KR20020039855A - Method for preparing latex having superior stability - Google Patents
Method for preparing latex having superior stability Download PDFInfo
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- KR20020039855A KR20020039855A KR1020000069676A KR20000069676A KR20020039855A KR 20020039855 A KR20020039855 A KR 20020039855A KR 1020000069676 A KR1020000069676 A KR 1020000069676A KR 20000069676 A KR20000069676 A KR 20000069676A KR 20020039855 A KR20020039855 A KR 20020039855A
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- rubber latex
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- 229920000126 latex Polymers 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000004816 latex Substances 0.000 title claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 52
- -1 diene compound Chemical class 0.000 claims abstract description 33
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 11
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 11
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012874 anionic emulsifier Substances 0.000 claims abstract description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 5
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 claims abstract description 5
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 18
- 239000003505 polymerization initiator Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical class C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000344 soap Substances 0.000 claims description 5
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 150000008055 alkyl aryl sulfonates Chemical group 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 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 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- JUFQKGBQFXDZQO-UHFFFAOYSA-N C1(=CC=CC=C1)OC(=CC)CCCCCCCCC Chemical compound C1(=CC=CC=C1)OC(=CC)CCCCCCCCC JUFQKGBQFXDZQO-UHFFFAOYSA-N 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 11
- 229910052700 potassium Inorganic materials 0.000 description 10
- 239000011591 potassium Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical class [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008121 dextrose Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 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 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/10—Latex
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
[산업상 이용 분야][Industrial use]
본 발명은 안정성이 우수한 고무라텍스의 제조방법에 관한 것으로, 특히 고무라텍스의 제조에 있어서 반응형 유화제를 사용하여 안정성이 우수한 고무라텍스를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a rubber latex having excellent stability, and more particularly to a method for producing a rubber latex having excellent stability using a reactive emulsifier in the production of the rubber latex.
[종래 기술][Prior art]
투명 아크릴로니트릴-부타디엔-스티렌(ABS : acrylonitrile-butadiene-styrene) 수지의 제조에 있어서, 투명도는 굴절율이 적절하게 조절되었을 때 분산되어진 고무질 중합체의 입자경 크기와 입자 분포, 및 후공정에서 생성된 응고물 등에 크게 영향을 받는다.In the preparation of transparent acrylonitrile-butadiene-styrene (ABS) resins, the transparency is determined by the particle size and particle distribution of the rubbery polymer dispersed when the refractive index is properly controlled, and the coagulation produced in the subsequent process. It is greatly affected by water.
내충격성과 투명성이 우수한 아크릴로니트릴-부타디엔-스티렌 수지를 얻기 위해서는 대구경 고무라텍스가 필요한데, 이를 제조하기 위한 종래의 방법으로는 하기와 같은 방법들이 알려져 있다.In order to obtain an acrylonitrile-butadiene-styrene resin having excellent impact resistance and transparency, a large diameter rubber latex is required. As a conventional method for preparing the same, the following methods are known.
ⅰ) 소구경 고무라텍스를 제조하여 초산, 인산 등과 같은 무기산성물 또는고분자 응집제와 같은 유기산성물질을 첨가하여 pH를 낮추고 입자를 융 착시켜서 대구경 고무라텍스를 제조하는 방법;Iii) preparing small-diameter rubber latex, adding inorganic acids such as acetic acid, phosphoric acid, or organic acidic substances such as polymer flocculant to lower pH and fusion particles to produce large-diameter rubber latex;
ⅱ) 소구경 고무라텍스를 냉동시켜 대구경 입자를 제조하는 방법;Ii) a method for producing large-diameter particles by freezing small-diameter rubber latex;
ⅲ) 중합 도중 아크릴레이트계 공중합체 라텍스를 첨가하거나 또는 다가금속 의 전해질을 첨가하여 대구경 고무라텍스를 제조하는 방법;Iii) a method for preparing a large diameter rubber latex by adding an acrylate copolymer latex or adding a polyvalent metal electrolyte during the polymerization;
ⅳ) 소구경 고무라텍스에 전단력을 가하여 대구경 고무라텍스를 제조하는 방 법;Iii) a method for producing large diameter rubber latex by applying shear force to small diameter rubber latex;
ⅴ) 아크릴로니트릴 단량체를 공단량체로 소량 도입하는 방법Iii) a small amount of acrylonitrile monomer introduced into the comonomer
ⅵ) 유화제의 양과 이온의 세기를 적절하게 조절하여 대구경 고무라텍스를 제조하는 방법.Iii) A method for producing large diameter rubber latex by appropriately adjusting the amount of emulsifier and the ionic strength.
상기 ⅰ) 내지 ⅳ)의 방법은 단시간내에 대구경 고무라텍스의 제조가 가능하다는 장점이 있으나, 응고물이 많이 생성되고 중합의 재현성이 부족하며 적절한 크기로 조절하기 힘들다는 문제가 있다. 따라서 응고물을 거르는 장치, 및 과정이 필요하지만, 상기 과정 중에 생성된 원치 않는 크기의 응고물이 첨가되는 문제점이 발생하고, 이는 투명도를 크게 저하시키는 원인이 된다. 또한 ⅴ)의 방법은 고무라텍스 중합 후 미반응 단량체를 제거해야 하는 문제점이 있고, 특히 저온충격강도에서 순수한 디엔계 고무라텍스를 사용하는 경우보다 투명도가 떨어지는 단점이 있다. 또한 ⅵ)의 방법은 반응시간이 오래 걸리고 유화제 농도가 낮아야 하므로, 응고물이 많이 생성되고 교반시 반응열을 제거하기 어렵다는 문제점이 있다.The method of iii) to iii) has the advantage that it is possible to manufacture large diameter rubber latex within a short time, but there is a problem that a lot of coagulum is produced and the reproducibility of polymerization is insufficient and it is difficult to control to an appropriate size. Therefore, a device for filtering the coagulum and a process are required, but a problem arises in that an unwanted coagulum produced during the process is added, which causes a significant decrease in transparency. In addition, the method of iii) has a problem in that unreacted monomers have to be removed after rubber latex polymerization, and in particular, transparency is lower than that of pure diene rubber latex at low temperature impact strength. In addition, the method of iii) requires a long reaction time and a low concentration of the emulsifier, so that a large amount of coagulum is generated and it is difficult to remove the reaction heat during stirring.
본 발명은 상기 종래 기술의 문제점을 고려하여, 안정성이 우수한 고무라텍스의 제조방법을 제공하는 것을 목적으로 한다.In view of the problems of the prior art, it is an object of the present invention to provide a method for producing a rubber latex having excellent stability.
본 발명의 다른 목적은 안정성을 증가시켜 응고물 생성을 줄이고, 고무 입경 분포가 좁은 고무라텍스를 제조할 수 있을 뿐만 아니라, 고충격성, 및 고투명성이 우수한 투명 아크릴로니트릴-부타디엔-스티렌 수지를 제조할 수 있는 안정성이 우수한 고무라텍스를 제공하는 것이다.Another object of the present invention is to increase the stability, to reduce the formation of coagulum, to produce a rubber latex having a narrow rubber particle size distribution, as well as to prepare a transparent acrylonitrile-butadiene-styrene resin having excellent high impact and high transparency. It is to provide a rubber latex with excellent stability.
[과제를 해결하기 위한 수단][Means for solving the problem]
본 발명은 상기 목적을 달성하기 위하여, 안정성이 우수한 고무라텍스의 제조방법에 있어서,In order to achieve the above object, the present invention provides a rubber latex manufacturing method excellent in stability,
ⅰ) 공액디엔 화합물 단량체Iii) conjugated diene compound monomer
에 ⅱ) 반응형 유화제를 가하여 유화중합하는 단계를 포함하는 안정성이 우수한 고무라텍스의 제조방법을 제공한다.Ii) adding a reactive emulsifier to provide a method for producing a rubber latex having excellent stability including the step of emulsion polymerization.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
[작용][Action]
본 발명은 공액디엔 화합물 단량체에 반응형 유화제를 가하여 유화중합함으로써 안정성을 증가시켜 응고물 생성을 줄이고, 고무 입경 분포가 좁은 고무라텍스를 제조할 수 있을 뿐만 아니라, 고충격성, 및 고투명성이 우수한 투명 아크릴로니트릴-부타디엔-스티렌 수지를 제조할 수 있는 안정성이 우수한 고무라텍스를 제조하는 것이다.The present invention increases the stability by adding a reactive emulsifier to the conjugated diene compound monomer to increase the stability to reduce the formation of coagulum, and to prepare a rubber latex with a narrow rubber particle size distribution, as well as high impact and high transparency It is to prepare a rubber latex having excellent stability capable of producing acrylonitrile-butadiene-styrene resin.
본 발명은 이를 위하여, 상기 고무라텍스는The present invention for this purpose, the rubber latex is
ⅰ) 공액디엔 화합물 단량체 100 중량부;Iii) 100 parts by weight of the conjugated diene compound monomer;
에 ⅱ) 반응형 유화제 0.01 내지 3.0 중량부를 가하여 유화중합으로 중합한다.Ii) 0.01 to 3.0 parts by weight of a reactive emulsifier is added to polymerize by emulsion polymerization.
더욱 구체적으로는,More specifically,
a) 반응기에a) in the reactor
ⅰ) 공액디엔 화합물 단량체 50 내지 100 중량부;Iii) 50 to 100 parts by weight of the conjugated diene compound monomer;
ⅱ) 반응형 유화제 0.5 중량부 이하;Ii) 0.5 parts by weight or less of a reactive emulsifier;
ⅲ) 비반응형 유화제 1 내지 4 중량부;V) 1 to 4 parts by weight of a non-reactive emulsifier;
ⅳ) 중합개시제 0.2 내지 1.5 중량부;Iii) 0.2 to 1.5 parts by weight of a polymerization initiator;
ⅴ) 전해질 0.5 내지 2 중량부;V) 0.5 to 2 parts by weight of electrolyte;
ⅵ) 분자량 조절제 0.1 내지 0.5 중량부; 및Iii) 0.1 to 0.5 parts by weight of a molecular weight modifier; And
ⅶ) 이온교환수 75 내지 100 중량부Viii) 75 to 100 parts by weight of ion-exchanged water
를 일괄투여하여 65∼75 ℃에서 4∼15 시간 동안 반응시키는 단계;Dosing in a batch to react at 65 to 75 ° C. for 4 to 15 hours;
b) 상기 a) 단계의 반응물에b) reactants of step a)
ⅰ) 나머지 공액디엔 화합물 단량체 50 중량부 이하; 및V) 50 parts by weight or less of the remaining conjugated diene compound monomers; And
ⅵ) 분자량 조절제 0.1 내지 0.5 중량부Iii) 0.1 to 0.5 parts by weight of molecular weight regulator
를 일괄투여 또는 연속투여하여 70∼85 ℃에서 10∼20 시간 동안 반응시키는To batch or continuous dosing and reacted at 70 to 85 ° C. for 10 to 20 hours.
단계; 및step; And
c) 상기 b) 단계의 반응물의 중합전환율이 총 화합물의 30∼70 %가 되면c) the polymerization conversion rate of the reactant of step b) is 30-70% of the total compound
ⅱ) 반응형 유화제 0.01 내지 3.0 중량부Ii) 0.01 to 3.0 parts by weight of a reactive emulsifier
를 가하는 단계Steps to apply
를 포함하는 방법으로 제조되는 것이 바람직하다.It is preferable to be prepared by a method comprising a.
상기 ⅰ) 공액디엔 화합물 단량체는 총 100 중량부 중 중합개시전 50 내지 100 중량부를 일괄투여하여 반응시킨 후, 나머지 공액디엔 화합물 단량체를 일괄투여, 또는 연속투여하여 반응시킨다.(Iii) The conjugated diene compound monomers are reacted by collectively administering 50 to 100 parts by weight of the total conjugated diene compound monomers before the start of polymerization, and then the remaining conjugated diene compound monomers are collectively administered or continuously administered.
또한 ⅰ) 공액디엔 화합물 단량체는 공액디엔 화합물을 단독, 또는 스티렌, α-메틸스티렌 등의 방향족 비닐 화합물, 및 아크릴로니트릴 등과 같은 비닐시안 화합물과 혼합하여 사용할 수 있고, 총 단량체 혼합물 중 15 중량부 이내로 사용하는 것이 바람직하다.Iii) The conjugated diene compound monomers may be used alone or in combination with aromatic vinyl compounds such as styrene and α-methylstyrene, and vinyl cyan compounds such as acrylonitrile, and 15 parts by weight of the total monomer mixture. It is preferable to use within.
상기 ⅰ) 공액디엔 화합물은 1,3-부타디엔, 이소프렌, 클로로프렌, 및 피레리덴으로 이루어진 군으로부터 1 종 이상 선택되어 사용할 수 있다.(Iii) The conjugated diene compound may be selected from one or more selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and pyreriden.
본 발명의 고무라텍스의 제조방법에 사용되는 상기 ⅱ) 반응형 유화제는 알릴기, (메타)아크릴로일기, 및 프로페닐기를 가지는 음이온계 유화제, 또는 중성계 유화제 등이 사용될 수 있다.The ii) reactive emulsifier used in the rubber latex manufacturing method of the present invention may be an anionic emulsifier having an allyl group, a (meth) acryloyl group, and a propenyl group, or a neutral emulsifier.
상기 알릴기를 가지는 음이온 유화제로는 폴리옥시에틸렌 알릴그리시딜 노닐페닐 에테르의 설페이트염을 대표적으로 들 수 있으며, 시장에서 유용한 것으로는 ADEKARIA SOAP SE 계열(Asahi Denka 사의 제품) 등이 있으며, 알릴기를 가지는 중성계 유화제로는 폴리옥시에틸렌 알릴그리시딜 노닐페닐 에테르 계열이 있으며, 시장에서 유용한 것으로는 ADEKARIA SOAP NE 계열(Asahi Denka 사의 제품) 등이 있다. (메타)아크릴로일기를 가지는 음이온계 유화제로 시장에서 유용한 것은 ELEMINOL RS 계열(Sanyo Kasei 사의 제품)이 있고, 중성계 유화제로는 RMA-560 계열(Nippon Surfactant 사의 제품)이 있다. 프로펜기를 가지는 음이온계 유화제로는 폴리옥시에틸렌 알릴그리시딜 노닐 프로페닐 페닐 에테르의 암모늄설페이트염을 대표적으로 들 수 있으며, 시장에서 유용한 것으로는 AQUARON HS 계열이 있으며, 중성계 유화제로는 AQUARON BC(Daiichi Kogyo Seyaku 사의 제품) 계열이 있다. 이러한 반응형 유화제는 단독, 또는 2 종 이상의 혼합물로 사용할 수 있으며, 비반응형 유화제와 혼합하여 사용할 수 있다.Anionic emulsifiers having an allyl group may include sulfate salts of polyoxyethylene allylglycidyl nonylphenyl ether. Examples of useful anionic emulsifiers include ADEKARIA SOAP SE series (manufactured by Asahi Denka), and neutral allyl groups. Systemic emulsifiers include polyoxyethylene allylglycidyl nonylphenyl ether series, and useful ones on the market include the ADEKARIA SOAP NE series (product of Asahi Denka). The anionic emulsifier having a (meth) acryloyl group is useful in the market as the ELEMINOL RS series (manufactured by Sanyo Kasei), and the neutral emulsifier is the RMA-560 series (manufactured by Nippon Surfactant). Anionic emulsifiers having a propene group include ammonium sulfate salts of polyoxyethylene allylglycidyl nonyl propenyl phenyl ether, and useful in the market include AQUARON HS series, and neutral emulsifiers include AQUARON BC ( Daiichi Kogyo Seyaku's products) series. These reactive emulsifiers may be used alone or as a mixture of two or more thereof, and may be used by mixing with a non-reactive emulsifier.
또한 상기 ⅱ) 반응형 유화제는 유화중합시 0.01 내지 3.0 중량부를 첨가하는 것이 바람직하며, 바람직하게는 3.0 이하로 사용하는 것이 바람직하다. 3.0 이상이면 아크릴로니트릴-부타디엔-스티렌 중합 후의 응집 공정에서 라텍스의 모액이 잘 분리되지 않아 응집이 저조할 수 있다.In addition, the ii) reactive emulsifier is preferably added 0.01 to 3.0 parts by weight during the emulsion polymerization, it is preferable to use less than 3.0. If it is 3.0 or more, the mother liquor of latex may not be isolate | separated well in the aggregation process after acrylonitrile butadiene-styrene polymerization, and aggregation may be low.
상기 ⅲ) 비반응 유화제는 알킬 아릴 설포네이트, 알카리메틸 알킬 설페이트, 설포네이트화된 알킬에스테르, 지방산의 비누, 및 로진산의 알카리염으로 이루어지는 군으로부터 1 종 이상 선택되어 사용할 수 있다.(Iii) The non-reacting emulsifier may be selected from one or more selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and alkali salts of rosin acid.
본 발명의 제조방법은 통상적인 유화중합에서 사용되는 분자량 조절제, 및 중합개시제를 첨가하여 고무라텍스를 제조할 수 있다.In the production method of the present invention, a rubber latex can be prepared by adding a molecular weight regulator and a polymerization initiator used in conventional emulsion polymerization.
상세하게는, 상기 ⅳ) 중합개시제는 나트륨 퍼설페이트, 또는 칼륨 퍼설페이트의 수용성 퍼설페이트; 큐멘하이드로 퍼옥사이드, 디이소프로필 벤젠 하이드로퍼옥사이드, 아조비스 이소부틸로니트릴, 3급 부틸 하이드로퍼옥사이드, 파라메탄 하이드로퍼옥사이드, 또는 벤조일퍼옥사이드의 지용성 중합개시제; 및 산화-환원계 중합계시제로 이루어진 군으로부터 1 종 이상 선택되어 사용할 수 있다.Specifically, the iii) polymerization initiator is a water-soluble persulfate of sodium persulfate, or potassium persulfate; Fat-soluble polymerization initiators of cumenehydro peroxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, or benzoyl peroxide; And an oxidation-reduction type polymerization initiator can be used by selecting at least one type.
또한 ⅴ) 전해질은 KCl, NaCl, KHCO3, NaHCO3, Na2CO3, K2CO3, KHSO3, NaHSO3, K4P2O7, Na4P2O7, K3PO4, Na3PO4, Na2HPO4, 및 Na2HPO4로 이루어진 군으로부터 1 종 이상 선택하여 사용할 수 있다.And iii) KCl, NaCl, KHCO 3 , NaHCO 3 , Na 2 CO 3 , K 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7 , Na 4 P 2 O 7 , K 3 PO 4 , At least one selected from the group consisting of Na 3 PO 4 , Na 2 HPO 4 , and Na 2 HPO 4 can be used.
상기 ⅵ) 분자량조절제는 머캅탄류가 바람직하며, 그 예로는 n-옥틸머캅탄(NOM: n-octylmercaptane), n-도데실머캅탄(DDM: n-dodecylmercaptane ), 및 t-도데실머캅탄(TDDM: t-dodecyl mercaptane)으로 이루어지는 군으로부터 1 종 이상 선택하여 사용할 수 있다.(Iii) Preferably, the molecular weight regulators are mercaptans, for example n-octylmercaptane (NOM: n-octylmercaptane), n-dodecylmercaptane (DDM: n-dodecylmercaptane), and t-dodecylmercaptan (TDDM: t-dodecyl mercaptane) can be used by selecting one or more kinds.
중합온도는 고무라텍스의 겔함량 및 팽윤도를 조정하기에 매우 중요하며, 이때 중합개시제의 선정도 고려되어야 한다. 저온내충격성이 우수한 아크릴로니트릴 -부타디엔-스티렌 수지를 얻기 위해서 적절한 고무라텍스의 평균입경은 2600 Å 내지 5000 Å이 적당하고 입경 표준편차는 25 %가 적당하다. 또한 전체 겔함량은 60 내지 95 %가 적당하고 팽윤지수는 18 내지 40 정도가 적당하다. 이때 고무질중합체의 평균입경이 2600 Å 이하이면 저온내충격성이 저하되고, 5000 Å 이상이면 아크릴로니트릴-부타디엔-스티렌 수지에 적용할 때 중합체의 안정성이 저하되어 응고물이 다량생성된다.The polymerization temperature is very important for adjusting the gel content and swelling degree of the rubber latex, and the selection of the polymerization initiator should also be considered. In order to obtain an acrylonitrile-butadiene-styrene resin having excellent low temperature impact resistance, an average particle diameter of suitable rubber latex is preferably 2600 mm to 5000 mm and a standard deviation of particle size is 25%. In addition, the total gel content is suitably 60 to 95% and the swelling index is about 18 to 40. In this case, when the average particle diameter of the rubbery polymer is 2600 mm 3 or less, the low temperature impact resistance is lowered, and when the average particle diameter is 5000 mm 3 or more, the stability of the polymer decreases when applied to the acrylonitrile-butadiene-styrene resin, thereby producing a large amount of coagulum.
이하의 실시예 및 비교예를 통하여 본 발명을 더욱 상세하게 설명한다. 단, 실시예는 본 발명을 예시하기 위한 것이지 이들만으로 한정하는 것은 아니다.The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.
[실시예]EXAMPLE
실시예 1Example 1
질소치환된 중합반응기(오토클레이브)에 이온교환수 75 중량부, 단량체로 1,3-부타디엔 100 중량부, 유화제로 로진산 칼륨염 2.0 중량부, 올레인산 칼륨염 0.4 중량부, 전해질로 탄산칼륨(K2CO3) 2.0 중량부, 분자량조절제로 3급 도데실머캅탄(TDDM) 0.3 중량부, 중합개시제로 과황산 칼륨 0.2 중량부를 일괄투여하고 반응온도 70 ℃에서 10 시간 동안 반응시켰다. 상기 반응물의 중합전환율이 50 %가 되면 반응유화제인 AQUARON HS-10 0.3 중량부를 일괄투여하고 온도를 75 ℃로 올려 20 시간 동안 더욱더 반응시킨 후, 중합전환율이 90 %가 되면 중합억제제를 투입하고 반응을 종결tlu 고무라텍스를 수득하였다.In a nitrogen-substituted polymerization reactor (autoclave) 75 parts by weight of ion-exchanged water, 100 parts by weight of 1,3-butadiene as monomer, 2.0 parts by weight of potassium rosin salt as emulsifier, 0.4 parts by weight of potassium oleate salt, potassium carbonate as electrolyte K 2 CO 3 ) 2.0 parts by weight, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, 0.2 parts by weight of potassium persulfate as a polymerization initiator were reacted at a reaction temperature of 70 ℃ for 10 hours. When the polymerization conversion rate of the reactants is 50%, 0.3 parts by weight of AQUARON HS-10, which is a reaction emulsifier, is added in a batch, and the temperature is increased to 75 ° C. for 20 hours. This terminated tlu rubber latex.
실시예 2Example 2
질소치환된 중합반응기에 이온교환수 75 중량부, 단량체로 1,3-부타디엔 100 중량부, 유화제로 로진산 칼륨염 2.0 중량부, 올레인산 칼륨염 0.4 중량부, 반응형 유화제로 AQUARON HS-10 0.1 중량부, 전해질로 탄산칼륨 2.0 중량부, 분자량조절제로 3급 도데실머캅탄 0.3 중량부, 중합개시제로 과황산 칼륨 0.2 중량부를 일괄투여하고 반응온도 70 ℃에서 10 시간 동안 반응시켜 중합전환율이 90 %가 되면 중합억제제를 투입하고 반응을 종결시켜 고무라텍스를 수득하였다.75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 100 parts by weight of 1,3-butadiene as monomer, 2.0 parts by weight of potassium rosin salt as emulsifier, 0.4 parts by weight of potassium oleate salt, AQUARON HS-10 0.1 as reactive emulsifier Parts by weight, 2.0 parts by weight of potassium carbonate as electrolyte, 0.3 parts by weight of tertiary dodecylmercaptan as molecular weight regulator, 0.2 parts by weight of potassium persulfate as polymerization initiator and reacted for 10 hours at a reaction temperature of 70 ° C, resulting in 90% polymerization conversion. When the polymerization inhibitor was added to terminate the reaction to give a rubber latex.
실시예 3Example 3
질소치환된 중합반응기에 이온교환수 75 중량부, 단량체로 1,3-부타디엔 100중량부, 유화제로 로진산 칼륨염 2.0 중량부, 올레인산 칼륨염 0.4 중량부, 전해질로 탄산칼륨 2.0 중량부, 분자량조절제로 3급 도데실머캅탄 0.3 중량부, 중합개시제로 과황산 칼륨 0.2 중량부를 일괄투여하고 반응온도 70 ℃에서 10 시간 동안 반응시켰다. 상기 반응물의 중합전환율이 50 %가 되면 3급 도데실머캅탄 0.1 중량부, 로진산 칼륨 0.4 중량부, 반응유화제인 AQUARON HS-10 3 중량부를 연속투여하고 온도를 75 ℃로 올려 20 시간 동안 더욱더 반응시킨 후, 중합전환율이 90 %가 되면 중합억제제를 투입하고 반응을 종결시켜 고무라텍스를 수득하였다.75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 100 parts by weight of 1,3-butadiene as monomer, 2.0 parts by weight of potassium rosin salt as emulsifier, 0.4 parts by weight of potassium oleate salt, 2.0 parts by weight of potassium carbonate as electrolyte, molecular weight 0.3 parts by weight of tertiary dodecyl mercaptan as a regulator and 0.2 parts by weight of potassium persulfate as a polymerization initiator were collectively administered and reacted at a reaction temperature of 70 ° C. for 10 hours. When the polymerization conversion rate of the reactants is 50%, 0.1 parts by weight of tertiary dodecylmercaptan, 0.4 parts by weight of potassium rosinate, and 3 parts by weight of AQUARON HS-10 which is a reaction emulsifier are continuously administered, and the temperature is raised to 75 ° C. for 20 hours. After the polymerization conversion was 90%, the polymerization inhibitor was added and the reaction was terminated to obtain a rubber latex.
실시예 4Example 4
질소치환된 중합반응기에 이온교환수 75 중량부, 단량체로 1,3-부타디엔 80 중량부, 유화제로 로진산 칼륨염 2.0 중량부, 올레인산 칼륨염 0.4 중량부, 전해질로 탄산칼륨 2.0 중량부, 분자량조절제로 3급 도데실머캅탄 0.3 중량부, 중합개시제로 과황산 칼륨 0.2 중량부를 일괄투여하고 반응온도 70 ℃에서 10 시간 동안 반응시켰다. 상기 반응물의 중합전환율이 50 %가 되면 1,3-부타디엔 20 중량부, 로진산 칼륨 0.4 중량부, 반응유화제인 AQUARON HS-10 0.2 중량부를 넣고 온도를 75 ℃로 올려 20 시간 동안 더욱더 반응시킨 후, 중합전환율이 90 %가 되면 중합억제제를 투입하고 반응을 종결시켜 고무라텍스를 수득하였다.75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 80 parts by weight of 1,3-butadiene as monomer, 2.0 parts by weight of potassium rosin acid salt as emulsifier, 0.4 parts by weight of potassium oleate salt, 2.0 parts by weight of potassium carbonate as electrolyte, molecular weight 0.3 parts by weight of tertiary dodecyl mercaptan as a regulator and 0.2 parts by weight of potassium persulfate as a polymerization initiator were collectively administered and reacted at a reaction temperature of 70 ° C. for 10 hours. When the polymerization conversion rate of the reactant is 50%, 20 parts by weight of 1,3-butadiene, 0.4 parts by weight of potassium rosin acid, 0.2 parts by weight of AQUARON HS-10 which is a reaction emulsifier are added, and the temperature is raised to 75 ° C. for 20 hours. When the polymerization conversion rate was 90%, a polymerization inhibitor was added and the reaction was terminated to obtain a rubber latex.
비교예 1Comparative Example 1
질소치환된 중합반응기에 이온교환수 75 중량부, 단량체로 1,3-부타디엔 100 중량부, 유화제로 로진산 칼륨염 2.0 중량부, 올레인산 칼륨염 0.4 중량부, 전해질로 탄산칼륨 2.0 중량부, 분자량조절제로 3급 도데실머캅탄 0.3 중량부, 중합개시제로 과황산 칼륨 0.2 중량부를 일괄투여하고 반응온도 70 ℃에서 10 시간 동안 반응시킨 후, 중합전환율이 90 %가 되면 중합억제제를 투입하고 반응을 종결시켜 고무라텍스를 수득하였다.75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 100 parts by weight of 1,3-butadiene as monomer, 2.0 parts by weight of potassium rosin salt as emulsifier, 0.4 parts by weight of potassium oleate salt, 2.0 parts by weight of potassium carbonate as electrolyte, molecular weight 0.3 parts by weight of tertiary dodecyl mercaptan as a control agent and 0.2 parts by weight of potassium persulfate as a polymerization initiator were reacted at a reaction temperature of 70 ° C. for 10 hours, and when the polymerization conversion rate reached 90%, a polymerization inhibitor was added to terminate the reaction. To give a rubber latex.
비교예 2Comparative Example 2
질소치환된 중합반응기에 이온교환수 75 중량부, 단량체로 1,3-부타디엔 80 중량부, 유화제로 로진산 칼륨염 2.0 중량부, 올레인산 칼륨염 0.4 중량부, 전해질로 탄산칼륨 2.0 중량부, 분자량조절제로 3급 도데실머캅탄 0.3 중량부, 중합개시제로 과황산 칼륨 0.2 중량부를 일괄투여하고 반응온도 70 ℃에서 10 시간 동안 반응시켰다. 상기 반응물의 중합전환율이 50 %가 되면 1,3-부타디엔 20 중량부, 로진산 칼륨 0.4 중량부를 넣고 온도를 75 ℃로 올려 20 시간 동안 더욱더 반응시킨 후, 중합전환율이 90 %가 되면 중합억제제를 투입하고 반응을 종결시켜 고무라텍스를 수득하였다.75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 80 parts by weight of 1,3-butadiene as monomer, 2.0 parts by weight of potassium rosin acid salt as emulsifier, 0.4 parts by weight of potassium oleate salt, 2.0 parts by weight of potassium carbonate as electrolyte, molecular weight 0.3 parts by weight of tertiary dodecyl mercaptan as a regulator and 0.2 parts by weight of potassium persulfate as a polymerization initiator were collectively administered and reacted at a reaction temperature of 70 ° C. for 10 hours. When the polymerization conversion rate of the reactants is 50%, 20 parts by weight of 1,3-butadiene and 0.4 parts by weight of potassium rosinate are added and the temperature is increased to 75 ° C. for 20 hours, and the polymerization inhibitor is 90%. Charged and the reaction was terminated to give a rubber latex.
상기 실시예 1 내지 4, 및 비교예 1, 2에서 수득한 고무라텍스의 겔함량 및 팽윤지수, 입자경 및 입자경분포, 및 생성응고물을 하기와 같은 ㄱ), ㄴ), 및 ㄷ)의 방법으로 측정하였다.The gel content and swelling index, particle size and particle size distribution, and the resulting coagulum of the rubber latex obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were prepared by the following methods a), b), and c). Measured.
ㄱ) 겔함량 및 팽윤지수A) gel content and swelling index
고무질 중합체 라텍스를 묽은 산이나 금속염을 사용하여 응고시키고 세척하여 60 ℃의 진공오븐에서 24 시간 동안 건조하였다. 상기의 과정으로 수득한 고무덩어리를 잘게 자른 후, 1 g의 고무절편을 톨루엔 100 g에 넣고 48 시간 동안 실온의 암실에서 보관하였다. 이를 졸과 겔로 분리하고 하기의 수학식 1, 및 2에 따라겔함량 및 팽윤지수를 측정하여 그 결과를 표 1에 나타내었다.The rubbery polymer latex was coagulated with dilute acid or metal salt, washed and dried in a vacuum oven at 60 ° C. for 24 hours. After the rubber mass obtained by the above process was finely chopped, 1 g of rubber fragments were put in 100 g of toluene and stored in a dark room at room temperature for 48 hours. This was separated into a sol and a gel and the gel content and swelling index were measured according to the following Equations 1 and 2, and the results are shown in Table 1.
[수학식 1][Equation 1]
[수학식 2][Equation 2]
ㄴ) 입자경 및 입자경분포B) particle size and particle size distribution
다이나믹 레이져라이트 스케트링법으로 Nicomp 370HPL을 이용하여 측정하였다.It was measured using the Nicomp 370HPL by the dynamic laser light scattering method.
ㄷ) 생성응고물C) produced coagulum;
하기의 수학식 3에 의하여 측정하였다.It measured by the following formula (3).
[표 1]TABLE 1
상기 표 1에 나타낸 바와 같이, 반응형 유화제를 첨가한 실시예 1, 2, 3, 및 4의 경우 비교예 1, 및 2에 비하여 팽윤지수가 크고 응고물 생성이 적음을 확인할 수 있었다. 또한 단량체를 가하여 중합전환율이 총 화합물의 30∼70 %일 때 반응형 유화제를 가한 경우, 단량체와 반응형 유화제를 동시에 가한 경우보다 응고물 생성이 적음을 알 수 있었다.As shown in Table 1, in Examples 1, 2, 3, and 4 to which the reactive emulsifier was added, it was confirmed that the swelling index was larger than that of Comparative Examples 1 and 2, and the coagulation product was less produced. In addition, when the monomer was added and the polymerization conversion was 30 to 70% of the total compound, it was found that when the reactive emulsifier was added, coagulation was less produced than when the monomer and the reactive emulsifier were added simultaneously.
[사용예][Example]
사용예 1Example 1
질소치환된 중합반응기에 상기 실시예 1에서 수득한 고무라텍스 18 중량부를 투입하고 이온교환수 80 중량부, 올레인산나트륨 유화제 0.2 중량부, 메틸메타크릴레이트 14.38 중량부, 스티렌 5.62 중량부, 아크릴로니트릴 2.5 중량부, 3급 도데실머캅탄 0.2 중량부, 피로인산나트륨 0.048 중량부, 덱스트로즈 0.012 중량부, 황화제1철 0.001 중량부, 큐멘하이드로퍼옥사이드 0.04 중량부를 50 ℃에서 일괄투여하고 반응온도를 73 ℃까지 2 시간에 걸쳐 올리면서 반응시켰다. 여기에 이온교환수 70 중량부, 올레인산나트륨 0.4 중량부, 메틸메타크릴레이트 43.12 중량부, 스티렌 16.88 중량부, 아크릴로니트릴 7.5 중량부, 3급 도데실머캅탄 0.25 중량부, 필인산나트륨 0.048 중량부, 덱스트로즈 0.012 중량부, 황화제1철 0.001 중량부, 큐멘하이드로퍼옥사이드 0.10 중량부의 혼합 유화용액을 4 시간 동안 연속투여한 후, 다시 76 ℃로 승온하고 1 시간 동안 숙성시켜 반응을 종료하였다. 이 때 중합전환율은 99.5 %였고, 고형응고분은 0.05 %였다.18 parts by weight of the rubber latex obtained in Example 1 was added to a nitrogen-substituted polymerization reactor, 80 parts by weight of ion-exchanged water, 0.2 parts by weight of sodium oleate emulsifier, 14.38 parts by weight of methyl methacrylate, 5.62 parts by weight of styrene, and acrylonitrile. 2.5 parts by weight, tertiary dodecyl mercaptan 0.2 part by weight, sodium pyrophosphate 0.048 part by weight, dextrose 0.012 part by weight, ferrous sulfide 0.001 part by weight, cumene hydroperoxide 0.04 part by weight at 50 ℃ and the reaction temperature Reacted while raising to 73 degreeC over 2 hours. Here, 70 parts by weight of ion-exchanged water, 0.4 parts by weight of sodium oleate, 43.12 parts by weight of methyl methacrylate, 16.88 parts by weight of styrene, 7.5 parts by weight of acrylonitrile, 0.25 parts by weight of tertiary dodecyl mercaptan, and 0.048 parts by weight of sodium phosphate , 0.012 parts by weight of dextrose, 0.001 parts by weight of ferrous sulfide, and 0.10 parts by weight of cumene hydroperoxide were continuously administered for 4 hours, and then heated to 76 ° C. and aged for 1 hour to complete the reaction. . At this time, the polymerization conversion was 99.5% and the solid coagulum was 0.05%.
사용예 2Example 2
상기 사용예 1과 동일한 방법으로 하되, 실시예 2에서 수득한 고무라텍스를 사용하여 제조하였다.Was prepared in the same manner as in Example 1, using the rubber latex obtained in Example 2.
사용예 3Example 3
상기 사용예 1과 동일한 방법으로 하되, 실시예 3에서 수득한 고무라텍스를 사용하여 제조하였다.Was prepared in the same manner as in Example 1, using the rubber latex obtained in Example 3.
사용예 4Example 4
상기 사용예 1과 동일한 방법으로 하되, 실시예 4에서 수득한 고무라텍스를 사용하여 제조하였다.Was prepared in the same manner as in Example 1, using the rubber latex obtained in Example 4.
사용예 5Example 5
상기 사용예 1과 동일한 방법으로 하되, 비교예 1에서 수득한 고무라텍스를 사용하여 제조하였다.In the same manner as in Use Example 1, was prepared using the rubber latex obtained in Comparative Example 1.
사용예 6Use Example 6
상기 사용예 1과 동일한 방법으로 하되, 비교예 2에서 수득한 고무라텍스를 사용하여 제조하였다.Was prepared in the same manner as in Example 1, using the rubber latex obtained in Comparative Example 2.
상기 사용예 1 내지 6에서 제조된 그라프트 공중합체를 염화칼슘 수용액 5.0 중량부로 응고시키고 세척하여 수득한 분말을 비교한 결과를 하기 표 2에 나타내었다.The graft copolymers prepared in Examples 1 to 6 were coagulated with 5.0 parts by weight of an aqueous calcium chloride solution, and the powders obtained by washing were shown in Table 2 below.
[표 2]TABLE 2
상기 표 2에 나타낸 바와 같이, 반응형 유화제를 첨가하여 제조한 고무라텍스를 사용하여 제조한 그라프트 공중합체인 사용예 1, 2, 3, 및 4의 경우, 반응형 유화제를 첨가하지 않은 사용예 5, 및 6보다 헤이즈값이 우수하고, 중합 후의 응고물 생성이 적음을 확인 할 수 있었다.As shown in Table 2, in Examples 1, 2, 3, and 4, which are graft copolymers prepared using a rubber latex prepared by adding a reactive emulsifier, use example 5 without a reactive emulsifier was added. It was confirmed that the haze value was superior to, and 6, and the formation of coagulum after polymerization was less.
본 발명의 제조방법은 안정성을 증가시켜 응고물 생성을 줄이고 고무 입경 분포가 좁은 고무라텍스를 제조할 수 있을 뿐만 아니라, 고충격성, 및 고투명성이 우수한 투명 아크릴로니트릴-부타디엔-스티렌 수지를 제조할 수 있는 안정성이 우수한 고무라텍스를 제공할 수 있다.The production method of the present invention can increase the stability to reduce the formation of coagulum and to produce a rubber latex having a narrow rubber particle size distribution, as well as to prepare a transparent acrylonitrile-butadiene-styrene resin excellent in high impact and high transparency. It is possible to provide a rubber latex with excellent stability.
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Cited By (6)
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KR100923626B1 (en) * | 2007-11-07 | 2009-10-23 | 주식회사 엘지화학 | Method for preparing thermoplastic resin having superior gloss, impact strength and whiteness |
WO2014208965A1 (en) * | 2013-06-28 | 2014-12-31 | (주) 엘지화학 | Method for preparing thermoplastic resin composition with remarkable surface clearness and gloss |
EP2759553A4 (en) * | 2011-11-24 | 2015-06-24 | Lg Chemical Ltd | Production method for nitrile rubber |
KR20160073005A (en) * | 2014-12-16 | 2016-06-24 | 주식회사 엘지화학 | Preparation method of diene rubber polymer and acrylonitrile-butadiene-styrene graft copolymer comprising the same |
US9920153B2 (en) | 2013-06-28 | 2018-03-20 | Lg Chem, Ltd. | Method of preparing thermoplastic resin composition having superior surface clearness and gloss |
KR20230039948A (en) * | 2021-09-15 | 2023-03-22 | 금호석유화학 주식회사 | Composition for latex polymerization, latex for dip molding and dip molded article prepared therefrom |
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JPH08333489A (en) * | 1995-06-05 | 1996-12-17 | Japan Synthetic Rubber Co Ltd | Rubberlike polymer latex for base rubber of rubber-reinforced vinyl polymer, rubber-reinforced vinyl polymer, and thermoplastic polymer composition |
JPH09296015A (en) * | 1996-04-30 | 1997-11-18 | Kao Corp | Manufacture of abs polymer latex |
JPH11117189A (en) * | 1997-10-15 | 1999-04-27 | Asahi Chem Ind Co Ltd | Copolymer latex for paper coating and composition for paper coating |
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KR100923626B1 (en) * | 2007-11-07 | 2009-10-23 | 주식회사 엘지화학 | Method for preparing thermoplastic resin having superior gloss, impact strength and whiteness |
EP2759553A4 (en) * | 2011-11-24 | 2015-06-24 | Lg Chemical Ltd | Production method for nitrile rubber |
US9163096B2 (en) | 2011-11-24 | 2015-10-20 | Lg Chem, Ltd. | Method for producing nitrile rubber |
WO2014208965A1 (en) * | 2013-06-28 | 2014-12-31 | (주) 엘지화학 | Method for preparing thermoplastic resin composition with remarkable surface clearness and gloss |
US9920153B2 (en) | 2013-06-28 | 2018-03-20 | Lg Chem, Ltd. | Method of preparing thermoplastic resin composition having superior surface clearness and gloss |
KR20160073005A (en) * | 2014-12-16 | 2016-06-24 | 주식회사 엘지화학 | Preparation method of diene rubber polymer and acrylonitrile-butadiene-styrene graft copolymer comprising the same |
US10385154B2 (en) | 2014-12-16 | 2019-08-20 | Lg Chem, Ltd. | Method for preparing diene-based rubber polymer, diene-based rubber polymer prepared therefrom and acrylonitrile-butadiene-styrene graft copolymer of core-shell structure comprising the same |
KR20230039948A (en) * | 2021-09-15 | 2023-03-22 | 금호석유화학 주식회사 | Composition for latex polymerization, latex for dip molding and dip molded article prepared therefrom |
WO2023043115A1 (en) * | 2021-09-15 | 2023-03-23 | 금호석유화학 주식회사 | Composition for latex polymerization, latex for dip molding, and dip molded products manufactured therefrom |
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