場合によっては、フェノール化合物にスチレン（またはメチルスチレン）を反応させて得られるスチレン化アルキルフェノール誘導体の混合物における２モル付加体の割合を、ガスクロマトグラフィー（ＧＣ）法などによって予め測定しておくことにより、最終的に得られる陰イオン性界面活性剤における割合として採用してもよい。 Here, as described above, in the emulsifier for emulsion polymerization or the cleaning agent according to the present invention, the proportion of the compound in which 1 is 2 (2 mol adduct) in 100 mol% of the anionic surfactant is within a predetermined range. The ratio is controlled by changing the blending ratio of styrene or methylstyrene in the reaction system when reacting styrene or methylstyrene with the phenol compound. Is possible. In addition, the value of the ratio of the 2 mol adduct in the anionic surfactant represented by the general formula (1) can be measured by a measurement method well known to those skilled in the art. Further, as described in the Examples section which will be described later, in some cases, the ratio of 2-mole adducts in a mixture of styrenated alkylphenol derivatives obtained by reacting a phenol compound with styrene (or methylstyrene) is measured by gas chromatography. You may employ | adopt as a ratio in the anionic surfactant finally obtained by measuring beforehand by a graphic (GC) method etc.
一般式（Ｉ）で表される化合物（陰イオン性界面活性剤）の好ましい用途として、乳化重合用乳化剤がある。本発明に係る陰イオン性界面活性剤を乳化重合用の乳化剤として用いて乳化重合を行うことによって、きわめて優れた重合安定性が達成されうる。 A preferred use of the compound represented by the general formula (I) (anionic surfactant) is an emulsifier for emulsion polymerization. By performing emulsion polymerization using the anionic surfactant according to the present invention as an emulsifier for emulsion polymerization, extremely excellent polymerization stability can be achieved.
本発明に係る乳化重合用乳化剤を用いて乳化重合されうる単量体（重合性モノマー）について特に制限はなく、従来公知の重合性モノマーが用いられうるが、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピルなどのアクリル酸またはメタクリル酸のエステル類；臭化ビニル、塩化ビニル、塩化ビニリデンなどのハロゲン化ビニル類；酢酸、プロピオン酸、第三級合成飽和カルボン酸等の脂肪酸類のビニルエステル類：スチレン、α−メチルスチレンなどの芳香族ビニル類：エチレン、ブタジエンなどのモノオレフィンまたは共役ジオレフィン類：アクリロニトリルなどのシアン化ビニル類：アクリルアミドなどのα，β−不飽和アミド類：アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸などのα，β−不飽和カルボン酸類が挙げられる。 There is no particular limitation on the monomer (polymerizable monomer) that can be emulsion-polymerized using the emulsifier for emulsion polymerization according to the present invention, and conventionally known polymerizable monomers can be used. For example, methyl (meth) acrylate, Of acrylic acid or methacrylic acid such as ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Esters; vinyl halides such as vinyl bromide, vinyl chloride and vinylidene chloride; vinyl esters of fatty acids such as acetic acid, propionic acid and tertiary synthetic saturated carboxylic acids: aromatics such as styrene and α-methylstyrene Vinyls: Monoolefins such as ethylene and butadiene or conjugated diolefins: Acrylonitrile Which vinyl cyanides: alpha, such as acrylamide, beta-unsaturated amides: acrylic acid, methacrylic acid, itaconic acid, maleic acid, alpha such as fumaric acid, beta-unsaturated carboxylic acids.
重合開始剤としては、通常乳化重合用に使用される開始剤を特に限定することなく使用でき、例えばカリウム、ナトリウム、アンモニウムの過硫酸塩または過ホウ酸塩、過酸化水素などの無機過酸化物；過酸化ベンゾイル、ジ−ｔ−ブチルパーオキシド、過酢酸などの有機過酸化物；２，２−アゾビスイソブチロニトリル、４−アゾビス−（４−シアノペンタノイック）酸またはそのアルカリ金属塩などのラジカル生成重合開始剤を使用することができ、その使用量は好ましくは０．０１〜３．０質量％、より好ましくは０．１〜２．０％、さらに好ましくは０．１〜１．０重量％である。 As the polymerization initiator, initiators usually used for emulsion polymerization can be used without any particular limitation. For example, potassium, sodium, ammonium persulfate or perborate, inorganic peroxides such as hydrogen peroxide Organic peroxides such as benzoyl peroxide, di-t-butyl peroxide and peracetic acid; 2,2-azobisisobutyronitrile, 4-azobis- (4-cyanopentanoic) acid or alkali metals thereof A radical generating polymerization initiator such as a salt can be used, and the amount used is preferably 0.01 to 3.0% by mass, more preferably 0.1 to 2.0%, and still more preferably 0.1 to 1.0% by weight.
また、重合開始剤として過酸化物を使用する場合に必要があれば、当該過酸化物とアスコルビン酸、可溶性亜硫酸塩、ハイドロサルファイト、チオ硫酸塩などの還元剤とを併用することができ、また水中で重金属イオンを発生する金属単量体または硫酸第一鉄などの水中で金属イオンを発生する金属化合物とを組み合わせてレドックス系重合開始剤として使用することもできる。 Moreover, if necessary when using a peroxide as a polymerization initiator, the peroxide can be used in combination with a reducing agent such as ascorbic acid, soluble sulfite, hydrosulfite, thiosulfate, In addition, a metal monomer that generates heavy metal ions in water or a metal compound that generates metal ions in water such as ferrous sulfate can be used as a redox polymerization initiator.
また、連鎖移動剤も併用することができ、そのようなものとして例えばｔ−ドデシルメルカプタン、ドデシルメルカプタン、四塩化炭素、クロロホルム、トリフェニルメタンなどを使用することができる。 A chain transfer agent can also be used in combination, and as such, for example, t-dodecyl mercaptan, dodecyl mercaptan, carbon tetrachloride, chloroform, triphenylmethane and the like can be used.
さらにまた、乳化重合技術において慣用の添加剤、例えばキレート化剤、緩衝剤、有機酸の塩、溶媒などを使用することができる。溶媒としては、水のほか、アルコール、グリコール、グリコールエーテルなどの有機溶媒が用いられうるが、好ましくは水が溶媒として用いられる。 Furthermore, additives commonly used in the emulsion polymerization technique, for example, chelating agents, buffering agents, salts of organic acids, solvents and the like can be used. As the solvent, in addition to water, organic solvents such as alcohol, glycol, glycol ether and the like can be used, but water is preferably used as the solvent.
本発明に係る一般式（１）で表される陰イオン性界面活性剤を含む乳化重合用乳化剤の使用量は、重合性モノマー１００質量部に対して、好ましくは０．５〜１０質量部であり、より好ましくは１〜７質量部であり、さらに好ましくは１〜５質量部である。 The usage-amount of the emulsifier for emulsion polymerization containing the anionic surfactant represented by General formula (1) which concerns on this invention is preferably 0.5-10 mass parts with respect to 100 mass parts of polymerizable monomers. Yes, more preferably 1-7 parts by mass, still more preferably 1-5 parts by mass.
本発明に係る乳化重合用乳化剤を用いた乳化重合において、一般式（１）で表される陰イオン性界面活性剤は単独でも充分にその機能を発揮するが、必要に応じて従来公知の界面活性剤、反応性乳化剤、高分子量乳化剤、保護コロイドなどを併用することもできる。併用できる界面活性剤としては、例えば陰イオン性界面活性剤としては長鎖アルキル硫酸塩、長鎖アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、アルキルジフェニルエーテルジスルホン酸塩などであり、また非イオン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、プルロニック型界面活性剤などを挙げることができる。 In the emulsion polymerization using the emulsifier for emulsion polymerization according to the present invention, the anionic surfactant represented by the general formula (1) exhibits its function sufficiently even when used alone. Activators, reactive emulsifiers, high molecular weight emulsifiers, protective colloids and the like can also be used in combination. Examples of surfactants that can be used in combination include long chain alkyl sulfates, long chain alkyl benzene sulfonates, polyoxyethylene alkyl phenyl ether sulfates, alkyl diphenyl ether disulfonates, and the like. Examples of the ionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, and pluronic surfactant.
併用できる高分子乳化剤の例としては、ポリビニルアルコール、ポリ（メタ）アクリル酸塩、ポリヒドロキシアルキレン（メタ）アクリレートなどが挙げられ、また併用できる保護コロイドとしてはアルギン酸ナトリウムなどのようなアニオン性保護コロイド、ヒドロキシエチルセルロースのような非イオン性保護コロイドなどが例として挙げられる。 Examples of polymer emulsifiers that can be used in combination include polyvinyl alcohol, poly (meth) acrylates, polyhydroxyalkylene (meth) acrylates, and examples of protective colloids that can be used in combination include anionic protective colloids such as sodium alginate. Examples include nonionic protective colloids such as hydroxyethyl cellulose.
陰イオン性界面活性剤、非イオン性界面活性剤、高分子乳化剤および／または保護コロイドと併用する場合は、本発明に係る陰イオン性界面活性剤１質量部あたりそれぞれ０．０５〜１０質量部程度が適当である。 When used in combination with an anionic surfactant, a nonionic surfactant, a polymer emulsifier and / or a protective colloid, 0.05 to 10 parts by mass per 1 part by mass of the anionic surfactant according to the present invention. The degree is appropriate.
本発明において、重合体エマルジョンは、通常公知の乳化重合方法により得ることができる。そのような方法としては、（１）一括仕込み法、（２）単量体添加法、（３）単量体エマルジョン添加法があり、好ましい方法は単量体エマルジョン添加法である。 In the present invention, the polymer emulsion can be obtained by a generally known emulsion polymerization method. As such a method, there are (1) a batch charging method, (2) a monomer addition method, and (3) a monomer emulsion addition method, and a preferable method is a monomer emulsion addition method.
以上のような乳化重合によって得られる重合体組成物も本発明では提供される。すなわち、本発明の他の形態によれば、本発明に係る乳化重合用乳化剤と、重合性モノマーと、溶媒（特に好ましくは、水）と、を含む重合体組成物もまた、提供される。当該重合体組成物は、エマルジョンの形態であることが好ましい。 The present invention also provides a polymer composition obtained by emulsion polymerization as described above. That is, according to the other form of this invention, the polymer composition containing the emulsifier for emulsion polymerization which concerns on this invention, a polymerizable monomer, and a solvent (especially preferably water) is also provided. The polymer composition is preferably in the form of an emulsion.
一般式（Ｉ）で表される化合物（陰イオン性界面活性剤）の他の好ましい用途として、洗浄剤が挙げられる。上述したように、本発明に係る陰イオン性界面活性剤を洗浄剤として用いると、低泡性に優れるという効果が奏される。本発明に係る陰イオン性界面活性剤を洗浄剤として用いる場合の被洗浄物としては、繊維、金属、ガラス、セラミックスなどが挙げられるが、これらに限定されるわけではない。 Another preferred application of the compound represented by the general formula (I) (anionic surfactant) is a cleaning agent. As described above, when the anionic surfactant according to the present invention is used as a cleaning agent, an effect of being excellent in low foaming property is exhibited. Examples of the object to be cleaned when the anionic surfactant according to the present invention is used as a cleaning agent include, but are not limited to, fiber, metal, glass, ceramics and the like.
以下、実施例を用いて本発明をより詳細に説明するが、本発明の技術的範囲は下記の形態のみには限定されない。なお、以下の記載において、「部」は質量部を表し、「％」は質量％を表す。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, the technical scope of this invention is not limited only to the following form. In the following description, “part” represents part by mass, and “%” represents mass%.
［陰イオン性界面活性剤の製造例］
まず、原料としてｍ，ｐ−クレゾールを用い、これにスチレンを反応させてスチレン化クレゾール誘導体を得た。次いで、得られたスチレン化クレゾール誘導体のフェノール性水酸基に、塩基触媒としての水酸化ナトリウムの存在下でエチレンオキシドを７モル付加した。そして、硫酸化剤としてスルファミン酸を用いて硫酸エステル化し、得られた硫酸エステル化体をアンモニアを用いて中和することにより、一般式（１）で表される化合物（陰イオン性界面活性剤）であるポリオキシエチレン（７）［ジスチレン化（メチルフェニルエーテル）］硫酸エステルアンモニウム塩を得た。
[Production Example of Anionic Surfactant]
First, m, p-cresol was used as a raw material, and this was reacted with styrene to obtain a styrenated cresol derivative. Subsequently, 7 mol of ethylene oxide was added to the phenolic hydroxyl group of the obtained styrenated cresol derivative in the presence of sodium hydroxide as a base catalyst. Then, sulfamic acid is used as a sulfating agent, and the resulting sulfated product is neutralized with ammonia to obtain a compound represented by the general formula (1) (an anionic surfactant). ) Polyoxyethylene (7) [distyrenated (methylphenyl ether)] sulfate ammonium salt was obtained.
この際、原料であるｍ，ｐ−クレゾールにスチレンを反応させる際の反応系におけるスチレンの配合割合を変えることで、１モル付加体／２モル付加体／３モル付加体の割合（モル比）が異なる１０種の陰イオン性界面活性剤（１）〜（１０）を合成した。なお、得られた陰イオン性界面活性剤（１）〜（１０）のそれぞれについて、対応するスチレン化クレゾール誘導体（１）〜（１０）の１モル付加体／２モル付加体／３モル付加体の割合（モル比）を、以下の手法により測定した。結果を下記の表１に示す。この各付加体の割合（モル比）は、得られた陰イオン性界面活性剤（１）〜（１０）における各付加体の割合（モル比）と同一である。 At this time, by changing the blending ratio of styrene in the reaction system when styrene is reacted with m, p-cresol as a raw material, the ratio (molar ratio) of 1 mol adduct / 2 mol adduct / 3 mol adduct 10 kinds of anionic surfactants (1) to (10) having different values were synthesized. In addition, about each of obtained anionic surfactant (1)-(10), 1 mol adduct / 2 mol adduct / 3 mol adduct of corresponding styrenated cresol derivatives (1)-(10). The ratio (molar ratio) was measured by the following method. The results are shown in Table 1 below. The ratio (molar ratio) of each adduct is the same as the ratio (molar ratio) of each adduct in the obtained anionic surfactants (1) to (10).
（各付加体の割合（モル比）の測定方法）
サンプル：スチレン化クレゾール誘導体
測定条件
ＧＣ：ＧＣ−１４Ｂ(島津製作所製)
カラム：ＳＥ−３０
カラム温度：１００℃→（２０℃／ｍｉｎ）→３００℃
ＩＮＪ、ＤＥＴ：３２０℃
サンプル量：０．４μｌ（５０％メタノール溶液）。
(Method for measuring the ratio (molar ratio) of each adduct)
Sample: Styrenated cresol derivative Measurement conditions GC: GC-14B (manufactured by Shimadzu Corporation)
Column: SE-30
Column temperature: 100 ° C. → (20 ° C./min)→300° C.
INJ, DET: 320 ° C
Sample volume: 0.4 μl (50% methanol solution).
［重合体エマルジョンの製造］
（実施例１）
アクリル酸ブチル１００部、メタクリル酸メチル７０部、スチレン３０部、アクリル酸４部、イオン交換水１０５部、過硫酸アンモニウム１部および陰イオン性界面活性剤（３）（２モル付加体の割合＝７０．５０モル％）４部を混合して単量体エマルジョン３１４部を調製した。
[Production of polymer emulsion]
Example 1
100 parts of butyl acrylate, 70 parts of methyl methacrylate, 30 parts of styrene, 4 parts of acrylic acid, 105 parts of ion-exchanged water, 1 part of ammonium persulfate and anionic surfactant (3) (2 mole adduct ratio = 70 (.50 mol%) 4 parts were mixed to prepare 314 parts of a monomer emulsion.
次に、攪拌機、温度計、還流冷却器および滴下ロートを備えた反応器に脱イオン水１００部および上記単量体エマルジョン１５．７部を仕込んで攪拌を開始し、窒素気流中で８０℃に昇温し、３０分間初期重合させた。 Next, a reactor equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel was charged with 100 parts of deionized water and 15.7 parts of the monomer emulsion, and stirring was started. The temperature was raised and initial polymerization was performed for 30 minutes.
続いて、残りの単量体エマルジョン２９８．３部を８０℃にて３時間かけて連続的に滴下して重合させ、滴下終了後１時間熟成を行って、重合体エマルジョンを得た。 Subsequently, 298.3 parts of the remaining monomer emulsion was continuously dropped at 80 ° C. over 3 hours for polymerization, and after completion of the dropping, aging was performed for 1 hour to obtain a polymer emulsion.
（実施例２）
陰イオン性界面活性剤（３）に代えて、陰イオン性界面活性剤（４）（２モル付加体の割合＝７２．００モル％）を用いたこと以外は、上述した実施例１と同様の手法により、重合体エマルジョンを得た。
(Example 2)
It replaced with the anionic surfactant (3), and it was the same as that of Example 1 mentioned above except having used the anionic surfactant (4) (ratio of 2 mol adduct = 72.00 mol%). According to the method, a polymer emulsion was obtained.
（実施例３）
陰イオン性界面活性剤（３）に代えて、陰イオン性界面活性剤（５）（２モル付加体の割合＝７４．９０モル％）を用いたこと以外は、上述した実施例１と同様の手法により、重合体エマルジョンを得た。
(Example 3)
In place of the anionic surfactant (3), the anionic surfactant (5) (2 mol adduct ratio = 74.90 mol%) was used, except that the same as in Example 1 described above. According to the method, a polymer emulsion was obtained.
（実施例４）
陰イオン性界面活性剤（３）に代えて、陰イオン性界面活性剤（６）（２モル付加体の割合＝７７．１０モル％）を用いたこと以外は、上述した実施例１と同様の手法により、重合体エマルジョンを得た。
Example 4
In place of the anionic surfactant (3), the anionic surfactant (6) (2 mol adduct ratio = 77.10 mol%) was used, except that the same as in Example 1 described above. According to the method, a polymer emulsion was obtained.
（実施例５）
陰イオン性界面活性剤（３）に代えて、陰イオン性界面活性剤（７）（２モル付加体の割合＝８０．２０モル％）を用いたこと以外は、上述した実施例１と同様の手法により、重合体エマルジョンを得た。
(Example 5)
It replaced with the anionic surfactant (3), and it was the same as that of Example 1 mentioned above except having used the anionic surfactant (7) (ratio of 2 mol adduct = 80.20 mol%). According to the method, a polymer emulsion was obtained.
（比較例１）
陰イオン性界面活性剤（３）に代えて、陰イオン性界面活性剤（１）（２モル付加体の割合＝５９．５０モル％）を用いたこと以外は、上述した実施例１と同様の手法により、重合体エマルジョンを得た。
(Comparative Example 1)
It replaced with the anionic surfactant (3), and it was the same as that of Example 1 mentioned above except having used the anionic surfactant (1) (ratio of 2 mol adduct = 59.50 mol%). According to the method, a polymer emulsion was obtained.
（比較例２）
陰イオン性界面活性剤（３）に代えて、陰イオン性界面活性剤（２）（２モル付加体の割合＝６４．５０モル％）を用いたこと以外は、上述した実施例１と同様の手法により、重合体エマルジョンを得た。
(Comparative Example 2)
It replaced with the anionic surfactant (3), and it was the same as that of Example 1 mentioned above except having used the anionic surfactant (2) (ratio of 2 mol adduct = 64.50 mol%). According to the method, a polymer emulsion was obtained.
（比較例３）
陰イオン性界面活性剤（３）に代えて、陰イオン性界面活性剤（８）（２モル付加体の割合＝８４．１０モル％）を用いたこと以外は、上述した実施例１と同様の手法により、重合体エマルジョンを得た。
(Comparative Example 3)
It replaced with the anionic surfactant (3), and it was the same as that of Example 1 mentioned above except having used the anionic surfactant (8) (ratio of 2 mol adduct = 84.10 mol%). According to the method, a polymer emulsion was obtained.
（比較例４）
陰イオン性界面活性剤（３）に代えて、陰イオン性界面活性剤（９）（２モル付加体の割合＝８６．８０モル％）を用いたこと以外は、上述した実施例１と同様の手法により、重合体エマルジョンを得た。
(Comparative Example 4)
It replaced with the anionic surfactant (3), and it was the same as that of Example 1 mentioned above except having used the anionic surfactant (9) (ratio of 2 mol adduct = 86.80 mol%). According to the method, a polymer emulsion was obtained.
（比較例５）
陰イオン性界面活性剤（３）に代えて、陰イオン性界面活性剤（１０）（２モル付加体の割合＝９０．６０モル％）を用いたこと以外は、上述した実施例１と同様の手法により、重合体エマルジョンを得た。
(Comparative Example 5)
It replaced with the anionic surfactant (3), and it was the same as that of Example 1 mentioned above except having used the anionic surfactant (10) (ratio of 2 mol adduct = 90.60 mol%). According to the method, a polymer emulsion was obtained.
［重合体エマルジョンの評価］
上述した各実施例および各比較例において得られた重合体エマルジョンについて、以下の評価を行った。結果を下記の表２に示す。
[Evaluation of polymer emulsion]
The following evaluation was performed about the polymer emulsion obtained in each Example and each comparative example mentioned above. The results are shown in Table 2 below.
（１）重合安定性（凝集物量）
乳化重合終了後の重合体エマルジョンを１００メッシュスクリーンでろ過し、スクリーン上に残った凝集物を１１０℃で２時間乾燥させて秤量した質量を使用モノマーに対する質量％で表し、重合安定性の評価とした。この値が小さいほど重合安定性に優れることを示す。特に、工業的用途においては、この値が０．５以下であることが必須に求められ、好ましくは０．３以下であり、より好ましくは０．１以下であり、特に好ましくは０．０７以下であり、最も好ましくは０．０２以下である。
(1) Polymerization stability (aggregate amount)
The polymer emulsion after the completion of emulsion polymerization was filtered through a 100 mesh screen, the aggregate remaining on the screen was dried at 110 ° C. for 2 hours and weighed and expressed in mass% based on the monomer used. did. It shows that it is excellent in polymerization stability, so that this value is small. In particular, in industrial applications, it is essential that this value is 0.5 or less, preferably 0.3 or less, more preferably 0.1 or less, and particularly preferably 0.07 or less. And most preferably 0.02 or less.
（２）不揮発分
重合体エマルジョン１ｇをとり純水５ｇを加えた後、１０５℃で２時間乾燥させた後の蒸発残分を質量％で表した。
(2) Nonvolatile content After taking 1 g of the polymer emulsion and adding 5 g of pure water, the evaporation residue after drying at 105 ° C. for 2 hours was expressed in mass%.
（３）重合転化率
上記（２）で得られた不揮発分の値を重合時に設定した固形分で割った値を百分率（％）で表し、重合転化率とした。
(3) Polymerization conversion rate A value obtained by dividing the value of the non-volatile content obtained in the above (2) by the solid content set at the time of polymerization was expressed as a percentage (%) and was defined as the polymerization conversion rate.
（４）粘度
２５℃における重合体エマルジョンの中和前後の粘度をＢ型回転粘度計６０ｒｐｍおよび６ｒｐｍにて測定した（単位：ｍＰｓ）。
(4) Viscosity The viscosity before and after neutralization of the polymer emulsion at 25 ° C. was measured with a B-type rotational viscometer at 60 rpm and 6 rpm (unit: mPs).
表２に示す結果から、２モル付加体の割合が所定の範囲内の値に制御されてなる陰イオン性界面活性剤を乳化重合用乳化剤として用いることで、きわめて優れた重合安定性が達成されることがわかる。 From the results shown in Table 2, extremely excellent polymerization stability was achieved by using an anionic surfactant in which the ratio of the 2-mol adduct was controlled to a value within a predetermined range as an emulsifier for emulsion polymerization. I understand that
Claims (8)
で表される陰イオン性界面活性剤を含む、乳化重合用乳化剤または洗浄剤であって、
前記陰イオン性界面活性剤１００モル％に占めるｌが２である２モル付加体の割合が６５．０〜８４．０モル％であることを特徴とする、乳化重合用乳化剤または洗浄剤。 The following general formula (1):
An emulsifier or a detergent for emulsion polymerization, comprising an anionic surfactant represented by
An emulsifier for emulsion polymerization or a cleaning agent, wherein the proportion of a 2 mol adduct wherein 1 is 2 in 100 mol% of the anionic surfactant is 65.0 to 84.0 mol%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018181736A1 (en) * | 2017-03-29 | 2018-10-04 | Ａｇｃ株式会社 | Aqueous dispersion and production method for aqueous dispersion |
| JP2019094477A (en) * | 2017-11-24 | 2019-06-20 | 花王株式会社 | Surfactant composition for emulsion polymerization |
| JP2020081905A (en) * | 2018-11-15 | 2020-06-04 | 日本乳化剤株式会社 | Action improver of anti-rust agent, and composition for emulsion polymerization and anti-rust agent-containing emulsion using the same |
| JP2022516836A (en) * | 2018-12-18 | 2022-03-03 | インドラマ・ベンチャーズ・オキサイズ・エルエルシー | Benz Hydrillized Aromatic Surfactant |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56161403A (en) * | 1980-05-16 | 1981-12-11 | Sanyo Chem Ind Ltd | Production of vinyl type polymer emulsion |
| JPH08113602A (en) * | 1994-10-18 | 1996-05-07 | Nippon Niyuukazai Kk | Production of polymer emulsion |
| JP2010535891A (en) * | 2007-08-10 | 2010-11-25 | エトクス ケミカルズ リミテッド ライアビリティ カンパニー | Styrenated phenol ethoxylates in emulsion polymerization. |
-
2014
- 2014-09-30 JP JP2014200433A patent/JP6556991B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56161403A (en) * | 1980-05-16 | 1981-12-11 | Sanyo Chem Ind Ltd | Production of vinyl type polymer emulsion |
| JPH08113602A (en) * | 1994-10-18 | 1996-05-07 | Nippon Niyuukazai Kk | Production of polymer emulsion |
| JP2010535891A (en) * | 2007-08-10 | 2010-11-25 | エトクス ケミカルズ リミテッド ライアビリティ カンパニー | Styrenated phenol ethoxylates in emulsion polymerization. |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018181736A1 (en) * | 2017-03-29 | 2018-10-04 | Ａｇｃ株式会社 | Aqueous dispersion and production method for aqueous dispersion |
| CN110325582A (en) * | 2017-03-29 | 2019-10-11 | Ａｇｃ株式会社 | The manufacturing method of aqueous liquid dispersion and aqueous liquid dispersion |
| JP2019094477A (en) * | 2017-11-24 | 2019-06-20 | 花王株式会社 | Surfactant composition for emulsion polymerization |
| JP7060465B2 (en) | 2017-11-24 | 2022-04-26 | 花王株式会社 | Surfactant composition for emulsion polymerization |
| JP2020081905A (en) * | 2018-11-15 | 2020-06-04 | 日本乳化剤株式会社 | Action improver of anti-rust agent, and composition for emulsion polymerization and anti-rust agent-containing emulsion using the same |
| JP7088815B2 (en) | 2018-11-15 | 2022-06-21 | 日本乳化剤株式会社 | An agent for improving the action of a rust inhibitor, a composition for emulsion polymerization using the agent, and an emulsion containing a rust inhibitor. |
| JP2022516836A (en) * | 2018-12-18 | 2022-03-03 | インドラマ・ベンチャーズ・オキサイズ・エルエルシー | Benz Hydrillized Aromatic Surfactant |
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