JP5331366B2 - Method for preventing blocking of styrene elastomer resin pellets - Google Patents
Method for preventing blocking of styrene elastomer resin pellets Download PDFInfo
- Publication number
- JP5331366B2 JP5331366B2 JP2008096392A JP2008096392A JP5331366B2 JP 5331366 B2 JP5331366 B2 JP 5331366B2 JP 2008096392 A JP2008096392 A JP 2008096392A JP 2008096392 A JP2008096392 A JP 2008096392A JP 5331366 B2 JP5331366 B2 JP 5331366B2
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- polymer
- elastomer resin
- blocking
- pellets
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 60
- 238000000034 method Methods 0.000 title claims description 46
- 239000008188 pellet Substances 0.000 title claims description 39
- 229920005989 resin Polymers 0.000 title claims description 38
- 239000011347 resin Substances 0.000 title claims description 38
- 229920001971 elastomer Polymers 0.000 title claims description 37
- 239000000806 elastomer Substances 0.000 title claims description 35
- 230000000903 blocking effect Effects 0.000 title description 25
- 229920000642 polymer Polymers 0.000 claims description 42
- 238000004519 manufacturing process Methods 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 28
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000839 emulsion Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 12
- 229920003169 water-soluble polymer Polymers 0.000 claims description 11
- 229920000609 methyl cellulose Polymers 0.000 claims description 8
- 239000001923 methylcellulose Substances 0.000 claims description 8
- 238000005345 coagulation Methods 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- 230000015271 coagulation Effects 0.000 claims description 6
- 238000010257 thawing Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 230000001112 coagulating effect Effects 0.000 claims description 2
- 239000000498 cooling water Substances 0.000 description 27
- -1 acrylate ester Chemical class 0.000 description 15
- 229920001400 block copolymer Polymers 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 229920005992 thermoplastic resin Polymers 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000002981 blocking agent Substances 0.000 description 7
- 238000010538 cationic polymerization reaction Methods 0.000 description 7
- 235000010981 methylcellulose Nutrition 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 238000005453 pelletization Methods 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 229920002725 thermoplastic elastomer Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 4
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 4
- UHKPXKGJFOKCGG-UHFFFAOYSA-N 2-methylprop-1-ene;styrene Chemical compound CC(C)=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 UHKPXKGJFOKCGG-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 3
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000013016 damping Methods 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 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
- 230000002265 prevention Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- VCLWNCAUAKTVII-UHFFFAOYSA-N C=C.CC=C.C=CC1=CC=CC=C1 Chemical group C=C.CC=C.C=CC1=CC=CC=C1 VCLWNCAUAKTVII-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- 229920002907 Guar gum Polymers 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 235000010417 guar gum Nutrition 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
- 229960002154 guar gum Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- TXFONIGDXLPYOB-UHFFFAOYSA-N 1,3,5-trichloro-2-ethenylbenzene Chemical compound ClC1=CC(Cl)=C(C=C)C(Cl)=C1 TXFONIGDXLPYOB-UHFFFAOYSA-N 0.000 description 1
- CORMBJOFDGICKF-UHFFFAOYSA-N 1,3,5-trimethoxy 2-vinyl benzene Natural products COC1=CC(OC)=C(C=C)C(OC)=C1 CORMBJOFDGICKF-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- WRBCPVXVVDKWJW-UHFFFAOYSA-N 1,3-dichloro-2-(1-chloroethenyl)benzene Chemical compound ClC(=C)C1=C(Cl)C=CC=C1Cl WRBCPVXVVDKWJW-UHFFFAOYSA-N 0.000 description 1
- RPTSDKNERZWQIA-UHFFFAOYSA-N 1,3-dichloro-2-(2-chloroethenyl)benzene Chemical compound ClC=CC1=C(Cl)C=CC=C1Cl RPTSDKNERZWQIA-UHFFFAOYSA-N 0.000 description 1
- YJCVRMIJBXTMNR-UHFFFAOYSA-N 1,3-dichloro-2-ethenylbenzene Chemical compound ClC1=CC=CC(Cl)=C1C=C YJCVRMIJBXTMNR-UHFFFAOYSA-N 0.000 description 1
- MYXGLEOAVQTFAK-UHFFFAOYSA-N 1,3-dimethyl-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=C(C)C=CC=C1C MYXGLEOAVQTFAK-UHFFFAOYSA-N 0.000 description 1
- QICPIQJTGZXQQJ-UHFFFAOYSA-N 1,3-dimethyl-2-prop-1-enylbenzene Chemical compound CC=CC1=C(C)C=CC=C1C QICPIQJTGZXQQJ-UHFFFAOYSA-N 0.000 description 1
- GWRGEEAABGHXBR-UHFFFAOYSA-N 1,4-bis(2-chloropropan-2-yl)benzene Chemical compound CC(C)(Cl)C1=CC=C(C(C)(C)Cl)C=C1 GWRGEEAABGHXBR-UHFFFAOYSA-N 0.000 description 1
- VTPQLJUADNBKRM-UHFFFAOYSA-N 1-(bromomethyl)-4-ethenylbenzene Chemical compound BrCC1=CC=C(C=C)C=C1 VTPQLJUADNBKRM-UHFFFAOYSA-N 0.000 description 1
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- KAWKOONCEXAZMZ-UHFFFAOYSA-N 1-chloro-2-(1-chloroethenyl)benzene Chemical compound ClC(=C)C1=CC=CC=C1Cl KAWKOONCEXAZMZ-UHFFFAOYSA-N 0.000 description 1
- XKPCIGDIOQKJEB-UHFFFAOYSA-N 1-chloro-2-(2-chloroethenyl)benzene Chemical compound ClC=CC1=CC=CC=C1Cl XKPCIGDIOQKJEB-UHFFFAOYSA-N 0.000 description 1
- VCRHUWNATPGGTO-UHFFFAOYSA-N 1-chloro-3-(1-chloroethenyl)benzene Chemical compound ClC(=C)C1=CC=CC(Cl)=C1 VCRHUWNATPGGTO-UHFFFAOYSA-N 0.000 description 1
- XJCQFMIXTZNXMF-UHFFFAOYSA-N 1-chloro-3-(2-chloroethenyl)benzene Chemical compound ClC=CC1=CC=CC(Cl)=C1 XJCQFMIXTZNXMF-UHFFFAOYSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- VLEPDKZOJYVEMK-UHFFFAOYSA-N 1-chloro-4-(1-chloroethenyl)benzene Chemical compound ClC(=C)C1=CC=C(Cl)C=C1 VLEPDKZOJYVEMK-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- PECUPOXPPBBFLU-UHFFFAOYSA-N 1-ethenyl-3-methoxybenzene Chemical compound COC1=CC=CC(C=C)=C1 PECUPOXPPBBFLU-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
- OGMSGZZPTQNTIK-UHFFFAOYSA-N 1-methyl-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1C OGMSGZZPTQNTIK-UHFFFAOYSA-N 0.000 description 1
- CZUZGUCIXCUKSC-UHFFFAOYSA-N 1-methyl-2-prop-1-enylbenzene Chemical compound CC=CC1=CC=CC=C1C CZUZGUCIXCUKSC-UHFFFAOYSA-N 0.000 description 1
- XXTQHVKTTBLFRI-UHFFFAOYSA-N 1-methyl-3-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC(C)=C1 XXTQHVKTTBLFRI-UHFFFAOYSA-N 0.000 description 1
- UUOANSACYXAAOU-UHFFFAOYSA-N 1-methyl-3-prop-1-enylbenzene Chemical compound CC=CC1=CC=CC(C)=C1 UUOANSACYXAAOU-UHFFFAOYSA-N 0.000 description 1
- LSMSSYSRCUNIFX-UHFFFAOYSA-N 1-methyl-4-prop-1-enylbenzene Chemical compound CC=CC1=CC=C(C)C=C1 LSMSSYSRCUNIFX-UHFFFAOYSA-N 0.000 description 1
- PKUQHKARGJFSRA-UHFFFAOYSA-N 2,4-dichloro-1-(1-chloroethenyl)benzene Chemical compound ClC(=C)C1=CC=C(Cl)C=C1Cl PKUQHKARGJFSRA-UHFFFAOYSA-N 0.000 description 1
- XWEMGFGRWJFXST-UHFFFAOYSA-N 2,4-dichloro-1-(2-chloroethenyl)benzene Chemical compound ClC=CC1=CC=C(Cl)C=C1Cl XWEMGFGRWJFXST-UHFFFAOYSA-N 0.000 description 1
- OMNYXCUDBQKCMU-UHFFFAOYSA-N 2,4-dichloro-1-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C(Cl)=C1 OMNYXCUDBQKCMU-UHFFFAOYSA-N 0.000 description 1
- QIDIFDCCFHVZOR-UHFFFAOYSA-N 2,4-dimethyl-1-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=C(C)C=C1C QIDIFDCCFHVZOR-UHFFFAOYSA-N 0.000 description 1
- BOMOHWDVLAJWEI-UHFFFAOYSA-N 2,4-dimethyl-1-prop-1-enylbenzene Chemical compound CC=CC1=CC=C(C)C=C1C BOMOHWDVLAJWEI-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- KPJKMUJJFXZGAX-UHFFFAOYSA-N 2-chloropropan-2-ylbenzene Chemical compound CC(C)(Cl)C1=CC=CC=C1 KPJKMUJJFXZGAX-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 description 1
- OWRKXOZFTROHSH-UHFFFAOYSA-N 2-ethenyl-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1C=C OWRKXOZFTROHSH-UHFFFAOYSA-N 0.000 description 1
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 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
- 241000416162 Astragalus gummifer Species 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
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 239000000020 Nitrocellulose Substances 0.000 description 1
- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-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
- 229920002385 Sodium hyaluronate Polymers 0.000 description 1
- 229910001347 Stellite Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 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
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- KXKPYJOVDUMHGS-OSRGNVMNSA-N chondroitin sulfate Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](OS(O)(=O)=O)[C@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](C(O)=O)O1 KXKPYJOVDUMHGS-OSRGNVMNSA-N 0.000 description 1
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229940095674 pellet product Drugs 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 description 1
- 239000000770 propane-1,2-diol alginate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229940010747 sodium hyaluronate Drugs 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 1
- 229940032147 starch Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 235000010487 tragacanth Nutrition 0.000 description 1
- 239000000196 tragacanth Substances 0.000 description 1
- 229940116362 tragacanth Drugs 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
本発明は、スチレン系エラストマー樹脂ペレットのブロッキング防止方法に関するものである。 The present invention relates to a method for preventing blocking of styrenic elastomer resin pellets.
熱可塑性スチレン系エラストマーは溶融成形可能なゴム状物質であり、射出成形、押し出し成形、カレンダー成形等、通常熱可塑性樹脂で用いられる成形法により成形することができる。熱可塑性スチレン系エラストマーは、その強度と伸びおよび制振性に優れた性質を有しており、具体的な用途としては、エラストマー材料、樹脂、ゴム、アスファルト等の改質材、制振材、粘着剤のベースポリマー、樹脂改質剤の成分として用いることができる。 Thermoplastic styrenic elastomer is a melt-formable rubber-like substance, and can be molded by molding methods usually used for thermoplastic resins, such as injection molding, extrusion molding, and calendar molding. Thermoplastic styrene-based elastomers have excellent strength, elongation and vibration damping properties. Specific applications include elastomer materials, resins, rubber, asphalt modifiers, vibration damping materials, It can be used as a base polymer of an adhesive and a component of a resin modifier.
このように優れた性質、加工性を有する熱可塑性スチレン系エラストマーであるが、その反面、軟化点の低さから室温付近でも樹脂同士の付着、すなわちブロッキングが発生しやすい。このブロッキングは熱可塑性樹脂のペレット化、乾燥、梱包、成形に至るまで、あらゆる場面において取り扱いの困難な状況を発生させる。具体的には、樹脂をペレットに成形する段階においては、ペレット同士あるいはペレットが加工設備へ付着することにより運転の支障になる。また、ホッパー内部でペレットが閉塞し、払い出しが不能になることもよく知られた事実である。 Although it is a thermoplastic styrenic elastomer having excellent properties and processability as described above, on the other hand, adhesion between resins, that is, blocking is likely to occur even in the vicinity of room temperature due to its low softening point. This blocking creates difficult handling situations in all situations, from thermoplastic pelletization, drying, packaging and molding. Specifically, at the stage of molding the resin into pellets, the pellets or the pellets adhere to the processing equipment, which hinders operation. In addition, it is a well-known fact that pellets are clogged inside the hopper and dispensation becomes impossible.
このような熱可塑性エラストマー樹脂のブロッキングを改善する方法として、特許文献１のように熱可塑性エラストマーを結晶性ポリオレフィンで被覆する方法が開示されている。また特許文献２のように熱可塑性シートに対して親水性高分子化合物、脂肪酸金属塩、界面活性剤、導電性高分子を含有する制電層を積層する方法も開示されている。 As a method for improving the blocking of such a thermoplastic elastomer resin, as disclosed in Patent Document 1, a method of coating a thermoplastic elastomer with a crystalline polyolefin is disclosed. Further, as disclosed in Patent Document 2, a method of laminating an antistatic layer containing a hydrophilic polymer compound, a fatty acid metal salt, a surfactant, and a conductive polymer on a thermoplastic sheet is also disclosed.
これらは樹脂をペレット形状に成形する前に配合物を混練するペレットのブロッキング防止方法、あるいは成形シートのブロッキング防止方法である。しかしペレットのブロッキング防止のために添加する配合物、高分子成分によっては、エラストマーの物性自体の悪化が懸念される。また芯鞘型複合押出ダイなどのように専用設備が必要となり、簡便な方法とは言いがたい。 These are pellet blocking prevention methods for kneading the compound before molding the resin into pellets, or molding sheet blocking prevention methods. However, depending on the compound and polymer component added to prevent pellet blocking, there is a concern that the physical properties of the elastomer may deteriorate. In addition, special equipment such as a core-sheath type compound extrusion die is required, which is not a simple method.
一方、特許文献３には熱可塑性エラストマー樹脂ペレットに脂肪酸金属塩粉末、脂肪酸アミド粉末、ポリオレフィン粉末、シリカ粉末等を付着させる方法が開示されている。これらの方法では、ストランドカット中に水槽を用いてブロッキング防止剤を付与する場合や水中カットペレタイザにて付与する場合には、その水溶液に樹脂を接触させても効果的に樹脂表面にブロッキング防止剤が付着せずその効果が十分でないケースがしばしばであった。 On the other hand, Patent Document 3 discloses a method in which a fatty acid metal salt powder, a fatty acid amide powder, a polyolefin powder, a silica powder or the like is attached to a thermoplastic elastomer resin pellet. In these methods, when applying an antiblocking agent using a water tank during strand cutting or when applying with an underwater cut pelletizer, even if the resin is brought into contact with the aqueous solution, blocking is effectively prevented on the resin surface. In many cases, the agent did not adhere and the effect was not sufficient.
一方、イソブチレンとスチレン等の芳香族ビニル系単量体とをカチオン重合することによる、イソブチレンを主成分とする重合体ブロックと芳香族ビニル系単量体を主成分とする重合体ブロックからなるイソブチレン系ブロック共重合体の製造法については、例えば、特許文献４に、塩化メチルとメチルシクロヘキサンを組み合わせた混合溶媒中での製造方法が開示されている。 On the other hand, isobutylene comprising a polymer block mainly composed of isobutylene and a polymer block mainly composed of an aromatic vinyl monomer by cationic polymerization of isobutylene and an aromatic vinyl monomer such as styrene. As for the method for producing the system block copolymer, for example, Patent Document 4 discloses a production method in a mixed solvent in which methyl chloride and methylcyclohexane are combined.
また特許文献５にも、塩化メチレンとヘキサンからなる混合溶媒中での、イソブチレン重合体ブロックとスチレン重合体ブロックからなるイソブチレン系ブロック共重合体の製造方法が開示されている。 Patent Document 5 discloses a method for producing an isobutylene block copolymer comprising an isobutylene polymer block and a styrene polymer block in a mixed solvent comprising methylene chloride and hexane.
一般に、スチレン系エラストマー樹脂の回収方法には、薄膜蒸発機や押出機による溶媒除去後ストランドカット方式や水中カット方式でペレット化する方法やスチームストリッピングによって粉粒体化する方法が採用されているケースが多い。 Generally, as a method for recovering styrene-based elastomer resin, a method of pelletizing by a strand cutting method or an underwater cutting method after removing a solvent by a thin film evaporator or an extruder, or a method of granulating by steam stripping is adopted. There are many cases.
ストランドカット方式や水中カット方式でペレット化する方法においては水中でブロッキング防止剤を付与することが最も効果的で、特許文献６においても脂肪酸アミドを付与する製造方法が開示されている。この製造法によって一定ブロッキング性の良好なスチレン系エラストマー樹脂ペレットの安定生産が可能となるが、まだ十分とはいえない場合があった。さらに特許文献７のように、水性乳濁液と無機塩を添加する方法を水中カット方式に応用展開する方法もあるが、この方法では、水中カット循環タンク内の無機塩濃度が高くなり、押出機のダイを腐食させてしまう懸念があった。 In the method of pelletizing by the strand cut method or the underwater cut method, it is most effective to apply an antiblocking agent in water, and Patent Document 6 discloses a production method of providing a fatty acid amide. Although this production method enables stable production of styrenic elastomer resin pellets with good constant blocking properties, it may not be sufficient yet. Furthermore, as disclosed in Patent Document 7, there is a method of applying and developing the method of adding an aqueous emulsion and an inorganic salt to the underwater cutting method. However, in this method, the concentration of the inorganic salt in the underwater cutting circulation tank is increased, and the extrusion is performed. There was a concern of corroding the die of the machine.
特許文献６および７のブロッキング防止剤はいずれも液内に微粒子を有するもので、微粒子がペレット表面に付着することによってブロッキング防止性を発現している。これら参考文献以外の方法で、水性乳濁液から粉末や微粒子を得る方法の一つに凍結凝固法がある。凍結凝固とは乳化重合法によって得られた水性乳濁液を凍結することにより、重合体粒子を凝集、圧着することによって凝固させて乳化状態を破壊し、水性乳濁液から重合体を分離することである。例えば特許文献８では、アクリル系重合体凝固物を得る目的として、アクリル酸エステルおよびこれとの共重合体からなる内層とメタクリル酸エステルおよびこれとの共重合体からなる最外層からなる多層構造重合体の凍結凝固法が報告されているが、スチレン系エラストマー樹脂ペレット製造に適用できるものではない。 Each of the anti-blocking agents of Patent Documents 6 and 7 has fine particles in the liquid, and the anti-blocking property is expressed when the fine particles adhere to the pellet surface. One method for obtaining powders and fine particles from an aqueous emulsion by a method other than these references is a freeze coagulation method. Freeze coagulation freezes the aqueous emulsion obtained by the emulsion polymerization method, coagulates the polymer particles by coagulation and presses them to break the emulsion state, and separates the polymer from the aqueous emulsion. That is. For example, in Patent Document 8, for the purpose of obtaining an acrylic polymer coagulum, a multilayer structure comprising an inner layer composed of an acrylate ester and a copolymer thereof and an outermost layer composed of a methacrylate ester and a copolymer thereof is used. A freeze-coagulation method for coalescence has been reported, but it cannot be applied to the production of styrene elastomer resin pellets.
このようにスチレン系エラストマー樹脂ペレットを製造するにあたっての諸問題を解決し、ブロッキング性の良好な製品を安定的に生産する製造プロセスの開発が望まれていた。
本発明は、上記現状に鑑み、ブロッキング性の良好なスチレン系エラストマー樹脂ペレット製品を安定的に製造する方法を提供することを目的とするものである。 In view of the above-mentioned present situation, an object of the present invention is to provide a method for stably producing a styrenic elastomer resin pellet product having a good blocking property.
本発明は、 スチレン系エラストマー樹脂ペレットの製造方法であって、下記（１）〜（３）の工程からなる製造方法に関するものである。
（１）芳香族ビニル系単量体を主成分とする重合体の水性乳濁液を凍結凝固後、解凍することによって凝固組成物を作製する工程、
（２）固形分濃度が１．０重量％以上１０．０重量％以下である、（１）で得られた凝固組成物、水、及び水溶性高分子の混合物を調製する工程、
（３）スチレン系エラストマー樹脂ペレットに、（２）で得られた混合物を付着させる工程
好ましい実施態様としては、前記水溶性高分子がメチルセルロースである製造方法に関する。
The present invention relates to a method for producing styrene-based elastomer resin pellets, and relates to a production method comprising the following steps (1) to (3).
(1) A step of producing a coagulated composition by thawing after freezing and coagulating an aqueous emulsion of a polymer mainly composed of an aromatic vinyl monomer,
(2) a step of preparing a mixture of the coagulation composition obtained in (1), water, and a water-soluble polymer, wherein the solid content concentration is 1.0% by weight or more and 10.0% by weight or less;
(3) The process of making the mixture obtained by (2) adhere to a styrene-type elastomer resin pellet As a preferable embodiment, it is related with the manufacturing method whose said water-soluble polymer is methylcellulose.
好ましい実施態様としては、前記水槽中の水溶性高分子濃度が０．１〜１００ｐｐｍである製造方法に関する。 As a preferred embodiment, the present invention relates to a production method wherein the water-soluble polymer concentration in the water tank is 0.1 to 100 ppm.
好ましい実施態様としては、スチレン系エラストマー樹脂が、（Ａ）イソブチレンを主体として構成される重合体ブロックと（Ｂ）芳香族ビニル系単量体を主体として構成される重合体ブロックからなる重合体である製造方法に関する。 In a preferred embodiment, the styrene elastomer resin is a polymer comprising (A) a polymer block mainly composed of isobutylene and (B) a polymer block mainly composed of an aromatic vinyl monomer. It relates to a certain manufacturing method.
本発明によると、設備腐食要因の無機塩をブロッキング防止剤に用いることなく、ブロッキング性の良好なスチレン系エラストマー樹脂ペレットを安定的に得ることができる。また本発明によると、もしも何らかの理由により無機塩を用いる必要が生じた場合でも、その使用量を低く抑えることが可能である。 According to the present invention, styrenic elastomer resin pellets with good blocking properties can be stably obtained without using an inorganic salt that causes equipment corrosion as an antiblocking agent. Further, according to the present invention, even if it becomes necessary to use an inorganic salt for some reason, the amount used can be kept low.
〔スチレン系エラストマー〕
本発明における「スチレン系エラストマー」とは、スチレン及びその誘導体のモノマー（以後「芳香族ビニル系単量体」と呼ぶ）を重合して得られる重合体ブロックを構成単位として含むブロック共重合体である。スチレン系エラストマーの原料として使用されるスチレン系単量体としては特に限定されないが、スチレン、ｏ−、ｍ−又はｐ−メチルスチレン、α−メチルスチレン、β−メチルスチレン、２，６−ジメチルスチレン、２，４−ジメチルスチレン、α−メチル−ｏ−メチルスチレン、α−メチル−ｍ−メチルスチレン、α−メチル−ｐ−メチルスチレン、β−メチル−ｏ−メチルスチレン、β−メチル−ｍ−メチルスチレン、β−メチル−ｐ−メチルスチレン、２，４，６−トリメチルスチレン、α−メチル−２，６−ジメチルスチレン、α−メチル−２，４−ジメチルスチレン、β−メチル−２，６−ジメチルスチレン、β−メチル−２，４−ジメチルスチレン、ｏ−、ｍ−又はｐ−クロロスチレン、２，６−ジクロロスチレン、２，４−ジクロロスチレン、α−クロロ−ｏ−クロロスチレン、α−クロロ−ｍ−クロロスチレン、α−クロロ−ｐ−クロロスチレン、β−クロロ−ｏ−クロロスチレン、β−クロロ−ｍ−クロロスチレン、β−クロロ−ｐ−クロロスチレン、２，４，６−トリクロロスチレン、α−クロロ−２，６−ジクロロスチレン、α−クロロ−２，４−ジクロロスチレン、β−クロロ−２，６−ジクロロスチレン、β−クロロ−２，４−ジクロロスチレン、ｏ−、ｍ−又はｐ−ｔ−ブチルスチレン、ｏ−、ｍ−又はｐ−メトキシスチレン、ｏ−、ｍ−又はｐ−クロロメチルスチレン、ｏ−、ｍ−又はｐ−ブロモメチルスチレン、シリル基で置換されたスチレン誘導体等が挙げられる。スチレン系単量体としては、スチレン、α−メチルスチレン、ｐ−メチルスチレンからなる群から選ばれた１種以上の単量体を使用することが好ましく、コストの面からスチレン、α−メチルスチレン、あるいはこれらの混合物を用いることが特に好ましい。
[Styrene elastomer]
The “styrene elastomer” in the present invention is a block copolymer containing as a constituent unit a polymer block obtained by polymerizing monomers of styrene and its derivatives (hereinafter referred to as “aromatic vinyl monomers”). is there. The styrene monomer used as a raw material for the styrene elastomer is not particularly limited, but styrene, o-, m- or p-methyl styrene, α-methyl styrene, β-methyl styrene, 2,6-dimethyl styrene. 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m- Methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6 -Dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-, m- or p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichloro Styrene, α-chloro-o-chlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro -P-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β- Chloro-2,4-dichlorostyrene, o-, m- or pt-butylstyrene, o-, m- or p-methoxystyrene, o-, m- or p-chloromethylstyrene, o-, m- Alternatively, p-bromomethylstyrene, a styrene derivative substituted with a silyl group, and the like can be given. As the styrenic monomer, it is preferable to use one or more monomers selected from the group consisting of styrene, α-methylstyrene, and p-methylstyrene. From the viewpoint of cost, styrene and α-methylstyrene are used. Or a mixture of these is particularly preferred.
本発明の製造方法は、従来公知の「スチレン系エラストマー」、例えば一般にスチレン系熱可塑性エラストマーとよばれているブロック共重合体やスチレン−ブタジエンゴム（ＳＢＲ）に適用可能である。スチレン系熱可塑性エラストマーとしては、スチレン−エチレンブチレン共重合体−スチレン（Ｓ−ＥＢ−Ｓ）、スチレン−エチレンプロピレン共重合体−スチレン（Ｓ−ＥＰ−Ｓ）、スチレン−ブタジエン−スチレン（Ｓ−Ｂ−Ｓ）、スチレン−イソプレン−スチレン（Ｓ−Ｉ−Ｓ）、スチレン−イソブチレン−スチレン（Ｓ−ＩＢ−Ｓ）を挙げることができる。 The production method of the present invention is applicable to a conventionally known “styrene elastomer”, for example, a block copolymer or styrene-butadiene rubber (SBR) generally called a styrene thermoplastic elastomer. Styrenic thermoplastic elastomers include styrene-ethylene butylene copolymer-styrene (S-EB-S), styrene-ethylene propylene copolymer-styrene (S-EP-S), styrene-butadiene-styrene (S- B-S), styrene-isoprene-styrene (S-I-S), and styrene-isobutylene-styrene (S-IB-S).
また「スチレン系エラストマー」としては、イソブチレンを含むものが好ましく、特に（Ａ）イソブチレンを主体として構成される重合体ブロックと、（Ｂ）芳香族ビニル系単量体を主体として構成される重合体ブロックからなる「イソブチレン系ブロック共重合体」が好ましい。イソブチレン系ブロック共重合体は比較的粘着性が高く、ブロッキングが発生しやすい場合があるので、本発明の製造方法による改善効果が大きい。さらに強度・伸びに優れるイソブチレン系ブロック共重合体を安定的に生産できるという点から、本発明は、イソブチレンと芳香族ビニル系単量体などの単量体を、ルイス酸触媒および開始剤の存在下でカチオン重合して得られるイソブチレン系ブロック共重合体の製造に適用することが好ましい。 The “styrene elastomer” preferably contains isobutylene, and in particular, (A) a polymer block mainly composed of isobutylene and (B) a polymer mainly composed of an aromatic vinyl monomer. An “isobutylene block copolymer” composed of blocks is preferred. Since the isobutylene-based block copolymer has relatively high tackiness and is likely to cause blocking, the improvement effect by the production method of the present invention is great. Furthermore, from the point that it is possible to stably produce an isobutylene block copolymer excellent in strength and elongation, the present invention is based on the presence of a Lewis acid catalyst and an initiator such as isobutylene and an aromatic vinyl monomer. It is preferably applied to the production of an isobutylene block copolymer obtained by cationic polymerization under the following conditions.
（Ａ）のイソブチレンを主体として構成される重合体ブロックは、通常、イソブチレン単位を６０重量％以上、イソブチレン系重合体特有のガスバリア性を維持する観点から好ましくは８０重量％以上含有する重合体ブロックである。また、（Ｂ）の芳香族ビニル系単量体を主体として構成される重合体ブロックは、通常、芳香族ビニル系単量体単位を６０重量％以上、スチレン系エラストマーとしての強度、伸び等の物性を維持する観点から好ましくは８０重量％以上含有する重合体ブロックである。 The polymer block composed mainly of isobutylene of (A) is usually a polymer block containing 60% by weight or more of isobutylene units, and preferably 80% by weight or more from the viewpoint of maintaining gas barrier properties peculiar to isobutylene polymers. It is. In addition, the polymer block composed mainly of the aromatic vinyl monomer (B) usually has an aromatic vinyl monomer unit of 60% by weight or more, strength, elongation, etc. as a styrene elastomer. From the viewpoint of maintaining physical properties, the polymer block is preferably contained in an amount of 80% by weight or more.
上記ルイス酸触媒は、カチオン重合に使用できるものであれば特に限定されず、ＴｉＣｌ４、ＢＣｌ３、ＢＦ３、ＡｌＣｌ３、ＳｎＣｌ４等のハロゲン化金属を挙げることができるが、なかでも四塩化チタン（ＴｉＣｌ４）がイソブチレン系ブロック重合体の反応性とその触媒回収の容易さと回収触媒の安全性の観点から好ましい。 The Lewis acid catalyst is not particularly limited as long as it can be used for cationic polymerization, and examples thereof include metal halides such as TiCl 4 , BCl 3 , BF 3 , AlCl 3 , SnCl 4 , and tetrachloride. Titanium (TiCl 4 ) is preferred from the viewpoints of the reactivity of the isobutylene block polymer, the ease of catalyst recovery, and the safety of the recovered catalyst.
上記カチオン重合において用いられる重合溶媒としては特に限定されず、ハロゲン化炭化水素からなる溶媒、非ハロゲン系の溶媒又はこれらの混合物を用いることができる。好ましくは、炭素数３〜８の１級及び／又は２級のモノハロゲン化炭化水素と脂肪族及び／又は芳香族炭化水素との混合溶媒がイソブチレン系ブロック共重合体の溶解性の面から好ましい。 The polymerization solvent used in the cationic polymerization is not particularly limited, and a solvent composed of a halogenated hydrocarbon, a non-halogen solvent, or a mixture thereof can be used. Preferably, a mixed solvent of a primary and / or secondary monohalogenated hydrocarbon having 3 to 8 carbon atoms and an aliphatic and / or aromatic hydrocarbon is preferable from the viewpoint of solubility of the isobutylene block copolymer. .
上記炭素数３〜８の１級及び／又は２級のモノハロゲン化炭化水素としては特に限定されず、塩化メチル、塩化メチレン、１−クロロブタン、クロロベンゼンなどを挙げることができる。この中でも、イソブチレン系ブロック共重合体の溶解度、分解による無害化の容易さ、コスト等のバランスから、１−クロロブタンが好適である。 The primary and / or secondary monohalogenated hydrocarbon having 3 to 8 carbon atoms is not particularly limited, and examples thereof include methyl chloride, methylene chloride, 1-chlorobutane and chlorobenzene. Among these, 1-chlorobutane is preferable from the standpoint of the solubility of the isobutylene block copolymer, the ease of detoxification by decomposition, the cost, and the like.
また、上記脂肪族及び／又は芳香族系炭化水素としては特に限定されず、例えば、ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、トルエン等が挙げられる。メチルシクロヘキサン、エチルシクロヘキサン及びトルエンからなる群より選ばれる１種以上がコストおよびカチオン重合の反応性の観点から特に好ましい。 The aliphatic and / or aromatic hydrocarbons are not particularly limited, and examples thereof include pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, and toluene. One or more selected from the group consisting of methylcyclohexane, ethylcyclohexane and toluene are particularly preferred from the viewpoints of cost and reactivity of cationic polymerization.
なお、カチオン重合の際に用いる開始剤としては、下記式（Ｉ）で表される化合物を用いるのがカチオン重合の反応性の観点から好ましい。 In addition, it is preferable from a reactive viewpoint of cationic polymerization to use the compound represented by following formula (I) as an initiator used in the case of cationic polymerization.
（ＣＲ１Ｒ２Ｘ）ｎ Ｒ３ （Ｉ）
［式中、Ｘは、ハロゲン原子又は炭素数１〜６のアルコキシ基若しくはアシロキシ基を表す。Ｒ１及びＲ２は、同一又は異なって、水素原子又は炭素数１〜６の１価炭化水素基を表し、Ｒ１とＲ２は同一であっても異なっていてもよい。Ｒ３は多価芳香族炭化水素基又は多価脂肪族炭化水素基を表す。ｎは１〜６の自然数を示す。］
上記一般式（Ｉ）の化合物の具体例としては、１，４−ビス（α−クロル−イソプロピル）ベンゼン［Ｃ６Ｈ４（Ｃ（ＣＨ３）２Ｃｌ）２］が挙げられる［なお、１，４−ビス（α−クロル−イソプロピル）ベンゼンはジクミルクロライドとも呼ばれる］。
(CR 1 R 2 X) n R 3 (I)
[Wherein, X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group. R 1 and R 2 are the same or different and each represents a monovalent hydrocarbon group hydrogen atom or 1 to 6 carbon atoms, R 1 and R 2 may be different even in the same. R 3 represents a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic hydrocarbon group. n shows the natural number of 1-6. ]
Specific examples of the compound of the general formula (I) include 1,4-bis (α-chloro-isopropyl) benzene [C 6 H 4 (C (CH 3 ) 2 Cl) 2 ]. , 4-bis (α-chloro-isopropyl) benzene is also called dicumyl chloride].
イソブチレン系ブロック共重合体の重合に際しては、更に必要に応じて電子供与体成分を共存させることもできる。このような化合物として、例えば、ピリジン類、アミン類、アミド類、スルホキシド類、エステル類、又は、金属原子に結合した酸素原子を有する金属化合物等を挙げることができる。 In the polymerization of the isobutylene block copolymer, an electron donor component can be further present if necessary. Examples of such compounds include pyridines, amines, amides, sulfoxides, esters, or metal compounds having an oxygen atom bonded to a metal atom.
実際の重合を行うに当たっては、各成分を冷却下、例えば−１００℃以上０℃未満の温度で混合する。エネルギーコストと重合の安定性を釣り合わせるために、特に好ましい温度範囲は−８０℃〜−３０℃である。 In carrying out the actual polymerization, each component is mixed at a temperature of, for example, −100 ° C. or more and less than 0 ° C. under cooling. In order to balance the energy cost and the stability of the polymerization, a particularly preferred temperature range is −80 ° C. to −30 ° C.
またイソブチレン系ブロック共重合体の数平均分子量にも特に制限はないが、流動性、加工性、物性等の面から、３００００〜５０００００であることが好ましく、５００００〜４０００００であることが特に好ましい。 The number average molecular weight of the isobutylene block copolymer is not particularly limited, but is preferably 30,000 to 500,000, particularly preferably 50,000 to 400,000 from the viewpoint of fluidity, workability, physical properties, and the like.
重合後のイソブチレン系ブロック共重合体を含有する重合体溶液は、水またはアルカリ水と接触させて、触媒を失活して反応を停止させた後、引き続き水洗を行い、触媒残査や金属イオンを抽出、除去して、精製ドープを得ることができる。 After the polymerization, the polymer solution containing the isobutylene block copolymer is brought into contact with water or alkaline water to deactivate the catalyst to stop the reaction, followed by washing with water to remove catalyst residues and metal ions. Can be extracted and removed to obtain a purified dope.
失活及び水洗温度は特に制限されるものではないが、常温〜１００℃の範囲が好ましい。また、失活及び水洗に使用する水量は、特に限定されるものではないが、重合体溶液に対する水の体積比が１／１０〜１０の範囲が触媒失活の効率と生産性のバランスから好ましい。 The deactivation and water washing temperatures are not particularly limited, but are preferably in the range of room temperature to 100 ° C. The amount of water used for deactivation and washing is not particularly limited, but a volume ratio of water to the polymer solution of 1/10 to 10 is preferable from the balance between catalyst deactivation efficiency and productivity. .
このようにして得られた精製重合体溶液、すなわち触媒を失活、除去したイソブチレン系ブロック共重合体を含有する重合終了後の溶液をフラッシュ蒸発、薄膜式蒸発、撹拌槽、濡れ壁式等の蒸発機を単独あるいは複数用いることにより所望濃度の溶媒量にまで溶媒を除去することができる。このようにして得られたエラストマー樹脂はストランドカットあるいは水中カット方式により、それぞれ求められる形状のペレットに加工することができる。 The purified polymer solution thus obtained, i.e., the solution after completion of the polymerization containing the deactivated isobutylene block copolymer, is subjected to flash evaporation, thin film evaporation, stirring tank, wet wall type, etc. By using one or more evaporators, the solvent can be removed up to a desired amount of solvent. The elastomer resin thus obtained can be processed into pellets having the required shapes by a strand cut method or an underwater cut method.
なお上記の通り、本発明のスチレン系エラストマー樹脂は、芳香族ビニル系単量体を重合して得られる重合体ブロックを構成単位として含む重合体であれば特に制限なく、従来公知の重合体を使用することが可能である。本発明のスチレン系エラストマー樹脂としては、例えば、一般にスチレン系熱可塑性エラストマーとよばれているブロック共重合体やスチレン−ブタジエンゴム（ＳＢＲ）を挙げることができる。スチレン系熱可塑性エラストマーとしては、スチレン−エチレンブチレン共重合体−スチレン（Ｓ−ＥＢ−Ｓ）、スチレン−エチレンプロピレン共重合体−スチレン（Ｓ−ＥＰ−Ｓ）、スチレン−ブタジエン−スチレン（Ｓ−Ｂ−Ｓ）、スチレン−イソプレン−スチレン（Ｓ−Ｉ−Ｓ）、スチレン−イソブチレン−スチレン（Ｓ−ＩＢ−Ｓ）を挙げることができる。
〔ペレット化設備のフロー例〕
図１は、ペレット化設備のフロー例である。
As described above, the styrene elastomer resin of the present invention is not particularly limited as long as it is a polymer containing a polymer block obtained by polymerizing an aromatic vinyl monomer as a constituent unit, and a conventionally known polymer is used. It is possible to use. Examples of the styrene elastomer resin of the present invention include a block copolymer generally called a styrene thermoplastic elastomer and styrene-butadiene rubber (SBR). Styrenic thermoplastic elastomers include styrene-ethylene butylene copolymer-styrene (S-EB-S), styrene-ethylene propylene copolymer-styrene (S-EP-S), styrene-butadiene-styrene (S- B-S), styrene-isoprene-styrene (S-I-S), and styrene-isobutylene-styrene (S-IB-S).
[Example of pelletizing equipment flow]
FIG. 1 is a flow example of a pelletizing facility.
重合体は蒸発操作終了後の溶融状態のまま押出機１を経由してダイス２から押出される。ダイス面には高速で回転するカッターが密着しており、ダイス及びカッターは水中に位置する構造となっている。循環冷却水は冷却水タンク４から循環ポンプ５により循環する。冷却水タンク４にはブロッキング防止剤および水溶性高分子を含有する水溶液を添加しておき、運転中は、好ましい濃度になるように濃度管理を行い適宜追加するのが好ましい。循環冷却水は途中熱交換器６を経由することにより適宜温度調節されるようになっている。 The polymer is extruded from the die 2 via the extruder 1 in the molten state after completion of the evaporation operation. A cutter that rotates at high speed is in close contact with the die surface, and the die and the cutter are located in water. The circulating cooling water is circulated from the cooling water tank 4 by the circulation pump 5. It is preferable that an aqueous solution containing an antiblocking agent and a water-soluble polymer is added to the cooling water tank 4 and the concentration is controlled so as to obtain a preferable concentration during operation. The temperature of the circulating cooling water is appropriately adjusted by passing through the heat exchanger 6 on the way.
カットされたペレットは循環冷却水中を分散したスラリー状態で３の脱水乾燥機へ送られる。脱水乾燥機ではペレットと循環冷却水が分離され、かつペレット表面水の乾燥が行われる。乾燥ペレットは乾燥機上部の開口部より系外に排出される。分離された循環冷却水は脱水乾燥機３から再度冷却水タンク４に戻され再利用される。
〔ブロッキング防止剤〕
本発明のブロッキング防止剤とは、スチレン系エラストマーのブロッキングを防止するために有効であることが当業者に知られている物質、あるいは当業者にとって有効であろうことが合理的に予測されうる物質をいい、特に本発明においては、乳化重合法によって得られる水性乳濁液よりなる各種熱可塑性樹脂をいう。具体的には、芳香族ビニル系単量体からなる重合体（ポリスチレン等）や、アクリル系単量体と芳香族ビニル系単量体からなる共重合体を挙げることができる。
{熱可塑性樹脂}
熱可塑性樹脂としては、粒子径の制御が比較的容易であることからビニル系ポリマーの乳化重合体またはその凝集体が好ましい。上記ビニル系ポリマーを構成する重合性モノマーとしては、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ジビニルベンゼンなどの芳香族ビニル系単量体のうち少なくとも１種類が含まれていることが好ましい。そのほかに、非芳香族ビニル系単量体として、（メタ）アクリル酸、クロトン酸などの不飽和カルボン酸類、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ｉ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレートなどの（メタ）アクリレート類、（メタ）アクリロニトリル、シアン化ビニリデンなどのシアン化ビニル化合物、塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、テトラフルオロエチレンなどのハロゲン化ビニル化合物が含まれていてもよい。これら非芳香族ビニル系単量体は２種以上を適宜併用してもよい。
The cut pellets are sent to the dehydrating dryer 3 in a slurry state in which circulating cooling water is dispersed. In the dehydrating dryer, the pellets and the circulating cooling water are separated, and the pellet surface water is dried. The dried pellets are discharged out of the system through the opening at the top of the dryer. The separated circulating cooling water is returned to the cooling water tank 4 from the dehydrating dryer 3 and reused.
[Anti-blocking agent]
The anti-blocking agent of the present invention is a substance that is known to those skilled in the art to be effective for preventing blocking of a styrenic elastomer, or a substance that can be reasonably expected to be effective for those skilled in the art. In particular, in the present invention, it refers to various thermoplastic resins comprising an aqueous emulsion obtained by an emulsion polymerization method. Specifically, a polymer composed of an aromatic vinyl monomer (polystyrene or the like) and a copolymer composed of an acrylic monomer and an aromatic vinyl monomer can be exemplified.
{Thermoplastic resin}
As the thermoplastic resin, a vinyl polymer emulsion polymer or an aggregate thereof is preferable because the particle size can be controlled relatively easily. The polymerizable monomer constituting the vinyl polymer is at least one of aromatic vinyl monomers such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and divinylbenzene. Preferably the type is included. In addition, as non-aromatic vinyl monomers, unsaturated carboxylic acids such as (meth) acrylic acid and crotonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i- Propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, ( (Meth) acrylates such as poly) propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, vinyl cyanide compounds such as (meth) acrylonitrile, vinylidene cyanide, vinyl chloride, vinylidene chloride, vinyl fluoride , Vinylidide fluoride , It may include vinyl halide compounds such as tetrafluoroethylene. Two or more of these non-aromatic vinyl monomers may be used in combination as appropriate.
熱可塑性樹脂の主成分である芳香族ビニル系単量体としては、上述したスチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ジビニルベンゼンなどが挙げられるが、これらは単独で用いてもよく、２種以上を併用してもよい。なかでも、コストの面から、スチレン、ｐ−メチルスチレン、α−メチルスチレン又はこれらの混合物が特に好ましい。 Examples of the aromatic vinyl monomer that is the main component of the thermoplastic resin include styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, divinyl benzene, and the like described above. These may be used alone or in combination of two or more. Of these, styrene, p-methylstyrene, α-methylstyrene or a mixture thereof is particularly preferable from the viewpoint of cost.
熱可塑性樹脂の芳香族ビニル系単量体の割合は、３０重量％以上１００重量％以下がそれを付着させる樹脂粉粒体の透明性を維持する観点で好ましく、５０重量％以上１００重量％以下が特に芳香族ビニル系単量体を含む樹脂粉粒体との親和性の観点からより好ましい。
（水性乳濁液の調整方法）
水性乳濁液を調整する方法は特に限定されないが、水性溶媒、重合開始剤、乳化剤等の存在下で、上記重合性モノマーを乳化重合することにより得ることができる。得られた水性乳濁液はそのまま本発明の製造方法において用いることができる。
（重合開始剤）
上記重合開始剤としては公知のラジカル重合開始剤などを使用でき、水溶性や油溶性の重合開始剤、熱分解型やレドックス型の重合開始剤などが使用される。たとえば通常の過硫酸塩などの無機開始剤、あるいは有機過酸化物、アゾ化合物などを単独で用いるか、上記化合物と亜硫酸塩、亜硫酸水素、チオ硫酸塩、第一金属塩、ナトリウムホルムアルデヒドスルホキシレートなどを組み合わせ、レドックス系で用いてもよい。重合開始剤として好ましい過硫酸塩としてはたとえば過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウムなどがあげられ、好ましい有機過酸化物としては、たとえばｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、過酸化ベンゾイル、過酸化ラウロイルなどがあげられる。
（乳化剤）
また、上記乳化剤としては公知のものが使用され、たとえば脂肪酸塩、アルキル硫酸エステル塩（ドデシル硫酸ナトリウムなど）、アルキルベンゼンスルホン酸塩、アルキルリン酸エステル塩、スルホコハク酸ジエステル塩などのアニオン系界面活性剤や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脂肪酸エステルなどの非イオン系界面活性剤などがあげられる。さらに重合開始剤として過硫酸カリウムなどを用いることでソープフリーによって芳香族ビニル系単量体を主成分とする熱可塑性樹脂粒子を含有する水性乳濁液を作製してもよい。
（重合条件）
熱可塑性樹脂を重合する際の温度や時間などにも特に限定はなく、使用目的に応じて所望の比粘度、粒子径になるように適宜調整すればよい。
水性乳濁液として添加される熱可塑性樹脂の量は、冷却水槽中の樹脂固形分濃度で０．５重量％から２０重量％であるのが好ましい。０．５重量％未満ではブロッキング防止剤としての効果が十分でない場合がある。また、２０重量部を超えると、冷却水槽内の粘度上昇、スケールの発生などによるトラブルを招くことがあり好ましくない。
〔ブロッキング防止剤の凍結方法と解凍方法〕
ブロッキング防止剤を凍結する方法は特に限定されないが、例えば冷凍室内での放置による方法や、製氷機による方法がある。また凍結方法と同様、解凍する方法も特には限定されないが、例えば放置、加熱、高熱伝導率体との接触による方法がある。これらの中からプロセス上の処理時間、コストを考慮して最適な方法を選択すればよい。
〔凝固組成物〕
本発明の工程（１）は、水性乳濁液を凍結凝固後、解凍させる工程であるが、この工程により凝固組成物を得ることができる。そして工程（２）は、「固形分濃度が１．０重量％以上１０重量％以下である、（１）で得られた凝固組成物、水、及び水溶性高分子の混合物」を調製する工程である。工程（２）で冷却水タンク中の固形分濃度を１．０重量％以上１０重量％以下に調製することが、ブロッキング防止性および安定生産性の観点から好ましい。工程（２）で得られる混合物の固形分濃度が１．０重量％未満だと、ブロッキング防止性を発現せず、１０重量％より高いと、冷却水タンク内で泡が発生し、その泡がタンク外へオーバーフローすることから生産が不可能になるという問題が発生する場合がある。これは脱水乾燥機からのタンクへの戻りが落水となっていること、またブロッキング防止剤内に発泡性の乳化剤が含まれていることが原因である。
The proportion of the aromatic vinyl monomer in the thermoplastic resin is preferably 30% by weight or more and 100% by weight or less from the viewpoint of maintaining the transparency of the resin particles to which it is attached, and is 50% by weight or more and 100% by weight or less. Is more preferable from the viewpoint of affinity with a resin powder containing an aromatic vinyl monomer.
(Method for adjusting aqueous emulsion)
The method for preparing the aqueous emulsion is not particularly limited, but it can be obtained by emulsion polymerization of the polymerizable monomer in the presence of an aqueous solvent, a polymerization initiator, an emulsifier and the like. The obtained aqueous emulsion can be used as it is in the production method of the present invention.
(Polymerization initiator)
As the polymerization initiator, a known radical polymerization initiator can be used, and a water-soluble or oil-soluble polymerization initiator, a thermal decomposition type or a redox type polymerization initiator, or the like is used. For example, usual inorganic initiators such as persulfates, organic peroxides, azo compounds, etc. are used alone, or the above compounds and sulfites, hydrogen sulfites, thiosulfates, first metal salts, sodium formaldehyde sulfoxylate Etc. may be used in combination with a redox system. Preferred examples of the persulfate as the polymerization initiator include sodium persulfate, potassium persulfate, and ammonium persulfate. Preferred examples of the organic peroxide include t-butyl hydroperoxide, cumene hydroperoxide, and benzoyl peroxide. And lauroyl peroxide.
(emulsifier)
In addition, known emulsifiers are used as the above-mentioned emulsifiers, for example, anionic surfactants such as fatty acid salts, alkyl sulfate esters (such as sodium dodecyl sulfate), alkylbenzene sulfonates, alkyl phosphate esters, and sulfosuccinate diester salts. And nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene fatty acid ester. Further, an aqueous emulsion containing thermoplastic resin particles mainly composed of an aromatic vinyl monomer may be prepared by soap-free by using potassium persulfate as a polymerization initiator.
(Polymerization conditions)
There is no particular limitation on the temperature and time when the thermoplastic resin is polymerized, and the temperature may be adjusted appropriately so as to obtain a desired specific viscosity and particle diameter according to the purpose of use.
The amount of thermoplastic resin added as an aqueous emulsion is preferably from 0.5 wt% to 20 wt% in terms of resin solids concentration in the cooling water bath. If it is less than 0.5% by weight, the effect as an anti-blocking agent may not be sufficient. On the other hand, if it exceeds 20 parts by weight, troubles due to increase in viscosity in the cooling water tank, generation of scale, etc. may be caused.
[Methods for freezing and thawing blocking inhibitors]
The method for freezing the anti-blocking agent is not particularly limited. For example, there are a method in which the anti-blocking agent is left in a freezer and a method using an ice maker. Further, like the freezing method, the thawing method is not particularly limited, but there is, for example, a method of leaving, heating, or contacting with a high thermal conductivity material. An optimum method may be selected from these in consideration of processing time and cost in the process.
[Coagulation composition]
Step (1) of the present invention is a step in which an aqueous emulsion is freeze-coagulated and then thawed. A coagulated composition can be obtained by this step. Step (2) is a step of preparing “a mixture of the solidified composition obtained in (1), the solid content concentration of which is 1.0 wt% or more and 10 wt% or less”, water, and a water-soluble polymer ”. It is. In the step (2), it is preferable that the solid content concentration in the cooling water tank is adjusted to 1.0% by weight or more and 10% by weight or less from the viewpoint of blocking prevention and stable productivity. When the solid content concentration of the mixture obtained in the step (2) is less than 1.0% by weight, the anti-blocking property is not expressed, and when it is higher than 10% by weight, bubbles are generated in the cooling water tank. There may be a problem in that production becomes impossible due to overflowing out of the tank. This is because the return from the dehydration dryer to the tank is falling, and the foaming emulsifier is contained in the antiblocking agent.
工程（２）での固形分濃度は、ブロッキング防止剤を１２０℃の乾燥機中で揮発分を除いた後の残留物の重量から算出したデータを基に、タンク内への仕込み量、つまり凝固組成物、水、及び水溶性高分子の仕込み量から換算した。
〔水溶性高分子〕
水溶性高分子の例としては、乳化作用、保護コロイド作用、分散作用を持つものであれば特に限定されないが、例えば、アラビアガム、カラギーナン、グアガム、ローカストビーンガム、ペクチン、トラガント、トウモロコシデンプン（コーンスターチ）、キサンタンガム、デキストリンなどの多糖類、ゼラチン、カゼイン、コンドロイチン硫酸ナトリウムなどのタンパク質類、エチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メチルセルロース、ニトロセルロース、カチオン化セルロースなどのセルロース類、リン酸化デンプンなどのデンプン類、アルギン酸ナトリウム、アルギン酸プロピレングリコールなどのアルギン酸類、ポリアクリル酸ナトリウム、カルボシキビニルポリマー、ポリアクリル酸アミド、アクリルアミド／アクリレート共重合体などのアクリル酸類、ポリビニルピロリドン、ポリビニルアルコール、ＰＶＰ／ＶＡ（ポリビニルピロリドン／ビニルアセテート）共重合体などのビニル系重合体類、その他ポリエチレングリコール、カチオン化グアガム、ヒアルロン酸ナトリウムなどが挙げられる。これらは単独で用いてもよいし、あるいは２種以上組み合わせて用いてもよい。なかでも、コスト面からメチルセルロース、ポリビニルアルコールが好ましい。加える水溶性高分子の量は、特に制限はないが、冷却水槽中０．１ｐｐｍから１００ｐｐｍが好ましい。０．１ｐｐｍ未満では効果が十分発揮できず、１００ｐｐｍを超えると冷却水槽中の泡立ちが顕著になり、処理できない。
The solid content concentration in step (2) is the amount charged into the tank, that is, solidified based on the data calculated from the weight of the residue after removing the volatile matter in the dryer at 120 ° C. It was converted from the charged amount of the composition, water, and water-soluble polymer.
(Water-soluble polymer)
Examples of the water-soluble polymer are not particularly limited as long as they have an emulsifying action, a protective colloid action, and a dispersing action. For example, gum arabic, carrageenan, guar gum, locust bean gum, pectin, tragacanth, corn starch (corn starch) ), Polysaccharides such as xanthan gum and dextrin, gelatin, casein, proteins such as sodium chondroitin sulfate, celluloses such as ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, nitrocellulose, cationized cellulose, phosphorylated starch Such as starch, sodium alginate, alginate such as propylene glycol alginate, sodium polyacrylate, carboxi Polymers, acrylic acids such as polyacrylamide, acrylamide / acrylate copolymers, vinyl polymers such as polyvinylpyrrolidone, polyvinyl alcohol, PVP / VA (polyvinylpyrrolidone / vinyl acetate) copolymers, other polyethylene glycols, cations Guar gum, sodium hyaluronate and the like. These may be used singly or in combination of two or more. Of these, methyl cellulose and polyvinyl alcohol are preferable from the viewpoint of cost. The amount of the water-soluble polymer to be added is not particularly limited, but is preferably 0.1 ppm to 100 ppm in the cooling water tank. If it is less than 0.1 ppm, the effect cannot be sufficiently exhibited, and if it exceeds 100 ppm, foaming in the cooling water tank becomes remarkable and treatment cannot be performed.
本発明で得られるスチレン系エラストマー樹脂ペレットは射出成形、押出し成形、カレンダー成形等、通常熱可塑性樹脂で用いられる成形法により成形することができる。また、エラストマー材料、樹脂、ゴム、アスファルト等の改質材、制振材、粘着剤のベースポリマー、樹脂改質剤の成分として用いることができる。 The styrenic elastomer resin pellets obtained in the present invention can be molded by a molding method usually used for thermoplastic resins, such as injection molding, extrusion molding, and calendar molding. Further, it can be used as a component of an elastomer material, resin, rubber, asphalt modifier, vibration damping material, adhesive base polymer, and resin modifier.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited only to these examples.
本実施例に示す重合体の分子量および引張強度は以下に示す方法で測定した。 The molecular weight and tensile strength of the polymer shown in this example were measured by the following methods.
分子量：Ｗａｔｅｒｓ社製ＧＰＣシステム（カラム：昭和電工（株）製Ｓｈｏｄｅｘ Ｋ−８０４（ポリスチレンゲル）、移動相：クロロホルム）。数平均分子量はポリスチレン換算で表記した。 Molecular weight: GPC system manufactured by Waters (column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK, mobile phase: chloroform). The number average molecular weight is expressed in terms of polystyrene.
得られた樹脂ペレットの耐ブロッキング性については、樹脂を１００℃の箱型乾燥機で乾燥後、内径５ｃｍのシリンダーに３０ｇ充填してピストンにて０．０３ＭＰａの荷重をかけて８５℃雰囲気下２時間保管した後、得られたペレットの流動性を目視で確認することで評価した。 Regarding the blocking resistance of the obtained resin pellets, the resin was dried in a box dryer at 100 ° C., then filled with 30 g in a cylinder having an inner diameter of 5 cm, and a piston was applied with a load of 0.03 MPa and the atmosphere was 85 ° C. 2 After storage for a long time, the fluidity of the obtained pellets was evaluated by visual confirmation.
芳香族ビニル系単量体を主成分とする重合体粒子の粒子径は（株）堀場製作所製レーザ回折／散乱式粒度分布測定装置ＬＡ−９２０を用いて体積基準平均粒子径として測定した。 The particle diameter of the polymer particles containing an aromatic vinyl monomer as a main component was measured as a volume-based average particle diameter using a laser diffraction / scattering particle size distribution analyzer LA-920 manufactured by Horiba, Ltd.
（製造例１）
撹拌機付き２０Ｌ反応容器に、１−クロロブタン（モレキュラーシーブスで乾燥したもの）５．１７ｋｇ、ヘキサン（モレキュラーシーブスで乾燥したもの）０．４５ｋｇ、ｐ−ジクミルクロライド７．７７ｇを加えた。反応容器を−７０℃に冷却した後、Ｎ，Ｎ−ジメチルアセトアミド４．４９ｇ、イソブチレン１．２９ｋｇを添加した。さらに四塩化チタン３３．９ｇを加えて重合を開始し、−７０℃で溶液を攪拌しながら２時間反応させた。次いで反応溶液にスチレン５５２ｇを添加し、さらに３０分間反応を続け、重合体溶液を得た。
(Production Example 1)
To a 20 L reaction vessel equipped with a stirrer, 5.17 kg of 1-chlorobutane (dried with molecular sieves), 0.45 kg of hexane (dried with molecular sieves), and 7.77 g of p-dimethyl milk chloride were added. After cooling the reaction vessel to −70 ° C., 4.49 g of N, N-dimethylacetamide and 1.29 kg of isobutylene were added. Further, 33.9 g of titanium tetrachloride was added to initiate polymerization, and the reaction was allowed to proceed for 2 hours while stirring the solution at -70 ° C. Next, 552 g of styrene was added to the reaction solution, and the reaction was further continued for 30 minutes to obtain a polymer solution.
得られた重合体溶液を大量の水中へあけて反応を停止させた。反応停止後、分液ロートで重合体溶液相と水相を分離した。同様の方法で重合体溶液相の水洗を２回行った後、水層が中性になっているのを確認してから重合体溶液相を払い出し、重合体溶液を得た。 The obtained polymer solution was poured into a large amount of water to stop the reaction. After the reaction was stopped, the polymer solution phase and the aqueous phase were separated with a separatory funnel. The polymer solution phase was washed twice with the same method, and after confirming that the aqueous layer was neutral, the polymer solution phase was discharged to obtain a polymer solution.
ＧＰＣ分析を行ったところ、数平均分子量が６６，０００、分子量分布が１．２８であった。 When GPC analysis was performed, the number average molecular weight was 66,000 and the molecular weight distribution was 1.28.
（製造例２）
撹拌機およびジャケット付き２００Ｌ反応容器に、スチレンモノマー（苛性水溶液で重合禁止剤を抽出除去したもの）２６．９ｋｇ、苛性ソーダによりｐＨ１０に調製した蒸留水を９０．３ｋｇ、ドデシル硫酸ナトリウムを１５０ｇ加え、窒素通気雰囲気下で７０℃に加熱しながら６０分間撹拌した。その後、過硫酸カリウムを７５ｇ添加して４時間反応させることによりポリスチレン粒子を含有する水性乳濁液を得た。
(Production Example 2)
To a 200 L reactor equipped with a stirrer and jacket, add 26.9 kg of styrene monomer (extracted and removed with a caustic aqueous solution of polymerization inhibitor), 90.3 kg of distilled water adjusted to pH 10 with caustic soda, and 150 g of sodium dodecyl sulfate. It stirred for 60 minutes, heating at 70 degreeC by ventilation | gas_flowing atmosphere. Thereafter, 75 g of potassium persulfate was added and reacted for 4 hours to obtain an aqueous emulsion containing polystyrene particles.
得られたポリスチレン粒子の粒子径は、体積基準平均粒子径で０．１７μｍであった。また水性乳濁液の固形分濃度は２３％であった。 The resulting polystyrene particles had a volume-based average particle size of 0.17 μm. The solid content concentration of the aqueous emulsion was 23%.
（実施例１）
製造例２で得られた水性乳濁液を、−２５℃の冷凍室内に保管し完全に凍結させ、その後冷凍室から取り出し、２０℃の室内に放置して解凍を行なう。この操作にて水性乳濁液内には凝固組成物が生じ、凝固組成物と、水を主成分とする液体とからなるこのスラリー液を、ブロッキング防止剤（１）とする。次にブロッキング防止剤（１）を冷却水タンク４に添加し、水槽中の固形分濃度を１．０％とした。さらに冷却水タンク４にブロッキング防止助剤としてのメチルセルロース（信越化学工業（株）製ＳＭ４００）を冷却水槽内濃度５ｐｐｍとなるように添加した。
Example 1
The aqueous emulsion obtained in Production Example 2 is stored in a freezing chamber at −25 ° C. and completely frozen, then taken out of the freezing chamber and left in a 20 ° C. room for thawing. By this operation, a coagulated composition is formed in the aqueous emulsion, and this slurry liquid comprising the coagulated composition and a liquid containing water as a main component is used as an anti-blocking agent (1). Next, the blocking inhibitor (1) was added to the cooling water tank 4 to adjust the solid content concentration in the water tank to 1.0%. Further, methylcellulose (SM400 manufactured by Shin-Etsu Chemical Co., Ltd.) as an antiblocking aid was added to the cooling water tank 4 so that the concentration in the cooling water tank was 5 ppm.
上記製造例１で得られた重合体溶液を図１に示すようなベント口付き二軸押出機に供給し、胴部バレル及びスクリューを１８０℃に温度調節しながら、押出機に付帯する孔径２．８ｍｍのダイスから水中カットシステムによって球状ペレットに加工した。 The polymer solution obtained in Production Example 1 is supplied to a twin-screw extruder with a vent port as shown in FIG. 1, and the diameter of the hole 2 attached to the extruder is adjusted while adjusting the temperature of the barrel barrel and screw to 180 ° C. .Spherical pellets were processed from an 8 mm die by an underwater cutting system.
これらを通して得られるペレットの耐ブロッキング性は、表１に示すように、ブロック化せず流動性は良好であった。また発泡は見られるものの、その泡成長速度は遅く、タンクから泡がオーバーフローするまでは生産が十分可能なものであった。 As shown in Table 1, the blocking resistance of the pellets obtained through these was not blocked and the flowability was good. Although foaming was observed, the foam growth rate was slow, and production was sufficiently possible until the foam overflowed from the tank.
（実施例２）
ブロッキング防止剤（１）を冷却水タンク４に添加し、水槽中の固形分濃度を３．０％とした以外は、実施例１と同様に実施した。
(Example 2)
It implemented similarly to Example 1 except having added the antiblocking agent (1) to the cooling water tank 4, and having made solid content concentration in a water tank into 3.0%.
これらを通して得られるペレットの耐ブロッキング性は、表１に示すように、ブロック化せず流動性は良好であった。また発泡は見られるものの、その泡成長速度は遅く、タンクから泡がオーバーフローするまでは生産が十分可能なものであった。 As shown in Table 1, the blocking resistance of the pellets obtained through these was not blocked and the flowability was good. Although foaming was observed, the foam growth rate was slow, and production was sufficiently possible until the foam overflowed from the tank.
（比較例１）
冷却水タンク４にブロッキング防止剤、メチルセルロースを添加しない、つまり冷却水槽内には水以外は投入しないこと以外は実施例１と同様に実施した。
(Comparative Example 1)
This was carried out in the same manner as in Example 1 except that the antiblocking agent and methylcellulose were not added to the cooling water tank 4, that is, no water other than water was put into the cooling water tank.
これらを通して得られるペレットの耐ブロッキング性は、表１に併せて示すように、互いに強固に付着しており、ほぐすこともできなかった。 As shown in Table 1, the blocking resistance of the pellets obtained through these adhered firmly to each other and could not be loosened.
（比較例２）
冷却水タンク４にメチルセルロースを添加しなかったこと以外は実施例１と同様に実施した。
(Comparative Example 2)
The same operation as in Example 1 was performed except that methylcellulose was not added to the cooling water tank 4.
これらを通して得られるペレットの耐ブロッキング性は、表１に併せて示すように、互いに付着しており、流動性は良好ではなかった。 As shown in Table 1, the blocking resistance of the pellets obtained through these adhered to each other, and the fluidity was not good.
（比較例３）
ブロッキング防止剤（１）を冷却水タンク４に添加し、水槽中の固形分濃度を０．９％とした以外は、実施例１と同様に実施した。
(Comparative Example 3)
This was carried out in the same manner as in Example 1 except that the antiblocking agent (1) was added to the cooling water tank 4 and the solid content concentration in the water tank was set to 0.9%.
これらを通して得られるペレットの耐ブロッキング性は、表１に併せて示すように、互いに付着しており、流動性は良好ではなかった。 As shown in Table 1, the blocking resistance of the pellets obtained through these adhered to each other, and the fluidity was not good.
（比較例４）
ブロッキング防止剤（１）を冷却水タンク４に添加し、水槽中の固形分濃度を１１％とした以外は、実施例１と同様に実施した。
(Comparative Example 4)
It implemented similarly to Example 1 except having added the antiblocking agent (1) to the cooling water tank 4, and having made solid content concentration in a water tank into 11%.
表１に併せて示すように、得られたペレットはブロック化せず流動性は良好であったが、タンク内の発泡が激しく１０分ほどで泡がタンクからオーバーフローして生産ができなかった。 As shown in Table 1, the obtained pellets were not blocked and the fluidity was good, but the foam in the tank was so strong that the foam overflowed from the tank in about 10 minutes, and production was not possible.
（比較例５）
実施例３において、冷却水タンク４には、予め冷却水槽中に、上記製造例２で得られたブロッキング防止剤としてのポリスチレン乳濁液を１．２重量％、凝集剤としての芒硝０．７１重量％（５０ｍｍｏｌ／Ｌ）となるように添加しておき、それに、ブロッキング防止助剤としてのメチルセルロースを冷却水槽内濃度１５ｐｐｍとなるように添加した。
(Comparative Example 5)
In Example 3, the cooling water tank 4 was previously filled with 1.2% by weight of the polystyrene emulsion as an antiblocking agent obtained in Production Example 2 in the cooling water tank, and 0.71 of sodium sulfate as a flocculant. It added so that it might become weight% (50 mmol / L), and the methylcellulose as an antiblocking adjuvant was added to it so that it might become 15 ppm in a cooling water tank concentration.
表１に併せて示すように、得られたペレットはブロック化せず流動性は良好であったが経時的に押出機のダイス（材質はステライト）が腐食し出し、処理を中断せざるをえなかった。 As shown in Table 1, the obtained pellets were not blocked and flowed well, but over time the die of the extruder (the material is stellite) began to corrode and the processing had to be interrupted. There wasn't.
１：押出し機
２：ダイス
３：脱水乾燥機
４：冷却水タンク
５：循環ポンプ
６：熱交換器
1: Extruder 2: Die 3: Dehydration dryer 4: Cooling water tank 5: Circulation pump 6: Heat exchanger
Claims (3)
（１）芳香族ビニル系単量体を主成分とする重合体の水性乳濁液を凍結凝固後、解凍することによって凝固組成物を作製する工程、
（２）固形分濃度が１．０重量％以上１０．０重量％以下である、（１）で得られた凝固組成物、水、及び水溶性高分子の混合物を調製する工程、
（３）スチレン系エラストマー樹脂ペレットに、（２）で得られた混合物を付着させる工程 The manufacturing method of the elastomer resin pellet which consists of the process of following (1)-(3).
(1) A step of producing a coagulated composition by thawing after freezing and coagulating an aqueous emulsion of a polymer mainly composed of an aromatic vinyl monomer,
(2) a step of preparing a mixture of the coagulation composition obtained in (1), water, and a water-soluble polymer, wherein the solid content concentration is 1.0% by weight or more and 10.0% by weight or less;
(3) A step of attaching the mixture obtained in (2) to the styrene-based elastomer resin pellets
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008096392A JP5331366B2 (en) | 2008-04-02 | 2008-04-02 | Method for preventing blocking of styrene elastomer resin pellets |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008096392A JP5331366B2 (en) | 2008-04-02 | 2008-04-02 | Method for preventing blocking of styrene elastomer resin pellets |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009249433A JP2009249433A (en) | 2009-10-29 |
| JP5331366B2 true JP5331366B2 (en) | 2013-10-30 |
Family
ID=41310441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008096392A Expired - Fee Related JP5331366B2 (en) | 2008-04-02 | 2008-04-02 | Method for preventing blocking of styrene elastomer resin pellets |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5331366B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101809394B1 (en) | 2013-12-24 | 2017-12-14 | 아사히 가세이 가부시키가이샤 | Hydrogenated block copolymer pellet, adhesive composition, and surface protective film |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4472044B2 (en) * | 1999-05-17 | 2010-06-02 | 株式会社クラレ | Method for producing polymer aggregate |
| JP2002293946A (en) * | 2001-01-26 | 2002-10-09 | Kanegafuchi Chem Ind Co Ltd | Method for preventing blocking of isobutylene-based block copolymer pellets |
| JPWO2007007837A1 (en) * | 2005-07-14 | 2009-01-29 | 株式会社カネカ | Method for producing resin powder |
-
2008
- 2008-04-02 JP JP2008096392A patent/JP5331366B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101809394B1 (en) | 2013-12-24 | 2017-12-14 | 아사히 가세이 가부시키가이샤 | Hydrogenated block copolymer pellet, adhesive composition, and surface protective film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009249433A (en) | 2009-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5010465B2 (en) | Method for producing coagulated latex particles | |
| CA2550005C (en) | Interpolymer resin particles | |
| EA022941B1 (en) | Process to increase the melt flow index of an expandable vinyl aromatic polymer | |
| JP2009073931A (en) | Method for manufacturing resin granular powder | |
| JP5331366B2 (en) | Method for preventing blocking of styrene elastomer resin pellets | |
| JPWO2006092897A1 (en) | Method for producing coagulated latex particles | |
| NO140272B (en) | PROCEDURE FOR PREVENTING POLYMER CONSTRUCTION IN THE MANUFACTURE OF VINYL CHLORIDE POLYMERS | |
| CN1326914C (en) | Polymer particle composition and process for producing the same | |
| JP2009197049A (en) | Method for preventing blocking of styrene-based elastomer resin pellet | |
| US7728055B2 (en) | Process for producing coagulated latex particles | |
| JP2012526884A (en) | Process for producing a suspension of PVC grafted onto an elastomer | |
| JP7332678B2 (en) | Method for producing (meth)acrylic polymer coagulate and molded article | |
| JP2010195968A (en) | Method for producing styrenic elastomer resin pellets | |
| JP2009263541A (en) | Method of producing pellets of styrene based elastomer resin | |
| JP2009073930A (en) | Blocking prevention method for styrenic elastomer resin pellet | |
| JP2004155880A (en) | Method for producing isobutylene-based thermoplastic elastomer resin | |
| JPWO2006008902A1 (en) | Method for producing polymer | |
| JPH03273014A (en) | Production of modified polyolefin particle | |
| JP2009249432A (en) | Granular product of styrene-based elastomer resin having improved blocking resistance | |
| JP5209925B2 (en) | Method for producing resin powder | |
| JPS5978202A (en) | Production of hydrophilic group-containing vinyl polymer | |
| JPWO2007007837A1 (en) | Method for producing resin powder | |
| JPS6037807B2 (en) | Manufacturing method of terpolymer-polyblend | |
| JP2007023116A (en) | Method for preventing blocking of styrene elastomer resin pellets | |
| JP3400010B2 (en) | Method for separating polymer from latex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110221 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120810 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120911 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121022 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130710 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130729 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5331366 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |