WO2023096220A1 - 디엔계 고무질 중합체의 제조방법 및 이를 포함하는 그래프트 중합체의 제조방법 - Google Patents
디엔계 고무질 중합체의 제조방법 및 이를 포함하는 그래프트 중합체의 제조방법 Download PDFInfo
- Publication number
- WO2023096220A1 WO2023096220A1 PCT/KR2022/017471 KR2022017471W WO2023096220A1 WO 2023096220 A1 WO2023096220 A1 WO 2023096220A1 KR 2022017471 W KR2022017471 W KR 2022017471W WO 2023096220 A1 WO2023096220 A1 WO 2023096220A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymerization
- weight
- diene
- parts
- rubbery polymer
- Prior art date
Links
- 150000001993 dienes Chemical class 0.000 title claims abstract description 125
- 229920001971 elastomer Polymers 0.000 title claims abstract description 113
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- 229920000578 graft copolymer Polymers 0.000 title claims description 52
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 209
- 239000000178 monomer Substances 0.000 claims abstract description 113
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 230000000977 initiatory effect Effects 0.000 claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 150000001412 amines Chemical class 0.000 claims abstract description 25
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 26
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 19
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 3
- 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 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 230000002794 monomerizing effect Effects 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 36
- 239000011342 resin composition Substances 0.000 description 23
- 229920005992 thermoplastic resin Polymers 0.000 description 21
- 239000002245 particle Substances 0.000 description 20
- 239000004816 latex Substances 0.000 description 19
- 229920000126 latex Polymers 0.000 description 19
- -1 ammonium persulfate diene Chemical class 0.000 description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 11
- 229910052700 potassium Inorganic materials 0.000 description 11
- 239000011591 potassium Substances 0.000 description 11
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 10
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 9
- 239000008121 dextrose Substances 0.000 description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 8
- 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 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000033116 oxidation-reduction process Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000012966 redox initiator Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- DKUDOZCGJINMJV-UHFFFAOYSA-N N,N-dimethylacetamide ethane-1,2-diamine Chemical compound C(CN)N.CC(=O)N(C)C DKUDOZCGJINMJV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 229940096992 potassium oleate Drugs 0.000 description 3
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000002897 diene group Chemical group 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- QZLAEIZEPJAELS-UHFFFAOYSA-N 2,4,4-trimethylpentane-2-thiol Chemical compound CC(C)(C)CC(C)(C)S QZLAEIZEPJAELS-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- RLFXJQPKMZNLMP-UHFFFAOYSA-N 2-phenylprop-2-enenitrile Chemical compound N#CC(=C)C1=CC=CC=C1 RLFXJQPKMZNLMP-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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- JBDFNORUNVZONM-UHFFFAOYSA-N 4-octoxy-4-oxo-3-sulfobutanoic acid Chemical compound CCCCCCCCOC(=O)C(S(O)(=O)=O)CC(O)=O JBDFNORUNVZONM-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-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
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-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
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-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
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 229940096818 dipentamethylenethiuram disulfide Drugs 0.000 description 1
- RZMWTGFSAMRLQH-UHFFFAOYSA-L disodium;2,2-dihexyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCC RZMWTGFSAMRLQH-UHFFFAOYSA-L 0.000 description 1
- VVSMKOFFCAJOSC-UHFFFAOYSA-L disodium;dodecylbenzene;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1 VVSMKOFFCAJOSC-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910000358 iron 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
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- KNBRWWCHBRQLNY-UHFFFAOYSA-N piperidine-1-carbothioylsulfanyl piperidine-1-carbodithioate Chemical compound C1CCCCN1C(=S)SSC(=S)N1CCCCC1 KNBRWWCHBRQLNY-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- PFMVLFSAAABWQD-UHFFFAOYSA-M potassium;octadecyl sulfate Chemical compound [K+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O PFMVLFSAAABWQD-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical group CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 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
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- UELAIMNOXLAYRW-UHFFFAOYSA-M sodium;1,4-dicyclohexyloxy-1,4-dioxobutane-2-sulfonate Chemical group [Na+].C1CCCCC1OC(=O)C(S(=O)(=O)[O-])CC(=O)OC1CCCCC1 UELAIMNOXLAYRW-UHFFFAOYSA-M 0.000 description 1
- AXBSROISAJEZHL-UHFFFAOYSA-M sodium;4-(3-ethyloctan-3-yloxy)-4-oxo-3-sulfobutanoate Chemical compound [Na+].CCCCCC(CC)(CC)OC(=O)C(S(O)(=O)=O)CC([O-])=O AXBSROISAJEZHL-UHFFFAOYSA-M 0.000 description 1
- MWZFQMUXPSUDJQ-KVVVOXFISA-M sodium;[(z)-octadec-9-enyl] sulfate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCCOS([O-])(=O)=O MWZFQMUXPSUDJQ-KVVVOXFISA-M 0.000 description 1
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 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
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
Definitions
- the present invention relates to a method for producing a diene-based rubbery polymer and a method for producing a graft polymer comprising the same, and in particular, the synergy between a diamine-based compound and a thermal decomposition initiator significantly lowers the polymerization initiation temperature and has excellent polymerization stability , A method for producing a diene-based rubbery polymer having excellent impact resistance and a method for producing a graft polymer including the same.
- a redox initiation system is most widely used as a polymerization initiation system.
- the redox initiation system has the advantage of being able to control the polymerization in a relatively short time because the polymerization initiation temperature is low and the polymerization rate is high.
- the redox initiation system may reduce polymerization stability during production of the diene-based rubbery polymer, and depending on the amount of the diene-based rubbery polymer used, an excessive amount of the diene-based rubbery polymer may be produced.
- a thermal decomposition initiator such as potassium persulfate
- the polymerization initiation and execution temperature is high, the polymerization rate is slow, and the polymerization stability is due to the high reaction pressure due to the high polymerization initiation and execution temperature. It is highly likely that this will deteriorate.
- processability and impact resistance of the graft polymer are deteriorated due to a decrease in rubber efficiency due to an increase in the crosslinking rate of the rubbery polymer.
- the problem to be solved by the present invention is to provide a method for preparing a diene-based rubbery polymer having a low polymerization initiation temperature, excellent polymerization stability, and excellent impact resistance even when a thermal decomposition initiator is used, and a method for preparing a graft polymer including the same.
- the present invention includes the steps of initiating and carrying out polymerization of monomers in the presence of an amine-based compound and a thermal decomposition initiator, wherein the amine-based compound is a compound represented by the following formula (1) and At least one selected from the group consisting of compounds represented by Formula 2 below, and the content of the amine-based compound is 0.03 to 0.70 parts by weight, based on 100 parts by weight of the total amount of monomers added during the production of the diene-based rubbery polymer.
- the monomer is a diene-based monomer; or a diene-based monomer and a vinyl aromatic-based monomer; and the polymerization is initiated at 25 to 50 ° C. to provide a method for producing a diene-based rubbery polymer:
- R 1 to R 4 are each independently hydrogen or a C 1 to C 10 alkyl group
- L is a C 1 to C 10 alkylene group.
- R 5 to R 7 are each independently hydrogen or a C 1 to C 5 alkyl group, but at least two of R 5 to R 7 are C 1 to C 5 alkyl groups.
- the compound represented by Formula 1 is at least one diene selected from the group consisting of N,N,N',N'-tetramethylethylenediamine and ethylenediamine It provides a method for producing a rubber-based polymer.
- the present invention provides a method for producing a diene-based rubbery polymer according to (1) or (2) above, wherein the compound represented by Formula 2 is dimethylamine.
- thermo decomposition initiator is at least one selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate diene system
- the thermal decomposition initiator is at least one selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate diene system
- the present invention also provides a method for producing a diene-based rubbery polymer according to any one of (1) to (4) above, wherein the polymerization is initiated at 25 to 35°C.
- the content of the thermal decomposition initiator is 0.01 part by weight based on 100 parts by weight of the total amount of monomers added during the production of the diene-based rubbery polymer. to 3.00 parts by weight of a diene-based rubbery polymer.
- the step of initiating and carrying out the polymerization of the monomers initiates the polymerization of the monomers in the presence of the amine-based compound and the thermal decomposition initiator doing; and adding the monomers at a polymerization conversion rate of 10 to 50% and polymerizing the diene-based rubbery polymer.
- the amount of the monomers added in the step of initiating the polymerization of the monomers is 100 parts by weight of the total amount of monomers added during the production of the diene-based rubbery polymer. 50 to 90 parts by weight, and the content of the monomers added in the polymerization step is 10 to 50 parts by weight based on 100 parts by weight of the total amount of monomers added during the production of the diene-based rubbery polymer.
- a method for producing a phosphorus diene-based rubbery polymer is provided.
- the present invention also provides a method for producing a diene-based rubbery polymer according to any one of (1) to (8) above, wherein the polymerization is emulsion polymerization.
- the present invention comprises the steps of preparing a diene-based rubber polymer by the manufacturing method according to any one of the above (1) to (9); and polymerizing a vinyl aromatic monomer and a vinyl cyanide monomer to the diene-based rubbery polymer.
- polymerization can be initiated and carried out at a relatively low temperature even when a thermal decomposition initiator is used, and the production efficiency can be significantly improved due to excellent polymerization stability.
- a graft polymer having excellent impact resistance can be produced.
- the 'polymerization conversion rate' indicates the degree to which monomers polymerize to form a polymer, and can be calculated by the following formula.
- Polymerization conversion rate (%) ⁇ (total weight of monomers added until polymerization was completed) - (total weight of unpolymerized monomers at the time of measuring polymerization conversion) ⁇ /(total weight of monomers added until polymerization was completed) weight) ⁇ 100
- the 'average particle diameter' may mean the arithmetic mean particle diameter in the particle size distribution measured by dynamic light scattering, specifically, the scattering intensity average particle diameter.
- the average particle diameter can be measured using Nicomp 370HPL equipment (product name, manufacturer: PSS Nicomp).
- the 'gel content' can be calculated after preparing a piece by coagulating, washing, and drying the diene-based rubbery polymer latex, and then separating the piece into a sol and a gel.
- the diene-based rubbery polymer latex may be solidified with a dilute aqueous solution of sulfuric acid and then washed.
- the washed material is primarily dried in a vacuum oven at 60° C. for 24 hours, and then cut into pieces with scissors to prepare slices. 1 g of this slice was put in 100 g of toluene, stored in a dark room at 23 ° C for 48 hours, separated into sol and gel, and the gel was secondarily dried in an oven at 85 ° C for 6 hours. (Weight) can be obtained and incorporated into the formula below to calculate the gel content.
- the 'diene-based monomer' may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene, among which 1,3-butadiene is preferred.
- the 'vinyl aromatic monomer' may be at least one selected from the group consisting of styrene, ⁇ -methyl styrene, ⁇ -ethyl styrene, and p-methyl styrene, of which styrene is preferred.
- the 'vinyl cyanide-based monomer' may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenyl acrylonitrile, and ⁇ -chloro acrylonitrile, of which acrylonitrile is preferred. do.
- the 'molecular weight regulator' is ⁇ -methyl styrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, t-octyl mercaptan, n-octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethyl It may be at least one selected from the group consisting of thiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylxantogen disulfide. Among these, t-dodecyl mercaptan is preferred.
- the 'peroxide-based initiator' may be at least one selected from the group consisting of cumene hydroperoxide, diisopropyl benzene hydroperoxide, t-butyl hydroperoxide, paramenthane hydroperoxide and benzoyl peroxide there is.
- the 'azo-based initiator' may be azobisisobutyronitrile.
- the 'emulsifier' is sodium dicyclohexyl sulfosuccinate, sodium dihexyl sulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, potassium di-2-ethylhexyl sulfosuccinate, sodium di-ethylhexyl sulfosuccinate, It may be at least one selected from the group consisting of octyl sulfosuccinate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleyl sulfate, potassium octadecyl sulfate, potassium loginate and sodium loginate, , of which sodium dodecyl benzene sulfonate is preferred.
- 'electrolyte' means KCl, NaCl, KOH, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7 , Na 4 P 2 O 7 , K It may be at least one selected from the group consisting of 3 PO 4 , Na 3 PO 4 , K 2 HPO 4 and Na 2 HPO 4 , among which at least one selected from the group consisting of KOH and K 2 CO 3 is preferred. .
- the 'oxidation-reduction catalyst' is selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, iron (II) sulfate, dextrose, tetrasodium pyrophosphate, anhydrous sodium pyrophosphate and sodium sulfate. It may be at least one selected from the group consisting of iron (II) sulfate, dextrose, and tetrasodium pyrophosphate.
- the 'aqueous solvent' may be ion-exchanged water or distilled water.
- 'alkyl group' is methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group,
- the 'alkylene group' may mean that the alkyl group has two bonding sites, that is, a divalent group.
- a method for producing a diene-based rubbery polymer includes the steps of initiating and conducting polymerization of monomers in the presence of an amine-based compound and a thermal decomposition initiator, wherein the amine-based compound is represented by Formula 1 below: compound and at least one selected from the group consisting of a compound represented by Formula 2, and the content of the amine-based compound is 0.03 to 0.70, based on 100 parts by weight of the total amount of monomers added during the preparation of the diene-based rubber polymer parts by weight, and the monomer is a diene-based monomer; or a diene-based monomer and a vinyl aromatic-based monomer; wherein the polymerization is initiated at 25 to 50° C.:
- R 1 to R 4 are each independently hydrogen or a C 1 to C 10 alkyl group
- L is a C 1 to C 10 alkylene group.
- R 5 to R 7 are each independently hydrogen or a C 1 to C 5 alkyl group, but at least two of R 5 to R 7 are C 1 to C 5 alkyl groups.
- polymerization When polymerization is initiated in the presence of an amine-based compound and a thermal decomposition initiator in the method for producing a diene-based rubbery polymer, polymerization can be initiated and carried out at a relatively low temperature even when a thermal decomposition initiator is used due to synergy between the amine-based compound and the thermal decomposition initiator.
- the polymerization stability is excellent, the production efficiency is remarkably improved, and the graft polymer having excellent impact resistance can be prepared.
- R 1 to R 4 are each independently hydrogen or a C 1 to C 4 alkyl group, and L may be a C 1 to C 4 alkylene group.
- the compound represented by Formula 1 may be at least one selected from the group consisting of N,N,N',N'-tetramethylethylenediamine and ethylenediamine.
- R 5 to R 7 are each independently hydrogen or a C 1 to C 5 alkyl group, but at least two of R 5 to R 7 are C 1 to C 5 alkyl groups, and R 5 to R 7 are Each independently hydrogen or a C 1 to C 4 alkyl group, but at least one of R 5 to R 7 is preferably hydrogen. If an alkyl group exceeding C 5 is introduced, since the molecular weight of the compound increases, the amount of N compared to the input amount of the compound decreases and the effect is remarkably lowered.
- the compound represented by Formula 2 may be dimethylamine.
- the amount of the amine-based compound may be 0.03 to 0.70 parts by weight, preferably 0.10 to 0.50 parts by weight, based on 100 parts by weight of the total amount of monomers added during the production of the diene-based rubbery polymer.
- the content of the amine-based compound is smaller than the above conditions, polymerization is not initiated at 25 to 50°C. If the content of the amine-based compound is excessive than the above conditions, the polymerization stability is lowered, and the coagulum is excessively generated, which lowers the production efficiency.
- the thermal decomposition initiator does not require the use of a metal oxide and a reducing agent together, thermal stability and whiteness of the graft polymer can be prevented from deterioration.
- the thermal decomposition initiator may be at least one selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate, and potassium sulfate is preferred from the viewpoint of price and polymerization stability.
- the amount of the thermal decomposition initiator may be 0.01 to 3.00 parts by weight, preferably 0.10 to 0.80 parts by weight, based on 100 parts by weight of the total amount of monomers added during the preparation of the diene-based rubbery polymer. If the above conditions are satisfied, the polymerization rate and polymerization stability can be balanced.
- the polymerization In the presence of the amine-based compound and the thermal decomposition initiator, polymerization of monomers is initiated, and therefore, the polymerization may be initiated at 25 to 50°C, preferably at 25 to 35°C. If the above conditions are satisfied, the energy required to raise the temperature of the reactor can be saved, and the polymerization efficiency can be improved. In addition, since the amount of coagulation is reduced during the preparation of the diene-based rubbery polymer and the final polymerization conversion rate is increased, polymerization stability and polymerization efficiency can be improved. Polymerization is not initiated below the above-mentioned temperature.
- the polymerization may be emulsion polymerization, and may be performed in the presence of at least one selected from the group consisting of an emulsifier, an electrolyte, a molecular weight modifier, and an aqueous solvent, as well as the amine-based compound and the thermal decomposition initiator.
- the type of the emulsifier is as described above, and the content of the emulsifier is 0.5 to 5.0 parts by weight, preferably 0.8 to 2.5 parts by weight, based on 100 parts by weight of the total amount of monomers added during the production of the diene-based rubbery polymer.
- the content of the emulsifier is 0.5 to 5.0 parts by weight, preferably 0.8 to 2.5 parts by weight, based on 100 parts by weight of the total amount of monomers added during the production of the diene-based rubbery polymer.
- the type of the electrolyte is as described above, and the amount of the electrolyte is 0.3 to 3.0 parts by weight, preferably 0.5 to 1.5 parts by weight, based on 100 parts by weight of the total amount of monomers added during the production of the diene-based rubbery polymer. can When the above conditions are satisfied, polymerization stability can be improved.
- the type of the molecular weight modifier is as described above, and the amount of the molecular weight modifier is 0.1 to 1.0 parts by weight, preferably 0.2 to 0.5 parts by weight, based on 100 parts by weight of the total amount of monomers added during the production of the diene-based rubbery polymer. It may be part by weight. If the above conditions are satisfied, the production time of the diene-based rubbery polymer can be shortened.
- the step of initiating and performing polymerization of the monomers may include initiating polymerization of the monomers in the presence of the amine-based compound and a thermal decomposition initiator; and adding the monomers at a polymerization conversion rate of 10 to 50% and performing polymerization.
- the monomer When the monomer is added at a polymerization conversion rate of 10 to 50%, preferably at a polymerization conversion rate of 20 to 40%, the polymerization pressure and polymerization temperature do not rise rapidly and the polymerization stability is improved to achieve the desired average A diene-based rubbery polymer having a particle size can be produced.
- the content of the monomers added in the step of initiating the polymerization of the monomers is 50 to 90 parts by weight, preferably 60 to 80 parts by weight, based on 100 parts by weight of the total amount of monomers added in the production of the diene-based rubbery polymer. It may be part by weight.
- the content of the monomers added in the polymerization step is 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the total amount of monomers added during the production of the diene-based rubbery polymer.
- Initiating and performing polymerization of the monomers may include initiating polymerization of the monomers in the presence of the amine-based compound and a thermal decomposition initiator; and polymerizing while continuously introducing the monomers from a polymerization conversion rate of 10 to 30% to a polymerization conversion rate of 40 to 70%.
- the polymerization conversion rate is 10 to 30% to the polymerization conversion rate is 40 to 70%, preferably from the polymerization conversion rate of 10 to 20% to the polymerization conversion rate is 50 to 70%.
- the generation of coagulum can be minimized, and thus the manufacturing efficiency can be improved.
- graft polymerization may proceed smoothly during the preparation of the graft polymer.
- the content of the monomers added in the step of initiating the polymerization of the monomers is 50 to 90 parts by weight, preferably 60 to 80 parts by weight, based on 100 parts by weight of the total amount of monomers added in the production of the diene-based rubbery polymer. It may be part by weight.
- the content of the monomers continuously added in the polymerization step is 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the total amount of monomers added during the production of the diene-based rubbery polymer. can be wealth When the above conditions are satisfied, polymerization stability can be improved.
- the diene-based rubbery polymer may have an average particle diameter of 50 to 500 nm, a gel content of 60 to 85% by weight, preferably an average particle diameter of 100 to 400 nm, and a gel content of 65 to 80% by weight. . If the above conditions are satisfied, a graft polymer with remarkably improved impact resistance can be prepared.
- a method for preparing a graft polymer according to another embodiment of the present invention includes preparing a diene-based rubbery polymer by the method according to an embodiment of the present invention; and polymerizing a vinyl aromatic monomer and a vinyl cyanide monomer to the diene-based rubbery polymer.
- the diene-based rubbery polymer may be in the form of latex dispersed in water in a colloidal state.
- the content of the diene-based rubbery polymer may be 45 to 75 parts by weight, preferably 50 to 70 parts by weight, based on 100 parts by weight of the total content of the diene-based rubbery polymer, the vinyl aromatic monomer, and the vinyl cyanide-based monomer. . If the above range is satisfied, the impact resistance and processability of the graft polymer may be further improved.
- the content of the vinyl aromatic monomer may be 15 to 45 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the total content of the diene-based rubbery polymer, the vinyl aromatic monomer, and the vinyl cyanide-based monomer. . If the above range is satisfied, chemical resistance, stiffness, impact resistance, processability and surface gloss of the graft polymer may be further improved.
- the content of the vinyl cyanide-based monomer may be 1 to 20 parts by weight, preferably 3 to 17 parts by weight, based on 100 parts by weight of the total content of the diene-based rubbery polymer, the vinyl aromatic monomer, and the vinyl cyanide-based monomer. there is. When the above range is satisfied, chemical resistance, stiffness, impact resistance, processability and surface gloss of the thermoplastic resin composition may be further improved.
- the polymerization may be performed in the presence of at least one selected from the group consisting of an emulsifier, an initiator, an oxidation-reduction catalyst, a molecular weight regulator, and ion exchange water.
- the amount of the emulsifier may be 0.01 to 2.00 parts by weight or 0.10 to 0.60 parts by weight, of which 0.10 to 1.50 parts by weight, based on 100 parts by weight of the total content of the diene-based rubbery polymer, the vinyl aromatic monomer, and the vinyl cyanide-based monomer. Part by weight is preferred.
- emulsion polymerization is easily performed, polymerization stability and latex stability are improved, and the residual amount in the graft polymer can be minimized.
- the amount of the initiator may be 0.010 to 1.000 parts by weight or 0.100 to 0.500 parts by weight, of which 0.100 to 0.500 parts by weight, based on 100 parts by weight of the total sum of the contents of the diene-based rubbery polymer, the vinyl aromatic monomer, and the vinyl cyanide-based monomer. Part by weight is preferred.
- emulsion polymerization can be easily performed and the residual amount in the graft polymer can be minimized.
- the amount of the oxidation-reduction catalyst may be 0.0100 to 0.5000 parts by weight or 0.0500 to 0.4000 parts by weight based on 100 parts by weight of the total content of the diene-based rubbery polymer, the vinyl aromatic monomer, and the vinyl cyanide-based monomer. It is preferable that it is 0.0500 to 0.4000 weight part of. If the above range is satisfied, the polymerization conversion rate can be further increased.
- the amount of the molecular weight modifier may be added in an amount of 0.01 to 1.00 parts by weight or 0.05 to 0.50 parts by weight based on 100 parts by weight of the total sum of the contents of the diene-based rubbery polymer, the vinyl aromatic monomer, and the vinyl cyanide-based monomer. It is preferably added in an amount of 0.05 to 0.50 parts by weight. If the above range is satisfied, the weight average molecular weight of the shell can be appropriately adjusted.
- thermoplastic resin composition according to another embodiment of the present invention includes a graft polymer prepared according to another embodiment of the present invention and a non-grafted polymer including a vinyl aromatic monomer unit and a vinyl cyanide monomer unit.
- the non-grafted polymer may impart heat resistance, rigidity, and processability to the thermoplastic resin composition.
- the non-grafted polymer may include the vinyl aromatic monomer unit and the vinyl cyanide monomer unit in a weight ratio of 85:15 to 60:40, preferably 80:20 to 65:35.
- the thermoplastic resin composition can better implement a balance of heat resistance, impact resistance and workability.
- the weight ratio of the graft polymer and the non-grafted polymer may be 15:85 to 35:65, preferably 20:80 to 30:70.
- chemical resistance, impact resistance, thermal stability, colorability, fatigue resistance, stiffness and processability of a molded article made of the thermoplastic resin composition may be further improved.
- a nitrogen-purged reactor 55 parts by weight of ion-exchanged water, 70 parts by weight of 1,3-butadiene, 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine, 0.30 parts by weight of potassium persulfate, and 1.0 parts by weight of potassium rosinate Parts by weight, 1.0 parts by weight of potassium oleate, 1.5 parts by weight of potassium carbonate, and 0.5 parts by weight of t-dodecyl mercaptan were added. Then, the temperature of the reactor was raised to 25° C., and the pressure of the reactor was set to 5 kg/cm 2 , and then polymerization was initiated.
- Polymerization was carried out while raising the temperature of the reactor at a constant rate to 35 ° C. at the same time as the polymerization was started.
- the polymerization conversion rate was 20%, 30 parts by weight of 1,3-butadiene and 0.2 parts by weight of potassium loginate were added, followed by polymerization.
- the temperature of the reactor was raised to 50° C., polymerization was performed for 10 hours, and polymerization was terminated to prepare a diene-based rubbery polymer latex.
- a monomer mixture comprising 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 0.05 parts by weight of t-butyl hydroperoxide, 0.5 parts by weight of potassium loginate and 0.5 parts by weight of t-dodecyl mercaptan manufactured.
- an activator mixture containing 0.0100 parts by weight of dextrose, 0.0100 parts by weight of tetrasodium pyrophosphate, and 0.0010 parts by weight of iron (II) sulfate was prepared.
- the graft polymer latex was coagulated, matured, washed, dehydrated and dried to prepare a graft polymer powder.
- thermoplastic resin composition ⁇ Preparation of thermoplastic resin composition>
- thermoplastic resin composition was prepared by mixing 27.5 parts by weight of the graft polymer powder and 72.5 parts by weight of a vinyl-based non-grafted polymer (styrene/acrylonitrile polymer, 92 HR of LG Chem).
- Example 1 except that 0.30 parts by weight of N,N,N',N'-tetramethylethylenediamine was added instead of 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine.
- a diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner.
- Example 1 except that 0.70 parts by weight of N,N,N',N'-tetramethylethylenediamine was added instead of 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine.
- a diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner.
- Example 1 the diene-based rubbery polymer, the graft polymer and the thermoplastic were prepared in the same manner as in Example 1, except that 0.30 part by weight of ethylenediamine was added instead of 0.03 part by weight of N,N,N',N'-tetramethylethylenediamine. A resin composition was prepared.
- Example 1 the diene-based rubbery polymer, the graft polymer and the thermoplastic were prepared in the same manner as in Example 1, except that 0.30 part by weight of dimethylamine was added instead of 0.03 part by weight of N,N,N',N'-tetramethylethylenediamine. A resin composition was prepared.
- a nitrogen-purged reactor 55 parts by weight of ion-exchanged water, 70 parts by weight of 1,3-butadiene, 0.3 parts by weight of potassium persulfate, 1.0 parts by weight of potassium loginate, 1.0 parts by weight of potassium oleate, 1.5 parts by weight of potassium carbonate, t- 0.5 parts by weight of dodecyl mercaptan was added. Then, the temperature of the reactor was raised to 70 °C, and the pressure of the reactor was set to 8 kg/cm 2 , and then polymerization was initiated. Polymerization was performed while raising the temperature of the reactor at a constant rate to 80 ° C. at the same time as the polymerization was initiated.
- a monomer mixture comprising 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 0.05 parts by weight of t-butyl hydroperoxide, 0.5 parts by weight of potassium loginate and 0.5 parts by weight of t-dodecyl mercaptan manufactured.
- an activator mixture containing 0.0100 parts by weight of dextrose, 0.0100 parts by weight of tetrasodium pyrophosphate, and 0.0010 parts by weight of iron (II) sulfate was prepared.
- the graft polymer latex was coagulated, matured, washed, dehydrated and dried to prepare a graft polymer powder.
- thermoplastic resin composition ⁇ Preparation of thermoplastic resin composition>
- thermoplastic resin composition was prepared by mixing 27.5 parts by weight of the graft polymer powder and 72.5 parts by weight of a vinyl-based non-grafted polymer (styrene/acrylonitrile polymer, 92 HR of LG Chem).
- the temperature of the reactor was raised to 70 °C, and the pressure of the reactor was set to 8 kg/cm 2 , and then polymerization was initiated. Polymerization was performed while raising the temperature of the reactor at a constant rate to 80 ° C. at the same time as the polymerization was initiated.
- the polymerization conversion rate was 20%, 30 parts by weight of 1,3-butadiene and 0.2 parts by weight of potassium loginate were added, followed by polymerization.
- the temperature of the reactor was raised to 85° C., polymerization was performed for 10 hours, and polymerization was terminated to prepare a diene-based rubbery polymer latex.
- a monomer mixture comprising 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 0.05 parts by weight of t-butyl hydroperoxide, 0.5 parts by weight of potassium loginate and 0.5 parts by weight of t-dodecyl mercaptan manufactured.
- an activator mixture containing 0.0100 parts by weight of dextrose, 0.0100 parts by weight of tetrasodium pyrophosphate, and 0.0010 parts by weight of iron (II) sulfate was prepared.
- the graft polymer latex was coagulated, matured, washed, dehydrated and dried to prepare a graft polymer powder.
- thermoplastic resin composition ⁇ Preparation of thermoplastic resin composition>
- thermoplastic resin composition was prepared by mixing 27.5 parts by weight of the graft polymer powder and 72.5 parts by weight of a vinyl-based non-grafted polymer (styrene/acrylonitrile polymer, 92 HR of LG Chem).
- Example 1 In Example 1, except that 0.02 parts by weight of N,N,N',N'-tetramethylethylenediamine was added instead of 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine. An attempt was made to produce a diene-based rubbery polymer in the same manner, but polymerization was not initiated and carried out. In order to initiate polymerization, the temperature of the reactor was raised to 50 °C, but polymerization was not initiated.
- Example 1 except that 0.71 parts by weight of N,N,N',N'-tetramethylethylenediamine was added instead of 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine.
- a diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner.
- Example 1 except that 0.80 parts by weight of N,N,N',N'-tetramethylethylenediamine was added instead of 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine.
- a diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner.
- Example 1 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine was not added before the polymerization was started, except that it was added 3 hours after the temperature of the reactor was raised to 25 ° C. Then, a diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner as in Example 1. Polymerization was initiated from the time when N,N,N',N'-tetramethylethylenediamine was added.
- Example 1 a diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that azobisisobutyronitrile (ABIN) was added instead of potassium persulfate, but at 25 ° C. Polymerization was not initiated. In order to initiate polymerization, the temperature of the reactor was raised to 50 °C, but polymerization was not initiated.
- ABIN azobisisobutyronitrile
- Example 1 a diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that t-butyl hydroperoxide was added instead of potassium persulfate, but an oxidation-reduction catalyst Polymerization was not initiated at 25 °C because no was added. In order to initiate polymerization, the temperature of the reactor was raised to 50 °C, but polymerization was not initiated.
- Example 1 the diene-based rubbery polymer, the graft polymer and the An attempt was made to prepare a thermoplastic resin composition, but polymerization was not initiated at 25°C. In order to initiate polymerization, the temperature of the reactor was raised to 50° C., but polymerization was not initiated.
- the maximum polymerization pressure (kg/cm 2 ) applied to the reactor was measured, and the results are shown in Tables 1 to 3 below.
- the polymerization maximum pressure means when the internal pressure of the reactor during polymerization is the highest.
- Average particle diameter (nm) Measured with Nicomp 380 equipment from Particle Sizing Systems Co., using a dynamic light scattering method.
- Coagulated matter (% by weight): After filtering the diene-based rubbery polymer latex through a 100 mesh wire mesh, the reaction product that did not pass through the wire mesh was dried in a hot air dryer at 100 ° C. for 1 hour, and the weight of the coagulated material was measured. , It was calculated by substituting into the following formula.
- Pellets were prepared by extruding the thermoplastic resin compositions of Examples and Comparative Examples, and specimens were prepared by extruding the pellets. The physical properties of this specimen were measured by the method described below, and the results are shown in Tables 1 to 3 below.
- Example 4 in which polymerization of diene-based monomers was initiated in the presence of ethylenediamine and potassium persulfate, the polymerization initiation temperature was 25°C.
- Example 4 had excellent polymerization stability, so less coagulum was generated, the average particle diameter of the diene-based rubbery polymer was appropriate, and the impact resistance of the specimen was excellent.
- Example 5 in which polymerization of diene-based monomers was initiated in the presence of dimethylamine and potassium persulfate, the polymerization initiation temperature was 25°C.
- Example 5 had excellent polymerization stability, less coagulum was generated, the average particle diameter of the diene-based rubbery polymer was appropriate, and the impact resistance of the specimen was excellent.
- Comparative Example 1 in which polymerization of diene-based monomers was initiated in the presence of potassium persulfate without the presence of an amine-based compound had a polymerization initiation temperature of 70°C. Comparative Example 1 had high polymerization initiation and performance temperatures, so the maximum polymerization pressure was high, and the polymerization stability was lowered compared to Examples 2, 4, and 5 in which potassium persulfate was added at the same content, so that the coagulum occurred in excess. In addition, the average particle diameter of the diene-based rubbery polymer was equivalent to Example 2, Example 4, and Example 5, but the impact resistance of the specimen was remarkably reduced.
- Comparative Example 2 in which polymerization of diene-based monomers was initiated in the presence of t-butyl hydroperoxide and an oxidation-reduction catalyst without the presence of an amine-based compound, the polymerization initiation temperature was 70°C. Comparative Example 2 had high polymerization initiation and high temperatures, so the maximum polymerization pressure was also high. Also, in Comparative Example 2, polymerization stability was lowered compared to Examples 1 to 5, resulting in an excessive amount of coagulum. In addition, the average particle diameter of the diene-based rubbery polymer was smaller than that of Examples 1 to 5, and the impact strength of the specimen was not excellent.
- Comparative Example 4 in which polymerization of diene-based monomers was initiated in the presence of 0.71 parts by weight of N,N,N',N'-tetramethylethylenediamine and potassium persulfate, the polymerization initiation temperature was 25 °C. However, in Comparative Example 4, polymerization stability was lowered compared to Examples 1 to 5, resulting in an excessive amount of coagulum. In Comparative Example 4, the average particle diameter of the diene-based rubbery polymer was smaller than that of Examples 1 to 5, and the impact resistance of the specimen was not excellent.
- Comparative Example 5 in which polymerization of diene-based monomers was initiated in the presence of 0.80 parts by weight of N,N,N',N'-tetramethylethylenediamine and potassium persulfate, the polymerization initiation temperature was 25 °C. However, in Comparative Example 5, polymerization stability was lowered compared to Examples 1 to 5, resulting in an excessive amount of coagulum. In addition, the average particle diameter of the diene-based rubbery polymer was equivalent to Examples 1 to 5, but the impact resistance of the specimen was not excellent.
- Comparative Example 7 Comparative Example 8, and Comparative Example 9 the temperature of the reactor was raised to 50 °C to initiate polymerization, but polymerization was not initiated in all of them.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
구분 | 실시예 1 | 실시예 2 | 실시예 3 | 실시예 4 | 실시예 5 | ||
디엔계 고무질 중합체의 제조 | 아민계 화합물 | 종류 | TMEDA | TMEDA | TMEDA | EDA | DMA |
함량(중량부) | 0.03 | 0.30 | 0.70 | 0.30 | 0.30 | ||
투입시점(중합전환율, %) | 0 | 0 | 0 | 0 | 0 | ||
개시제 | 종류 | KPS | KPS | KPS | KPS | KPS | |
함량(중량부) | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | ||
중합 개시 온도(℃) | 25 | 25 | 25 | 25 | 25 | ||
중합 온도(℃) | 35 | 35 | 35 | 35 | 35 | ||
중합 최대 압력 | 8.4 | 8.4 | 8.5 | 8.5 | 8.4 | ||
디엔계 고무질 중합체 | 평균 입경(㎚) | 310 | 310 | 310 | 310 | 310 | |
겔 함량(중량%) | 69 | 68 | 71 | 70 | 69 | ||
응고물(중량%) | 0.007 | 0.008 | 0.011 | 0.008 | 0.009 | ||
시편 | 충격강도(㎏·㎝/㎝) | 34.5 | 34.1 | 34.3 | 34.1 | 34.1 | |
TMEDA: N,N,N’,N’-테트라메틸에틸렌디아민 EDA: 에틸렌디아민 DMA: 디메틸아민 KPS: 포타슘 퍼설페이트 |
구분 | 비교예 1 | 비교예 2 | 비교예 3 | 비교예 4 | 비교예 5 | ||
디엔계 고무질 중합체의 제조 | 아민계 화합물 | 종류 | - | - | TMEDA | TMEDA | TMEDA |
함량(중량부) | 0 | 0 | 0.02 | 0.71 | 0.80 | ||
투입시점(중합전환율, %) | - | - | 0 | 0 | 0 | ||
개시제 | 종류 | KPS | t-BHP | KPS | KPS | KPS | |
함량(중량부) | 0.30 | 0.50 | 0.30 | 0.30 | 0.30 | ||
중합 개시 온도(℃) | 70 | 70 | 중합 × | 25 | 25 | ||
중합 온도(℃) | 80 | 80 | 중합 × | 35 | 35 | ||
중합 최대 압력 | 13.5 | 9.0 | 중합 × | 8.5 | 8.5 | ||
디엔계 고무질 중합체 | 평균 입경(㎚) | 310 | 280 | 중합 × | 295 | 310 | |
겔 함량(중량%) | 85 | 67 | 중합 × | 66 | 66 | ||
응고물(중량%) | 0.012 | 0.080 | - | 0.100 | 0.120 | ||
시편 | 충격강도(㎏·㎝/㎝) | 29.1 | 29.5 | - | 32.4 | 33.1 | |
TMEDA: N,N,N’,N’-테트라메틸에틸렌디아민 EDA: 에틸렌디아민 DMA: 디메틸아민 KPS: 포타슘 퍼설페이트 t-BHP: t-부틸 히드로퍼옥사이드 |
구분 | 비교예 6 | 비교예 7 | 비교예 8 | 비교예 9 | ||
디엔계 고무질 중합체의 제조 | 아민계 화합물 | 종류 | TMEDA | TMEDA | TMEDA | TEA |
함량(중량부) | 0.30 | 0.30 | 0.30 | 0.30 | ||
투입시점(중합전환율, %) | 반응기의 온도를 25 ℃로 승온한 후, 3 시간이 경과된 시점 | 0 | 0 | 0 | ||
개시제 | 종류 | KPS | AIBN | t-BHP | KPS | |
함량(중량부) | 0.30 | 0.30 | 0.05 | 0.30 | ||
중합 개시 온도(℃) | 25 | 중합 × | 중합 × | 중합 × | ||
중합 온도(℃) | 35 | 중합 × | 중합 × | 중합 × | ||
중합 최대 압력 | 10.4 | 중합 × | 중합 × | 중합 × | ||
디엔계 고무질 중합체 | 평균 입경(㎚) | 212 | 중합 × | 중합 × | 중합 × | |
겔 함량(중량%) | 75 | 중합 × | 중합 × | 중합 × | ||
응고물(중량%) | 0.500 | - | - | - | ||
시편 | 충격강도(㎏·㎝/㎝) | - | - | - | - | |
TMEDA: N,N,N’,N’-테트라메틸에틸렌디아민 EDA: 에틸렌디아민 DMA: 디메틸아민 KPS: 포타슘 퍼설페이트 ABIN: 아조비시소부티로니트릴 t-BHP: t-부틸 히드로퍼옥사이드 |
Claims (10)
- 아민계 화합물 및 열분해 개시제의 존재 하에, 단량체의 중합을 개시 및 수행하는 단계를 포함하고,상기 아민계 화합물은 하기 화학식 1로 표시되는 화합물 및 하기 화학식 2로 표시되는 화합물로 이루어진 군에서 선택되는 1 종 이상이고,상기 아민계 화합물의 함량은 디엔계 고무질 중합체의 제조 시 투입되는 단량체 함량의 총 합 100 중량부에 대하여, 0.03 내지 0.70 중량부이고,상기 단량체는 디엔계 단량체; 또는 디엔계 단량체와 비닐 방향족계 단량체;이고,상기 중합을 25 내지 50 ℃에서 개시하는 디엔계 고무질 중합체의 제조방법:<화학식 1>상기 화학식 1에서,R1 내지 R4는 각각 독립적으로 수소 또는 C1 내지 C10의 알킬기이고,L은 C1 내지 C10의 알킬렌기이다.<화학식 2>상기 화학식 2에서,R5 내지 R7은 각각 독립적으로 수소 또는 C1 내지 C5의 알킬기이나, R5 내지 R7 중 2 종 이상은 C1 내지 C5의 알킬기이다.
- 청구항 1에 있어서,상기 화학식 1로 표시되는 화합물은 N,N,N’,N’-테트라메틸에틸렌디아민 및 에틸렌디아민으로 이루어진 군에서 선택되는 1 종 이상인 디엔계 고무질 중합체의 제조방법.
- 청구항 1에 있어서,상기 화학식 2로 표시되는 화합물은 디메틸아민인 것인 디엔계 고무질 중합체의 제조방법.
- 청구항 1에 있어서,상기 열분해 개시제는 포타슘 퍼설페이트, 소듐 퍼설페이트 및 암모늄 퍼설페이트로 이루어진 군에서 선택되는 1종 이상인 것인 디엔계 고무질 중합체의 제조방법.
- 청구항 1에 있어서,상기 중합을 25 내지 35 ℃에서 개시하는 것인 디엔계 고무질 중합체의 제조방법.
- 청구항 1에 있어서,상기 열분해 개시제의 함량은 상기 디엔계 고무질 중합체의 제조 시 투입되는 단량체 함량의 총 합 100 중량부에 대하여, 0.01 내지 3.00 중량부인 것인 디엔계 고무질 중합체의 제조방법.
- 청구항 1에 있어서,상기 단량체의 중합을 개시 및 수행하는 단계는상기 아민계 화합물 및 열분해 개시제의 존재 하에, 상기 단량체의 중합을 개시하는 단계; 및중합전환율이 10 내지 50 %인 시점에 상기 단량체를 투입하고 중합하는 단계를 포함하는 것인 디엔계 고무질 중합체의 제조방법.
- 청구항 7에 있어서,상기 단량체의 중합을 개시하는 단계에서 투입하는 상기 단량체의 함량은, 상기 디엔계 고무질 중합체의 제조 시 투입되는 단량체 함량의 총 합 100 중량부에 대하여, 50 내지 90 중량부이고,상기 중합하는 단계에서 투입하는 상기 단량체의 함량은, 상기 디엔계 고무질 중합체의 제조 시 투입되는 단량체 함량의 총 합 100 중량부에 대하여, 10 내지 50 중량부인 것인 디엔계 고무질 중합체의 제조방법.
- 청구항 1에 있어서,상기 중합은 유화 중합인 것인 디엔계 고무질 중합체의 제조방법.
- 청구항 1에 따른 제조방법으로 디엔계 고무질 중합체를 제조하는 단계; 및상기 디엔계 고무질 중합체에 비닐 방향족계 단량체 및 비닐 시아나이드계 단량체를 중합하는 단계를 포함하는 그래프트 중합체의 제조방법.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP22898902.6A EP4357379A1 (en) | 2021-11-25 | 2022-11-08 | Method for producing diene-based rubbery polymer and method for producing graft polymer comprising same |
CN202280050732.4A CN117677644A (zh) | 2021-11-25 | 2022-11-08 | 二烯类橡胶状聚合物的制备方法和包含所述二烯类橡胶状聚合物的接枝聚合物的制备方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020210164269A KR20230077229A (ko) | 2021-11-25 | 2021-11-25 | 디엔계 고무질 중합체의 제조방법 및 이를 포함하는 그라프트 중합체의 제조방법 |
KR10-2021-0164269 | 2021-11-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023096220A1 true WO2023096220A1 (ko) | 2023-06-01 |
Family
ID=86539858
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2022/017471 WO2023096220A1 (ko) | 2021-11-25 | 2022-11-08 | 디엔계 고무질 중합체의 제조방법 및 이를 포함하는 그래프트 중합체의 제조방법 |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP4357379A1 (ko) |
KR (1) | KR20230077229A (ko) |
CN (1) | CN117677644A (ko) |
WO (1) | WO2023096220A1 (ko) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101423585A (zh) * | 2007-11-01 | 2009-05-06 | 中国石油天然气股份有限公司 | 一种交联型丁二烯-丙烯腈共聚橡胶的制备方法 |
CN101880364A (zh) * | 2010-06-25 | 2010-11-10 | 浙江大学 | 苯乙烯/丁二烯两嵌段共聚物纳米胶乳及其制备方法 |
CN102952237A (zh) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | 一种环氧化丁腈橡胶的制备方法 |
KR20160071249A (ko) * | 2014-12-11 | 2016-06-21 | 주식회사 엘지화학 | 대구경의 디엔계 고무 라텍스 제조 방법 및 이를 포함하는 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체 |
JP2017117597A (ja) * | 2015-12-22 | 2017-06-29 | 日本ゼオン株式会社 | 非水系二次電池電極用バインダー組成物の製造方法、非水系二次電池電極用スラリー組成物の製造方法、非水系二次電池用電極の製造方法、および非水系二次電池の製造方法 |
-
2021
- 2021-11-25 KR KR1020210164269A patent/KR20230077229A/ko active Search and Examination
-
2022
- 2022-11-08 WO PCT/KR2022/017471 patent/WO2023096220A1/ko active Application Filing
- 2022-11-08 EP EP22898902.6A patent/EP4357379A1/en active Pending
- 2022-11-08 CN CN202280050732.4A patent/CN117677644A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101423585A (zh) * | 2007-11-01 | 2009-05-06 | 中国石油天然气股份有限公司 | 一种交联型丁二烯-丙烯腈共聚橡胶的制备方法 |
CN101880364A (zh) * | 2010-06-25 | 2010-11-10 | 浙江大学 | 苯乙烯/丁二烯两嵌段共聚物纳米胶乳及其制备方法 |
CN102952237A (zh) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | 一种环氧化丁腈橡胶的制备方法 |
KR20160071249A (ko) * | 2014-12-11 | 2016-06-21 | 주식회사 엘지화학 | 대구경의 디엔계 고무 라텍스 제조 방법 및 이를 포함하는 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체 |
JP2017117597A (ja) * | 2015-12-22 | 2017-06-29 | 日本ゼオン株式会社 | 非水系二次電池電極用バインダー組成物の製造方法、非水系二次電池電極用スラリー組成物の製造方法、非水系二次電池用電極の製造方法、および非水系二次電池の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP4357379A1 (en) | 2024-04-24 |
KR20230077229A (ko) | 2023-06-01 |
CN117677644A (zh) | 2024-03-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2018084486A2 (ko) | Asa계 그라프트 공중합체의 제조방법, 이를 포함하는 열가소성 asa계 수지 조성물의 제조방법 및 asa계 성형품의 제조방법 | |
WO2017142172A1 (ko) | 고무질 중합체와 이의 제조방법, 그라프트 공중합체 및 열가소성 수지 조성물 | |
WO2021060743A1 (ko) | 그라프트 중합체의 제조방법 | |
WO2018084557A1 (ko) | 내후성이 우수한 열가소성 수지 조성물, 이의 제조방법 및 이를 포함하는 성형품 | |
WO2020032505A1 (ko) | 그라프트 공중합체의 제조방법, 그라프트 공중합체 및 이를 포함하는 열가소성 수지 성형품 | |
WO2020091370A1 (ko) | 열가소성 수지 조성물 | |
WO2018084408A1 (ko) | Abs계 수지 조성물의 제조방법 및 이를 포함하는 abs계 사출성형품의 제조방법 | |
WO2016195436A1 (ko) | 염화비닐계 중합체, 이의 제조방법 및 이를 포함하는 열가소성 수지 조성물 | |
WO2022010053A1 (ko) | 열가소성 수지 및 이의 제조방법 | |
WO2018174395A1 (ko) | Asa계 그라프트 공중합체의 제조방법, 이를 포함하는 열가소성 수지 조성물의 제조방법 및 성형품의 제조방법 | |
WO2018084436A1 (ko) | 충격강도가 향상된 abs계 그라프트 공중합체의 제조방법 및 이를 포함하는 abs계 사출성형품의 제조방법 | |
WO2021118063A1 (ko) | 알킬 아크릴레이트 화합물-비닐시안 화합물-방향족 비닐 화합물 그라프트 공중합체, 이의 제조방법 및 이를 포함하는 열가소성 수지 조성물 | |
WO2016182338A1 (ko) | 아크릴계 가공조제 및 이를 포함하는 염화비닐계 수지 조성물 | |
WO2019059664A1 (ko) | 그라프트 공중합체의 제조방법, 그라프트 공중합체 및 열가소성 수지 성형품 | |
WO2020101182A1 (ko) | 코어-쉘 공중합체, 이의 제조방법 및 이를 포함하는 열가소성 수지 조성물 | |
WO2023096220A1 (ko) | 디엔계 고무질 중합체의 제조방법 및 이를 포함하는 그래프트 중합체의 제조방법 | |
WO2020080735A1 (ko) | 그라프트 공중합체 분말의 제조방법 | |
WO2020050544A1 (ko) | 그라프트 공중합체의 제조방법 및 그라프트 공중합체 | |
WO2019098753A1 (ko) | 그라프트 공중합체의 제조방법 | |
WO2021066345A1 (ko) | 아크릴계 그라프트 공중합체, 이의 제조방법 및 이를 포함하는 열가소성 수지 조성물 | |
WO2021015485A1 (ko) | 아크릴계 공중합체 응집제 및 이를 이용한 그라프트 공중합체의 제조방법 | |
WO2022035071A1 (ko) | 투명 열가소성 수지 및 이의 제조방법 | |
WO2023008808A1 (ko) | 열가소성 수지 조성물 | |
WO2022085913A1 (ko) | 비닐시안 화합물-공액디엔 고무-방향족 비닐 화합물 그라프트 공중합체의 제조방법 및 이를 포함하는 열가소성 수지 조성물의 제조방법 | |
WO2020091336A1 (ko) | 열가소성 수지 조성물 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22898902 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022898902 Country of ref document: EP Ref document number: 22898902.6 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280050732.4 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2022898902 Country of ref document: EP Effective date: 20240116 |