KR102785992B1 - Acryl based copolymer composition, method for preparing the same and acryl based copolymer formulation comprising the same - Google Patents
Acryl based copolymer composition, method for preparing the same and acryl based copolymer formulation comprising the same Download PDFInfo
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- KR102785992B1 KR102785992B1 KR1020200019468A KR20200019468A KR102785992B1 KR 102785992 B1 KR102785992 B1 KR 102785992B1 KR 1020200019468 A KR1020200019468 A KR 1020200019468A KR 20200019468 A KR20200019468 A KR 20200019468A KR 102785992 B1 KR102785992 B1 KR 102785992B1
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- South Korea
- Prior art keywords
- acrylic copolymer
- derived
- monomer
- weight
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- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title description 25
- -1 Acryl Chemical group 0.000 title description 22
- 229920001577 copolymer Polymers 0.000 title description 4
- 238000009472 formulation Methods 0.000 title 1
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 114
- 239000000178 monomer Substances 0.000 claims abstract description 105
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004132 cross linking Methods 0.000 claims description 39
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 27
- 229940114926 stearate Drugs 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 9
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 7
- 230000001112 coagulating effect Effects 0.000 claims description 4
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 claims description 3
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 claims description 3
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 2
- 229940063655 aluminum stearate Drugs 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 229940114930 potassium stearate Drugs 0.000 claims description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- CVUNPKSKGHPMSY-UHFFFAOYSA-N ethyl 2-chloroprop-2-enoate Chemical compound CCOC(=O)C(Cl)=C CVUNPKSKGHPMSY-UHFFFAOYSA-N 0.000 claims 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 49
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 48
- 238000002156 mixing Methods 0.000 description 29
- 239000001530 fumaric acid Substances 0.000 description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 24
- 239000011976 maleic acid Substances 0.000 description 24
- 239000003921 oil Substances 0.000 description 21
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000000654 additive Substances 0.000 description 10
- 239000003995 emulsifying agent Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 8
- 229920000800 acrylic rubber Polymers 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229920000058 polyacrylate Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 230000001976 improved effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 2
- GDQGWFDELPKLJJ-UHFFFAOYSA-N (4-methyl-2-bicyclo[2.2.1]hept-5-enyl) 2-chloroacetate Chemical compound C1C(OC(=O)CCl)C2C=CC1(C)C2 GDQGWFDELPKLJJ-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- GPOGMJLHWQHEGF-UHFFFAOYSA-N 2-chloroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCl GPOGMJLHWQHEGF-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- KWCPPCKBBRBYEE-UHFFFAOYSA-N 3-chloropropyl prop-2-enoate Chemical compound ClCCCOC(=O)C=C KWCPPCKBBRBYEE-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 1
- QQQFIOWFLQTODN-UHFFFAOYSA-N 4-chlorobut-2-enyl prop-2-enoate Chemical compound ClCC=CCOC(=O)C=C QQQFIOWFLQTODN-UHFFFAOYSA-N 0.000 description 1
- MSZCRKZKNKSJNU-UHFFFAOYSA-N 4-chlorobutyl prop-2-enoate Chemical compound ClCCCCOC(=O)C=C MSZCRKZKNKSJNU-UHFFFAOYSA-N 0.000 description 1
- UVFFMASFIIKUOD-UHFFFAOYSA-N 5-(chloromethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCl)CC1C=C2 UVFFMASFIIKUOD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 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
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- DFEHSFZILGOAJK-UHFFFAOYSA-N ethenyl 2-bromoacetate Chemical compound BrCC(=O)OC=C DFEHSFZILGOAJK-UHFFFAOYSA-N 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- ATPFMBHTMKBVLS-UHFFFAOYSA-N n-[6-(cinnamylideneamino)hexyl]-3-phenylprop-2-en-1-imine Chemical compound C=1C=CC=CC=1C=CC=NCCCCCCN=CC=CC1=CC=CC=C1 ATPFMBHTMKBVLS-UHFFFAOYSA-N 0.000 description 1
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- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
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- 239000004014 plasticizer Substances 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- VMBJJCDVORDOCF-UHFFFAOYSA-N prop-2-enyl 2-chloroacetate Chemical compound ClCC(=O)OCC=C VMBJJCDVORDOCF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- UNZSHUCNBUBSGW-IFNWOZJISA-M sodium;(9z,12z,15z)-octadeca-9,12,15-trienoate Chemical compound [Na+].CC\C=C/C\C=C/C\C=C/CCCCCCCC([O-])=O UNZSHUCNBUBSGW-IFNWOZJISA-M 0.000 description 1
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- OAHWWXAJFXEIPX-UHFFFAOYSA-M tributyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC OAHWWXAJFXEIPX-UHFFFAOYSA-M 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/18—Increasing the size of the dispersed particles
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 아크릴계 공중합체 조성물에 관한 것으로, 보다 상세하게는 아크릴계 공중합체 및 금속 스테아레이트 또는 이의 염을 포함하고, 상기 아크릴계 공중합체는 주단량체 유래 반복단위 및 알파-메틸스티렌 다이머(α-methylstyrene dimer) 유래부를 포함하되, 상기 주단량체 유래 반복단위는, (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위, (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위 및 가교성 단량체 유래부를 포함하는 아크릴계 공중합체 조성물을 제공한다.The present invention relates to an acrylic copolymer composition, and more specifically, to an acrylic copolymer composition comprising an acrylic copolymer and a metal stearate or a salt thereof, wherein the acrylic copolymer comprises a repeating unit derived from a main monomer and a portion derived from an α-methylstyrene dimer, wherein the repeating unit derived from the main monomer comprises a repeating unit derived from a (meth)acrylic acid alkyl ester monomer, a repeating unit derived from a (meth)acrylic acid alkoxy alkyl ester monomer, and a portion derived from a crosslinkable monomer.
Description
본 발명은 아크릴계 공중합체 조성물, 이의 제조방법 및 이를 포함하는 아크릴계 공중합체 배합물에 관한 것으로, 보다 상세하게는 아크릴계 공중합체 조성물을 제조하고, 이를 포함하여 내유성 및 작업성이 우수하고 가교 속도가 빠른 아크릴계 공중합체 배합물로 응용하는 기술이 관한 것이다.The present invention relates to an acrylic copolymer composition, a method for producing the same, and an acrylic copolymer blend comprising the same, and more specifically, to a technique for producing an acrylic copolymer composition and applying the same to an acrylic copolymer blend having excellent oil resistance and workability and a fast crosslinking rate.
아크릴 고무는 아크릴산 에스테르를 주성분으로 하는 중합체로 내열성, 내유성 및 내오존성이 우수한 고무로 알려져 있으며 자동차 관련 분야 등에서 씰, 호스, 튜브, 벨트 등의 부품소재로 넓게 이용된다. 아크릴 고무는 소량이지만 자동차의 성능을 좌우하는 중요한 부분에 주로 사용되며, 그 특성상 진동 및 소음이 발생되는 부위에 적용되는 부분과 내열성 및 내유성이 필요한 부위에 적용되는 부분 등 중요한 부품으로 자리 잡고 있다.Acrylic rubber is a polymer with acrylic acid ester as its main component, and is known as a rubber with excellent heat resistance, oil resistance, and ozone resistance, and is widely used as a material for parts such as seals, hoses, tubes, and belts in the automobile-related field. Acrylic rubber is mainly used in small quantities but important parts that determine the performance of automobiles, and due to its characteristics, it is positioned as an important part, such as parts applied to areas where vibration and noise are generated and parts applied to areas that require heat resistance and oil resistance.
이러한 가교성 아크릴 고무는 일반적으로 카본블랙 등의 충전제와 가교제 등을 배합하여 제조된다. 배합 후의 가교성 아크릴 고무 배합물을 사용하여 원하는 형상을 가지는 성형체를 만들고 다양한 용도로 이용하고 있다. 이때 가교성 아크릴 고무의 가교 속도가 빠르면 성형체를 만드는 작업 시간을 단축할 수 있어 생산성을 향상시킬 수 있다.These crosslinked acrylic rubbers are generally manufactured by mixing fillers such as carbon black and crosslinking agents. The crosslinked acrylic rubber mixture after mixing is used to make molded articles having a desired shape and is used for various purposes. At this time, if the crosslinking speed of the crosslinked acrylic rubber is fast, the work time for making the molded article can be shortened, thereby improving productivity.
최근, 내연기관의 고출력화에 의해 열적 조건이 가혹해지고 엔진 오일의 고온 사용으로 인해 고무 부품의 성능 향상이 요구되고 있다. 이와 같이 가교성 아크릴 고무는 우수한 내유성을 필요로 한다. 또한, 성형품을 만드는 생산성을 향상시키기 위해 작업성을 향상시키고, 가교 속도를 빠르게 하는 것이 유리하다.Recently, due to the high output of internal combustion engines, thermal conditions have become more severe, and the performance of rubber parts has been demanded due to the high temperature use of engine oil. Accordingly, crosslinked acrylic rubber requires excellent oil resistance. In addition, it is advantageous to improve workability and increase the crosslinking speed in order to improve the productivity of making molded products.
본 발명에서 해결하고자 하는 과제는, 상기 발명의 배경이 되는 기술에서 언급한 문제들을 해결하기 위하여, 아크릴계 공중합체 조성물을 제조하고, 이를 포함하여 내유성 및 작업성이 우수하고, 가교 속도가 빠른 아크릴계 공중합체 배합물을 제공하는 것을 목적으로 한다.The problem to be solved in the present invention is to prepare an acrylic copolymer composition and provide an acrylic copolymer blend having excellent oil resistance and workability and a fast crosslinking speed, in order to solve the problems mentioned in the background technology of the above invention.
상기의 과제를 해결하기 위한 본 발명의 일 실시예에 따르면, 본 발명은 아크릴계 공중합체 및 금속 스테아레이트 또는 이의 염을 포함하고, 상기 아크릴계 공중합체는 주단량체 유래 반복단위 및 알파-메틸스티렌 다이머(α-methylstyrene dimer) 유래부를 포함하되, 상기 주단량체 유래 반복단위는, (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위, (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위 및 가교성 단량체 유래부를 포함하는 아크릴계 공중합체 조성물을 제공한다.According to one embodiment of the present invention for solving the above problems, the present invention provides an acrylic copolymer composition comprising an acrylic copolymer and a metal stearate or a salt thereof, wherein the acrylic copolymer comprises a repeating unit derived from a main monomer and a portion derived from an α-methylstyrene dimer, wherein the repeating unit derived from the main monomer comprises a repeating unit derived from a (meth)acrylic acid alkyl ester monomer, a repeating unit derived from a (meth)acrylic acid alkoxy alkyl ester monomer, and a portion derived from a crosslinkable monomer.
또한, 본 발명은 (메타)아크릴산 알킬 에스테르 단량체, (메타)아크릴산 알콕시 알킬 에스테르 단량체 및 가교성 단량체를 포함하는 주단량체 혼합물을 제조하는 단계; 상기 주단량체 혼합물에 알파-메틸스티렌 다이머를 투입하고 중합하여 아크릴계 공중합체를 수득하는 단계; 및 상기 아크릴계 공중합체에 금속 스테아레이트 또는 이의 염을 첨가한 후 응집하는 단계를 포함하는 아크릴계 공중합체 조성물의 제조방법을 제공한다.In addition, the present invention provides a method for producing an acrylic copolymer composition, comprising the steps of: producing a main monomer mixture including a (meth)acrylic acid alkyl ester monomer, a (meth)acrylic acid alkoxy alkyl ester monomer, and a crosslinking monomer; adding alpha-methylstyrene dimer to the main monomer mixture and polymerizing it to obtain an acrylic copolymer; and adding metal stearate or a salt thereof to the acrylic copolymer and then coagulating it.
또한, 본 발명은 본 발명에 따른 아크릴계 공중합체 조성물 및 충전제를 포함하는 아크릴계 공중합체 배합물을 제공한다.In addition, the present invention provides an acrylic copolymer blend comprising an acrylic copolymer composition and a filler according to the present invention.
본 발명에 따른 알파-메틸스티렌 다이머 및 금속 스테아레이트를 동시에 포함하는 아크릴계 공중합체 조성물은 중합물의 가교밀도를 향상시켜 내유성이 우수하고, 성형품 제작 시 작업성이 우수하며 가교 속도가 빠른 효과가 있다.An acrylic copolymer composition containing alpha-methylstyrene dimer and metal stearate according to the present invention has the effects of improving the crosslinking density of a polymer, thereby providing excellent oil resistance, excellent workability in producing a molded product, and a fast crosslinking speed.
본 발명의 설명 및 청구범위에서 사용된 용어나 단어는, 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여, 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in the description and claims of the present invention should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of the present invention, based on the principle that the inventor can appropriately define the concept of the term in order to explain his or her own invention in the best manner.
본 발명에서 용어 '유래 반복단위' 및 '유래부'는 어떤 물질로부터 기인한 성분, 구조 또는 그 물질 자체를 나타내는 것일 수 있고, 구체적인 예로, '유래 반복단위'는 중합체의 중합 시, 투입되는 단량체가 중합 반응에 참여하여 중합체 내에서 이루는 반복단위를 의미하는 것일 수 있으며, '유래부'는 중합체의 중합 시, 투입되는 연쇄 이동제가 중합 반응에 참여하여 중합물의 연쇄이동 반응을 유도하는 것일 수 있다.In the present invention, the terms 'derived repeating unit' and 'derived portion' may represent a component, structure, or the substance itself derived from a certain substance, and as a specific example, the 'derived repeating unit' may mean a repeating unit formed within a polymer by a monomer introduced during polymerization participating in a polymerization reaction, and the 'derived portion' may mean a chain transfer agent introduced during polymerization participating in a polymerization reaction to induce a chain transfer reaction of a polymer.
본 발명에서 용어 '고무'는 탄성을 가지는 가소성 물질을 나타내는 것으로, 러버, 엘라스토머, 또는 합성 라텍스 등을 의미하는 것일 수 있다.In the present invention, the term 'rubber' refers to a plastic material having elasticity, and may mean rubber, elastomer, or synthetic latex.
본 발명에서 용어 '공중합체(copolymer)'는 공단량체가 공중합되어 형성된 공중합체를 모두 포함하는 의미일 수 있고, 구체적인 예로, 랜덤 공중합체 및 블록 공중합체를 모두 포함하는 의미일 수 있다.In the present invention, the term 'copolymer' may mean all copolymers formed by copolymerizing comonomers, and as a specific example, may mean all random copolymers and block copolymers.
이하, 본 발명에 대한 이해를 돕기 위하여 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail to help understand the present invention.
본 발명에 따른 아크릴계 공중합체 조성물은 아크릴계 공중합체 및 금속 스테아레이트 또는 이의 염을 포함하고, 상기 아크릴계 공중합체는 주단량체 유래 반복단위 및 알파-메틸스티렌 다이머(α-methylstyrene dimer) 유래부를 포함하되, 상기 주단량체 유래 반복단위는, (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위, (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위 및 가교성 단량체 유래부를 포함하는 것일 수 있다.An acrylic copolymer composition according to the present invention comprises an acrylic copolymer and a metal stearate or a salt thereof, wherein the acrylic copolymer comprises a repeating unit derived from a main monomer and a portion derived from an α-methylstyrene dimer, wherein the repeating unit derived from the main monomer may comprise a repeating unit derived from a (meth)acrylic acid alkyl ester monomer, a repeating unit derived from a (meth)acrylic acid alkoxy alkyl ester monomer, and a portion derived from a crosslinkable monomer.
본 발명의 일 실시예에 따르면, 상기 (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위는 아크릴계 공중합체 내에서 유리전이 온도를 조절하여 최종 제품에서의 작업성, 내열성 및 내한성을 증가시키는 역할을 하는 성분으로서, 탄소수 1 내지 8의 알킬기를 함유하는 (메타)아크릴산 알킬 에스테르 단량체일 수 있다. 이때, 상기 탄소수 1 내지 8의 알킬기는 탄소수 1 내지 8의 선형 또는 고리형 알킬기를 포함하는 의미일 수 있다. 구체적인 예로, 상기 (메타)아크릴산 알킬 에스테르 단량체는 (메타)아크릴산 메틸, (메타)아크릴산 에틸, (메타)아크릴산 프로필, (메타)아크릴산 이소프로필, (메타)아크릴산 n-부틸, (메타)아크릴산 이소부틸, (메타)아크릴산 n-아밀, (메타)아크릴산 아이소아밀, (메타)아크릴산 n-헥실, (메타)아크릴산 2-에틸헥실, (메타)아크릴산 사이클로헥실 등일 수 있다. 여기서, (메타)아크릴산 알킬 에스테르 단량체는 1종 또는 2종 이상을 조합하여 사용할 수 있으며, 구체적인 예로, (메타)아크릴산 에틸, (메타)아크릴산 n-부틸 단량체 등일 수 있다.According to one embodiment of the present invention, the repeating unit derived from the (meth)acrylic acid alkyl ester monomer is a component that controls the glass transition temperature in an acrylic copolymer and thus increases workability, heat resistance, and cold resistance in a final product, and may be a (meth)acrylic acid alkyl ester monomer containing an alkyl group having 1 to 8 carbon atoms. In this case, the alkyl group having 1 to 8 carbon atoms may mean a linear or cyclic alkyl group having 1 to 8 carbon atoms. As a specific example, the (meth)acrylic acid alkyl ester monomer may be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. Here, the (meth)acrylic acid alkyl ester monomer may be used alone or in combination of two or more, and as a specific example, the monomer may be ethyl (meth)acrylate, n-butyl (meth)acrylate, etc.
상기 주단량체 유래 반복단위 내 상기 (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위의 함량은 65 내지 95 중량%, 75 내지 93 중량%, 또는 80 내지 90 중량%일 수 있고, 이 범위 내에서 본 발명에 따른 아크릴계 공중합체로부터 제조된 성형품의 작업성, 내열성 및 내한성이 우수한 효과가 있다.The content of the (meth)acrylic acid alkyl ester monomer-derived repeating unit in the above-mentioned main monomer-derived repeating unit may be 65 to 95 wt%, 75 to 93 wt%, or 80 to 90 wt%, and within this range, the molded article manufactured from the acrylic copolymer according to the present invention has excellent workability, heat resistance, and cold resistance.
상기 (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위는 아크릴계 공중합체 내에서 유리전이 온도를 조절하여 최종 제품에서의 작업성, 내열성 및 내한성을 증가시키는 역할을 하는 성분으로서, 탄소수 1 내지 8의 알콕시알킬기를 함유하는 (메타)아크릴산 알킬 에스테르 단량체를 의미하는 것일 수 있다. 구체적인 예로, 상기 (메타)아크릴산 알콕시 알킬 에스테르 단량체는 (메타)아크릴산 메톡시메틸, (메타)아크릴산 에톡시메틸, (메타)아크릴산 2-에톡시에틸, (메타)아크릴산 2-부톡시에틸, (메타)아크릴산2-메톡시에틸, (메타)아크릴산 2-프로폭시에틸, (메타)아크릴산 3-메톡시 프로필, (메타)아크릴산 4-메톡시부틸 등일 수 있다. 구체적인 예로, 상기 (메타)아크릴산 알콕시 알킬 에스테르 단량체는 (메타)아크릴산 2-메톡시에틸일 수 있다.The above (meth)acrylic acid alkoxy alkyl ester monomer-derived repeating unit is a component that controls the glass transition temperature in an acrylic copolymer and increases workability, heat resistance and cold resistance in the final product, and may refer to a (meth)acrylic acid alkyl ester monomer containing an alkoxyalkyl group having 1 to 8 carbon atoms. As a specific example, the (meth)acrylic acid alkoxy alkyl ester monomer may be (meth)acrylic acid methoxymethyl, (meth)acrylic acid ethoxymethyl, (meth)acrylic acid 2-ethoxyethyl, (meth)acrylic acid 2-butoxyethyl, (meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid 2-propoxyethyl, (meth)acrylic acid 3-methoxy propyl, (meth)acrylic acid 4-methoxybutyl, etc. As a specific example, the (meth)acrylic acid alkoxy alkyl ester monomer may be (meth)acrylic acid 2-methoxyethyl.
상기 주단량체 유래 반복단위 내 상기 (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위의 함량은 5 내지 35 중량%, 7 내지 25 중량%, 또는 10 내지 20 중량%일 수 있고, 이 범위 내에서 본 발명에 따른 아크릴계 공중합체로부터 성형된 성형품의 작업성 및 내유성이 우수한 효과가 있다.The content of the repeating unit derived from the (meth)acrylic acid alkoxy alkyl ester monomer in the repeating unit derived from the main monomer may be 5 to 35 wt%, 7 to 25 wt%, or 10 to 20 wt%, and within this range, the molded article molded from the acrylic copolymer according to the present invention has excellent workability and oil resistance.
한편, 본 발명에 따른 상기 주단량체 유래 반복단위에 포함되는 (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위 및 (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위의 총 함량은 80 내지 99.9 중량%, 85 내지 99.9 중량% 또는 90 내지 99.5 중량%일 수 있고, 이 범위 내에서 본 발명에 따른 아크릴계 공중합체로부터 제조된 성형품의 작업성 내한성 및 내열성이 우수한 효과가 있다.Meanwhile, the total content of the (meth)acrylic acid alkyl ester monomer-derived repeating unit and the (meth)acrylic acid alkoxy alkyl ester monomer-derived repeating unit included in the main monomer-derived repeating unit according to the present invention may be 80 to 99.9 wt%, 85 to 99.9 wt%, or 90 to 99.5 wt%, and within this range, the molded article manufactured from the acrylic copolymer according to the present invention has excellent workability, cold resistance, and heat resistance.
상기 가교성 단량체 유래부는 아크릴계 공중합체 내 가교성 관능기를 부여하기 위한 성분으로서, 부텐디온산 모노에스테르 단량체, 에폭시기 함유 단량체 및 할로겐 함유 단량체로 이루어진 군에서 선택되는 1종 이상일 수 있다.The above crosslinking monomer-derived portion is a component for providing a crosslinking functional group in an acrylic copolymer, and may be at least one selected from the group consisting of a butenedioic acid monoester monomer, an epoxy group-containing monomer, and a halogen-containing monomer.
상기 부텐디온산 모노에스테르 단량체는 부텐디온산, 즉 말레산 또는 푸마르산의 카르복실기와 알코올을 반응시켜 얻어진 말레산 모노에스테르 단량체 또는 푸마르산 모노에스테르 단량체일 수 있다. 상기 말레산 모노에스테르 단량체는 말레산 모노메틸, 말레산 모노에틸, 말레산 모노프로필, 말레인산 모노부틸, 말레산 모노펜틸, 말레산 모노데실 등의 말레산 모노알킬에스테르 단량체； 말레산 모노사이클로펜틸, 말레산 모노사이클로헥실, 말레산 모노사이클로헵틸, 말레산 모노사이클로옥틸, 말레산 모노메틸 사이클로헥실, 말레산 모노- 3,5-디메틸사이클로헥실, 말레산 모노디사이클로펜타닐, 말레산 모노이소보닐 등의 말레산 모노사이클로알킬 에스테르 단량체； 말레산 모노사이클로펜테닐, 말레산 모노사이클로헥세닐, 말레산 모노사이클로헵테닐, 말레산 모노사이클로옥테닐, 말레인산 디 사이클로펜타디에닐 등의 말레산 모노사이클로알케닐 에스테르 단량체; 등일 수 있다. 상기 푸마르산 모노에스테르 단량체는 푸마르산 모노메틸, 푸마르산 모노에틸, 푸마르산 모노프로필, 푸마르산 모노부틸, 푸마르산 모노헥실, 푸마르산 모노옥틸 등의 푸마르산 모노알킬에스테르 단량체； 푸마르산 모노사이클로펜틸, 푸마르산 모노사이클로헥실, 푸마르산 모노사이클로헵틸, 푸마르산 모노사이클로옥틸, 푸마르산 모노메틸 사이클로헥실, 푸마르산 모노- 3,5-디메틸사이클로헥실, 푸마르산 디사이클로펜타닐, 후말산이소보닐 등의 푸마르산 모노사이클로알킬 에스테르 단량체； 푸마르산 모노사이클로펜테닐, 푸마르산 모노사이클로헥세닐, 푸마르산 모노사이클로헵테닐, 푸마르산 모노사이클로옥테닐, 푸마르산 모노디사이클로펜타디에닐 등의 푸마르산 모노사이클로알케닐 에스테르 단량체 등일 수 있다. The above butenedioic acid monoester monomer may be a maleic acid monoester monomer or a fumaric acid monoester monomer obtained by reacting a carboxyl group of butenedioic acid, i.e. maleic acid or fumaric acid, with an alcohol. The above maleic acid monoester monomers may be maleic acid monoalkyl ester monomers such as maleic acid monomethyl, maleic acid monoethyl, maleic acid monopropyl, maleic acid monobutyl, maleic acid monopentyl, and maleic acid monodecyl; maleic acid monocyclopentyl, maleic acid monocyclohexyl, maleic acid monocycloheptyl, maleic acid monocyclooctyl, maleic acid monomethyl cyclohexyl, maleic acid mono-3,5-dimethylcyclohexyl, maleic acid monodicyclopentanyl, and maleic acid monoisobornyl; maleic acid monocycloalkenyl ester monomers such as maleic acid monocyclopentenyl, maleic acid monocyclohexenyl, maleic acid monocycloheptenyl, maleic acid monocyclooctenyl, and maleic acid dicyclopentadienyl; etc. The above fumaric acid monoester monomers may be fumaric acid monoalkyl ester monomers such as fumaric acid monomethyl, fumaric acid monoethyl, fumaric acid monopropyl, fumaric acid monobutyl, fumaric acid monohexyl, and fumaric acid monooctyl; fumaric acid monocycloalkyl ester monomers such as fumaric acid monocyclopentyl, fumaric acid monocyclohexyl, fumaric acid monocycloheptyl, fumaric acid monocyclooctyl, fumaric acid monomethyl cyclohexyl, fumaric acid mono-3,5-dimethylcyclohexyl, fumaric acid dicyclopentanyl, and fumaric acid isobornyl; fumaric acid monocycloalkenyl ester monomers such as fumaric acid monocyclopentenyl, fumaric acid monocyclohexenyl, fumaric acid monocycloheptenyl, fumaric acid monocyclooctenyl, and fumaric acid monodicyclopentadienyl.
상기 에폭시기 함유 단량체는 글리시딜(메타) 아크릴레이트, 비닐글리시딜에테르, 알릴글리시딜에테르, 메타크릴 글리시딜에테르 등일 수 있다. 구체적인 예로, 상기 에폭시기 함유 단량체는 글리시딜(메타) 아크릴레이트, 알릴글리시딜에테르 등일 수 있다. The above epoxy group-containing monomer may be glycidyl (meth)acrylate, vinyl glycidyl ether, allyl glycidyl ether, methacryl glycidyl ether, etc. As a specific example, the above epoxy group-containing monomer may be glycidyl (meth)acrylate, allyl glycidyl ether, etc.
상기 할로겐 함유 단량체는 비닐클로로아세테이트, 비닐 브로모 아세테이트, 알릴 클로로 아세테이트, 비닐 클로로 프로피오네이트, 비닐 클로로 부틸레이트, 비닐 브로모 부틸레이트, 2-클로로 아크릴산에틸, 3-클로로 프로필아크릴레이트, 4-클로로부틸 아크릴레이트, 2-클로로 에틸메타크릴레이트, 2-브로모 아크릴산에틸, 2-요오드 아크릴산에틸, 2-클로로에틸비닐에테르, 클로로 메틸 비닐 에테르, 4-클로로-2-부테닐 아크릴레이트, 비닐 벤질 클로라이드, 5-클로로메틸-2-노르보르넨, 5-클로로아세톡시 메틸-2-노르보르넨 등일 수 있다. 구체적인 예로, 상기 할로겐 함유 단량체는 비닐클로로아세테이트, 비닐 벤질 클로라이드, 2-클로로 아크릴산에틸, 2-클로로에틸비닐에테르 등일 수 있다.The above halogen-containing monomers may be vinylchloroacetate, vinyl bromo acetate, allyl chloro acetate, vinyl chloro propionate, vinyl chloro butylate, vinyl bromo butylate, 2-chloro ethyl acrylate, 3-chloro propyl acrylate, 4-chlorobutyl acrylate, 2-chloro ethyl methacrylate, 2-bromo acrylate, 2-iodo acrylate ethyl, 2-chloroethyl vinyl ether, chloro methyl vinyl ether, 4-chloro-2-butenyl acrylate, vinyl benzyl chloride, 5-chloromethyl-2-norbornene, 5-chloroacetoxy methyl-2-norbornene, and the like. As specific examples, the halogen-containing monomers may be vinylchloroacetate, vinyl benzyl chloride, 2-chloro ethyl acrylate, 2-chloroethyl vinyl ether, and the like.
상기 주단량체 유래 반복단위 내 가교성 단량체 유래부의 함량은 0.1 내지 20 중량%, 0.1 내지 15 중량% 또는 0.5 내지 10 중량%일 수 있고, 이 범위 내에서 본 발명에 따른 아크릴계 공중합체의 가교밀도가 높아지고, 아크릴계 공중합체로부터 제조된 성형품의 신장이 향상될 뿐만 아니라, 압축 영구 변형을 방지하는 효과가 있다.The content of the crosslinkable monomer-derived portion in the repeating unit derived from the main monomer may be 0.1 to 20 wt%, 0.1 to 15 wt%, or 0.5 to 10 wt%, and within this range, the crosslinking density of the acrylic copolymer according to the present invention is increased, the elongation of a molded article manufactured from the acrylic copolymer is improved, and there is an effect of preventing compression set.
상기 주단량체 유래 반복단위는 상기 (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위, (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위 및 가교성 단량체 유래부 이외에 상기 상기 (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위 및 (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위와 공중합 가능한 다른 단량체 유래 반복단위를 더 포함할 수 있다.The above-mentioned main monomer-derived repeating unit may further include, in addition to the (meth)acrylic acid alkyl ester monomer-derived repeating unit, the (meth)acrylic acid alkoxy alkyl ester monomer-derived repeating unit, and the crosslinkable monomer-derived portion, another monomer-derived repeating unit copolymerizable with the (meth)acrylic acid alkyl ester monomer-derived repeating unit and the (meth)acrylic acid alkoxy alkyl ester monomer-derived repeating unit.
본 발명의 일 실시예에 따르면, 본 발명에 따른 아크릴계 공중합체는 전술한 주단량체 유래 반복단위 및 알파-메틸스티렌 다이머 유래부를 포함할 수 있다.According to one embodiment of the present invention, the acrylic copolymer according to the present invention may include a repeating unit derived from the aforementioned main monomer and an alpha-methylstyrene dimer derived portion.
상기 알파-메틸스티렌 다이머는 하기 화학식 1로 표현되는 화합물일 수 있다.The above alpha-methylstyrene dimer may be a compound represented by the following chemical formula 1.
[화학식 1][Chemical Formula 1]
상기 알파-메틸스티렌 다이머는 아크릴계 공중합체의 중합 반응 시, 중합 속도를 늦추어 발생하는 열을 낮추는 역할을 하는 성분이다. 또한, 본 발명에 따른 아크릴계 공중합체는 상기 알파-메틸스티렌 다이머 유래부를 포함함으로써, 상기 아크릴계 공중합체와, 금속 스테아레이트 또는 이의 염이 함께 응집되어 아크릴계 공중합체 조성물이 제조되는 과정에서 아크릴계 공중합체 조성물이 딱딱하게 응고되는 현상을 방지함으로써, 응집 후 충전제와 배합이 용이하도록 하여 작업성을 향상시키는 효과를 나타낸다.The above alpha-methylstyrene dimer is a component that plays a role in reducing the heat generated by slowing down the polymerization rate during the polymerization reaction of the acrylic copolymer. In addition, the acrylic copolymer according to the present invention, by including the alpha-methylstyrene dimer-derived portion, prevents the acrylic copolymer composition from hardening during the process in which the acrylic copolymer and the metal stearate or its salt are coagulated together to manufacture the acrylic copolymer composition, thereby improving workability by making it easy to mix with a filler after coagulation.
상기 알파-메틸스티렌 다이머 유래부의 함량은 상기 주단량체 유래 반복단위 전체 100 중량부에 대하여 0.001 내지 0.01 중량부, 0.001 내지 0.007 중량부 또는 0.001 내지 0.004 중량부일 수 있고, 이 범위 내에서 본 발명에 따른 아크릴계 공중합체 조성물과 충전제를 배합하여 아크릴계 공중합체 배합물로 제조 시, 가교 속도가 빨라지고, 배합 작업성이 우수한 효과가 있다. 또한, 상기 아크릴계 공중합체 배합물로부터 제조된 성형품의 내유성, 신장률 및 인장강도가 향상될 수 있다.The content of the alpha-methylstyrene dimer-derived portion may be 0.001 to 0.01 parts by weight, 0.001 to 0.007 parts by weight, or 0.001 to 0.004 parts by weight based on 100 parts by weight of the total repeating unit derived from the main monomer, and when the acrylic copolymer composition according to the present invention and the filler are blended within this range to produce an acrylic copolymer blend, the crosslinking speed is accelerated and the blending workability is excellent. In addition, the oil resistance, elongation, and tensile strength of the molded article produced from the acrylic copolymer blend can be improved.
상기 아크릴계 공중합체의 중량평균 분자량은 200,000 g/mol 내지 4,000,000 g/mol, 300,000 g/mol 내지 3,000,000 g/mol 또는 500,000 g/mol 내지 2,500,000 g/mol일 수 있고, 이 범위 내에서 본 발명에 따른 아크릴계 공중합체의 제조 시간이 절감되고, 아크릴계 공중합체로부터 제조된 성형품은 우수한 기계적 물성 구현이 가능한 효과가 있다.The weight average molecular weight of the acrylic copolymer may be 200,000 g/mol to 4,000,000 g/mol, 300,000 g/mol to 3,000,000 g/mol, or 500,000 g/mol to 2,500,000 g/mol. Within this range, the manufacturing time of the acrylic copolymer according to the present invention is reduced, and a molded article manufactured from the acrylic copolymer has the effect of being able to implement excellent mechanical properties.
본 발명의 일 실시예에 따르면, 본 발명에 따른 아크릴계 공중합체 조성물은 전술한 아크릴계 공중합체, 및 금속 스테아레이트 또는 이의 염을 포함할 수 있다.According to one embodiment of the present invention, the acrylic copolymer composition according to the present invention may include the above-described acrylic copolymer, and a metal stearate or a salt thereof.
상기 금속 스테아레이트 또는 이의 염은 아크릴계 공중합체 조성물의 제조 시, 단량체 간의 가교를 유도하여 중합물의 가교밀도를 높이는 성분으로, 탄소수 5 내지 25의 포화 또는 불포화 지방산의 기능기에 존재하는 수소 대신 리튬(Li), 아연(Zn), 알루미늄(Al), 칼슘(Ca), 마그네슘(Mg), 코발트(Co), 구리(Cu), 티타늄(Ti), 나트륨(Na), 지르코늄(Zr), 칼륨(K), 바륨(Ba), 망간(Mn) 또는 주석(Sn)이 치환된 금속염일 수 있다. 구체적으로 나트륨 스테아레이트, 마그네슘 스테아레이트, 칼슘 스테아레이트, 아연 스테아레이트, 리튬 스테아레이트 및 알루미늄 스테아레이트로 이루어진 군에서 선택되는 1종 이상일 수 있다. The above metal stearate or its salt is a component that induces crosslinking between monomers when producing an acrylic copolymer composition to increase the crosslinking density of the polymer, and may be a metal salt in which lithium (Li), zinc (Zn), aluminum (Al), calcium (Ca), magnesium (Mg), cobalt (Co), copper (Cu), titanium (Ti), sodium (Na), zirconium (Zr), potassium (K), barium (Ba), manganese (Mn), or tin (Sn) is substituted for hydrogen present in a functional group of a saturated or unsaturated fatty acid having 5 to 25 carbon atoms. Specifically, the metal stearate or salt thereof may be at least one selected from the group consisting of sodium stearate, magnesium stearate, calcium stearate, zinc stearate, lithium stearate, and aluminum stearate.
상기 금속 스테아레이트 또는 이의 염의 함량은 상기 주단량체 유래 반복단위 전체 100 중량부에 대하여, 0.5 내지 5 중량부, 1 내지 4 중량부, 또는 2 내지 3 중량부일 수 있고, 이 범위 내에서 본 발명에 따른 아크릴계 공중합체 조성물과 충전제를 배합하여 아크릴계 공중합체 배합물로 제조 시, 가교 속도가 빨라지고, 상기 아크릴계 공중합체 배합물로부터 제조된 성형품의 내유성, 신장률 및 인장강도가 우수한 효과가 있다.The content of the metal stearate or its salt may be 0.5 to 5 parts by weight, 1 to 4 parts by weight, or 2 to 3 parts by weight, based on 100 parts by weight of the total repeating unit derived from the main monomer, and when the acrylic copolymer composition according to the present invention and the filler are blended within this range to produce an acrylic copolymer blend, the crosslinking speed is accelerated, and the oil resistance, elongation, and tensile strength of the molded article produced from the acrylic copolymer blend are excellent.
본 발명의 일 실시예에 따르면, 상기 아크릴계 공중합체 조성물의 무늬점도(ML1+4, 100 ℃)는 10 내지 70, 20 내지 60, 또는 25 내지 50일 수 있다. 이 범위 내에서 작업성이 우수한 효과가 있다.According to one embodiment of the present invention, the patterned viscosity (ML 1+4 , 100° C.) of the acrylic copolymer composition may be 10 to 70, 20 to 60, or 25 to 50. Within this range, excellent workability is achieved.
본 발명에 따르면, 아크릴계 공중합체 조성물의 제조방법이 제공된다. 본 발명에 따른 아크릴계 공중합체 조성물의 제조방법은, (메타)아크릴산 알킬 에스테르 단량체, (메타)아크릴산 알콕시 알킬 에스테르 단량체 및 가교성 단량체를 포함하는 주단량체 혼합물을 제조하는 단계; 상기 주단량체 혼합물에 알파-메틸스티렌 다이머를 투입하고 중합하여 아크릴계 공중합체를 수득하는 단계; 및 상기 아크릴계 공중합체에 금속 스테아레이트 또는 이의 염을 첨가한 후 응집하는 단계를 포함할 수 있다. According to the present invention, a method for producing an acrylic copolymer composition is provided. The method for producing an acrylic copolymer composition according to the present invention may include a step of producing a main monomer mixture including a (meth)acrylic acid alkyl ester monomer, a (meth)acrylic acid alkoxy alkyl ester monomer, and a crosslinking monomer; a step of adding alpha-methylstyrene dimer to the main monomer mixture and polymerizing it to obtain an acrylic copolymer; and a step of adding a metal stearate or a salt thereof to the acrylic copolymer and then coagulating it.
상기 주단량체 혼합물을 제조하는 단계는, 아크릴계 공중합체의 주쇄를 이루는 단량체를 배합하는 단계일 수 있으며, 상기 주단량체 혼합물을 형성하기 위하여 투입되는 단량체의 종류 및 투입량은 앞서 기재한 주단량체 유래 반복단위를 형성하기 위한 단량체의 종류 및 함량과 동일한 것일 수 있다.The step of preparing the main monomer mixture may be a step of blending monomers forming the main chain of an acrylic copolymer, and the type and amount of monomers introduced to form the main monomer mixture may be the same as the type and amount of monomers for forming the repeating unit derived from the main monomer described above.
또한, 상기 알파-메틸스티렌 다이머를 투입하고 중합하는 단계는, 아크릴계 공중합체 수득을 위한 중합 단계일 수 있으며, 상기 투입되는 알파-메틸스티렌 다이머의 투입량은 앞서 기재한 알파-메틸스티렌 다이머 유래부를 형성하기 위한 알파-메틸스티렌 다이머의 함량과 동일한 것일 수 있다.In addition, the step of introducing and polymerizing the alpha-methylstyrene dimer may be a polymerization step for obtaining an acrylic copolymer, and the amount of the introduced alpha-methylstyrene dimer may be the same as the content of the alpha-methylstyrene dimer for forming the alpha-methylstyrene dimer-derived portion described above.
또한, 상기 금속 스테아레이트를 첨가한 후 응집하는 단계는, 상기 단량체 간의 가교를 유도하여 가교밀도가 향상된 아크릴계 공중합체 조성물을 형성하는 단계일 수 있으며, 상기 투입되는 금속 스테아레이트 또는 이의 염의 종류 및 투입량은 앞서 기재한 아크릴계 공중합체 조성물 상의, 금속 스테아레이트 또는 이의 염의 종류 및 함량과 동일한 것일 수 있다.In addition, the step of coagulating after adding the metal stearate may be a step of forming an acrylic copolymer composition with improved crosslinking density by inducing crosslinking between the monomers, and the type and amount of the metal stearate or its salt to be introduced may be the same as the type and content of the metal stearate or its salt in the acrylic copolymer composition described above.
상기 아크릴계 공중합체 수득을 위한 중합 단계는 유화 중합, 괴상 중합, 현탁 중합, 용액 중합 등의 방법을 이용하여 실시될 수 있고, 개시제, 유화제, 중합 정지제, 이온 교환수, 분자량 조절제, 활성화제, 산화환원촉매 등의 첨가제를 추가로 이용하여, 회분식, 반회분식, 연속식 등의 유화 중합 방법에 의해 실시될 수 있다.The polymerization step for obtaining the above acrylic copolymer can be carried out using a method such as emulsion polymerization, bulk polymerization, suspension polymerization, solution polymerization, etc., and can be carried out by an emulsion polymerization method such as batch, semi-batch, continuous, etc., additionally using additives such as an initiator, an emulsifier, a polymerization terminator, an ion exchange water, a molecular weight regulator, an activator, and a redox catalyst.
상기 개시제는 일례로 과황산나트륨, 과황산칼륨, 과황산암모늄, 과인산칼륨, 과산화수소 등의 무기 과산화물; 디이소프로필벤젠 하이드로퍼옥사이드, t-부틸 하이드로퍼옥사이드, 큐멘 하이드로퍼옥사이드, p-멘탄 하이드로퍼옥사이드, 디-t-부틸 퍼옥사이드, t-부틸쿠밀 퍼옥사이드, 아세틸 퍼옥사이드, 이소부틸 퍼옥사이드, 옥타노일퍼옥사이드, 벤조일 퍼옥사이드, 3,5,5-트리메틸헥산올 퍼옥사이드, t-부틸 퍼옥시 이소부틸레이트 등의 유기 과산화물; 아조비스 이소부티로니트릴, 아조비스-2,4-디메틸발레로니트릴, 아조비스시클로헥산카르보니트릴, 아조비스 이소낙산(부틸산)메틸 등의 질소 화합물 등일 수 있다. 이들 중합 개시제는 단독 또는 2종 이상을 조합해 사용할 수 있다. 이러한 개시제는 주단량체 혼합물 100 중량부에 대하여, 0.005 중량부 내지 0.2 중량부로 사용될 수 있다.The above initiator may be, for example, inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; organic peroxides such as diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, benzoyl peroxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxy isobutyrate; nitrogen compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid methyl. These polymerization initiators can be used alone or in combination of two or more. These initiators can be used in an amount of 0.005 to 0.2 parts by weight per 100 parts by weight of the main monomer mixture.
한편, 유기 과산화물 또는 무기 과산화물 개시제는 환원제와의 조합으로 레독스계 중합 개시제로서 사용할 수 있다. 이 환원제로서는 특별히 제한되지 않지만 황산제일철, 나프텐산 제1 구리 등의 환원 상태에 있는 금속 이온을 함유하는 화합물；메탄설폰산 나트륨 등의 설폰산 화합물；디메틸아닐린 등의 아민 화합물；등을 들 수 있다. 이들의 환원제는 단독으로 또는 2종 이상을 조합해 이용할 수 있다. 상기 환원제는 과산화물 1 중량부에 대하여, 0.005 중량부 내지 20 중량부로 사용될 수 있다.Meanwhile, an organic peroxide or inorganic peroxide initiator can be used as a redox polymerization initiator in combination with a reducing agent. The reducing agent is not particularly limited, but may include compounds containing metal ions in a reduced state, such as ferrous sulfate and cuprous naphthenate; sulfonic acid compounds, such as sodium methanesulfonate; amine compounds, such as dimethylaniline; and the like. These reducing agents can be used singly or in combination of two or more. The reducing agent can be used in an amount of 0.005 to 20 parts by weight relative to 1 part by weight of the peroxide.
상기 유화제는 음이온계 유화제, 양이온계 유화제 및 비이온계 유화제로 이루어지는 군으로부터 1종 이상 선택될 수 있으며, 구체적인 예로, 폴리옥시에틸렌 알킬에테르, 폴리옥시에틸렌 알킬페놀 에테르, 폴리옥시에틸렌 알킬 에스테르, 폴리옥시에틸렌소르비탄 알킬에스테르 등의 비이온성 유화제；미리스틴산, 팔미트산, 올레산, 리놀렌산 등의 지방산의 염, 도데실 벤젠설폰산 나트륨 등의 알킬 벤젠설폰산염, 고급 알코올 황산에스테르염, 알킬술포숙신산염 등의 음이온성 유화제；알킬 트리메틸 암모늄 클로라이드, 디알킬암모늄 클로라이드, 벤질 암모늄 클로라이드 등의 양이온성 유화제；α,β-불포화 카르복실산의 설포 에스테르, α,β-불포화 카르복실산의 설페이트 에스테르, 설포 알킬 아릴 에테르 등의 공중합성 유화제 등을 들 수 있다. 그 중에서도, 음이온성 유화제가 적합하게 이용된다. 상기 유화제는 주단량체 혼합물 100 중량부에 대하여, 0.1 중량부 내지 10 중량부로 사용될 수 있다. The above emulsifier may be at least one selected from the group consisting of anionic emulsifiers, cationic emulsifiers, and nonionic emulsifiers, and specific examples thereof include nonionic emulsifiers such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, and polyoxyethylene sorbitan alkyl esters; anionic emulsifiers such as salts of fatty acids such as myristic acid, palmitic acid, oleic acid, and linolenic acid, alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate, higher alcohol sulfate esters, and alkyl sulfosuccinates; cationic emulsifiers such as alkyl trimethyl ammonium chloride, dialkyl ammonium chloride, and benzyl ammonium chloride; and copolymerizable emulsifiers such as sulfo esters of α,β-unsaturated carboxylic acids, sulfate esters of α,β-unsaturated carboxylic acids, and sulfo alkyl aryl ethers. Among them, an anionic emulsifier is suitably used. The emulsifier can be used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the main monomer mixture.
상기 이온교환수로는 물을 사용할 수 있으며, 상기 이온교환수는 주단량체 혼합물 100 중량부에 대하여, 100 중량부 내지 400 중량부로 사용될 수 있다.Water can be used as the ion exchange water, and the ion exchange water can be used in an amount of 100 to 400 parts by weight per 100 parts by weight of the main monomer mixture.
상기 분자량 조절제는 일례로 t-도데실머캅탄, n-도데실머캅탄, 옥틸머캅탄 등의 머캅탄류; 사염화탄소, 염화메틸렌, 브롬화 메틸렌 등의 할로겐화 탄화수소; 테트라에틸 디우람 디설파이드, 디펜타메틸렌 디우람 디설파이드, 디이소프로필키산토겐 디설파이드 등의 유황 함유 화합물 등일 수 있다. 상기 분자량 조절제는 주단량체 혼합물 100 중량부에 대하여, 0.1 중량부 내지 3 중량부로 사용될 수 있다.The above molecular weight regulator may be, for example, mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide; and sulfur-containing compounds such as tetraethyl diuram disulfide, dipentamethylene diuram disulfide, and diisopropylxanthogen disulfide. The above molecular weight regulator may be used in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the main monomer mixture.
상기 활성화제는 일례로 하이드로아황산나트륨, 소듐포름알데히드 설폭시레이트, 소듐에틸 렌디아민 테트라아세테이트, 황산 제1 철, 락토오즈, 덱스트로오스, 리놀렌산나트륨, 및 황산나트륨 중에서 선택된 1 종 이상일 수 있다. 상기 활성화제는 주단량체 혼합물 100 중량부에 대하여, 0.01 중량부 내지 0.15 중량부로 사용될 수 있다.The above activator may be, for example, at least one selected from sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, lactose, dextrose, sodium linolenate, and sodium sulfate. The above activator may be used in an amount of 0.01 to 0.15 parts by weight based on 100 parts by weight of the main monomer mixture.
상기 산화환원촉매는 일례로 소듐 포름알데하이드 술폭실레이트, 황산 제1철, 디소듐 에틸렌디아민테 트라아세테이트, 제2 황산구리 등일 수 있다. 상기 산화환원촉매는 주단량체 혼합물 100 중량부에 대하여, 0.01 중량부 내지 0.1 중량부로 사용될 수 있다.The above redox catalyst may be, for example, sodium formaldehyde sulfoxylate, ferrous sulfate, disodium ethylenediaminetetraacetate, copper sulfate (2), etc. The above redox catalyst may be used in an amount of 0.01 to 0.1 parts by weight based on 100 parts by weight of the main monomer mixture.
본 발명에 따르면, 본 발명에 따른 아크릴계 공중합체 배합물은 상기와 같이 수득된 아크릴계 공중합체 조성물 및 충전제를 포함할 수 있다.According to the present invention, the acrylic copolymer blend according to the present invention may include the acrylic copolymer composition obtained as described above and a filler.
상기 충전제는 카본블랙, 실리카, 카올린 클레이, 탤크, 규조토 등일 수 있다. The above filler may be carbon black, silica, kaolin clay, talc, diatomaceous earth, or the like.
상기 충전제의 사용 함량은 아크릴계 공중합체 100 중량부에 대하여, 20 중량부 내지 80 중량부, 30 중량부 내지 65 중량부, 또한 45 중량부 내지 55 중량부일 수 있으며, 이 범위 내에서 배합 작업성이 향상되고, 아크릴계 공중합체 배합물로부터 제조된 성형품의 기계적 물성이 우수한 효과가 있다.The amount of the filler used may be 20 to 80 parts by weight, 30 to 65 parts by weight, or 45 to 55 parts by weight, based on 100 parts by weight of the acrylic copolymer. Within this range, the mixing workability is improved, and the mechanical properties of a molded product manufactured from the acrylic copolymer blend are excellent.
한편, 본 발명에 따른 아크릴계 공중합체 배합물은 배합 가교 효과를 증진시키기 위해 황을 더 포함할 수 있다.Meanwhile, the acrylic copolymer blend according to the present invention may further contain sulfur to enhance the blending crosslinking effect.
또한, 상기 아크릴계 공중합체 배합물은 가교제 및 가교 촉진제를 선택적으로 더 포함할 수 있다. 상기 가교제는 2,4,6-트리머캅토-s-트리아진(2,4,6-Trimercapto-s-triazine) 또는 이의 염, 또는 아민 화합물, 구체적인 예로 다가 아민 화합물을 사용할 수 있다. In addition, the acrylic copolymer blend may optionally further include a crosslinking agent and a crosslinking accelerator. The crosslinking agent may be 2,4,6-Trimercapto-s-triazine or a salt thereof, or an amine compound, specifically a polyvalent amine compound.
다가 아민 화합물로서 구체적으로는 지방족 다가 아민 가교제, 방향족 다가 아민 가교제 등을 들 수 있다. Specific examples of polyvalent amine compounds include aliphatic polyvalent amine crosslinkers, aromatic polyvalent amine crosslinkers, etc.
지방족 다가 아민 가교제로서는 헥사메틸렌디아민, 헥사메틸렌디아민 카바메이트, N,N'-디신나밀리덴-1,6-헥산디아민 등을 들 수 있다.Examples of aliphatic polyamine crosslinking agents include hexamethylenediamine, hexamethylenediamine carbamate, and N,N'-dicinnamylidene-1,6-hexanediamine.
방향족 다가 아민 가교제로서는 4,4'-메틸렌 디아닐린, m-페닐렌디아민, 4,4'-디아미노디페닐에테르, 3,4'-디아미노디페닐에테르, 4,4'-(m-페닐렌디이소프로필리덴) 지아니 인, 4,4'-(p-페닐렌디이소프로필리덴) 지아니 인, 2,2'-비스〔4-(4-아미노페녹시) 페닐〕프로판, 4,4'-디아미노벤즈아닐리드, 4,4'-비스(4-아미노페녹시) 비페닐, m-크실렌 디아민, p-크실렌 디아민, 1,3,5-벤젠 트리아민, 1,3,5-벤젠 트리아미노메틸 등을 들 수 있다.Examples of the aromatic polyvalent amine crosslinking agents include 4,4'-methylene dianiline, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-(m-phenylenediisopropylidene) ziannine, 4,4'-(p-phenylenediisopropylidene) ziannine, 2,2'-bis〔4-(4-aminophenoxy) phenyl〕propane, 4,4'-diaminobenzanilide, 4,4'-bis(4-aminophenoxy) biphenyl, m-xylene diamine, p-xylene diamine, 1,3,5-benzene triamine, and 1,3,5-benzene triaminomethyl.
상기 가교제의 사용 함량은 아크릴계 공중합체 조성물 100 중량부에 대하여, 0.05 중량부 내지 20 중량부, 0.1 중량부 내지 10 중량부, 또한 0.3 중량부 내지 6 중량부일 수 있으며, 이 범위 내에서 가교물의 형성 유지가 용이하며, 탄성이 우수한 효과가 있다.The amount of the crosslinking agent used may be 0.05 parts by weight to 20 parts by weight, 0.1 parts by weight to 10 parts by weight, or 0.3 parts by weight to 6 parts by weight, based on 100 parts by weight of the acrylic copolymer composition. Within this range, it is easy to form and maintain a crosslinked product, and excellent elasticity is achieved.
상기 가교 촉진제는 상기 다가 아민 가교제와 조합해 이용할 수 있는 가교 촉진제일 수 있으며, 수중, 25 ℃에서의 염기 해리 상수가 10 내지 106, 또는 12 내지 106일 수 있다. 구체적인 예로, 상기 가교 촉진제는 구아니딘 화합물, 이미다졸 화합물, 제4급 오늄염, 제3급 포스핀 화합물, 약산의 알칼리 금속염 등을 들 수 있다. 구아니딘 화합물로서는 1,3-디페닐 구아니딘, 디-o-트릴 구아니딘 등을 들 수 있다. 이미다졸 화합물로서는2-메틸이미다졸, 2-페닐이미다졸 등을 들 수 있다. 제4급 오늄염으로서는 테트라 n-부틸 암모늄 브로마이드, 옥타데실 트리n-부틸 암모늄 브로마이드 등을 들 수 있다.The above cross-linking accelerator may be a cross-linking accelerator that can be used in combination with the above polyhydric amine cross-linking agent, and may have a base dissociation constant in water at 25° C. of 10 to 106, or 12 to 106. As specific examples, the cross-linking accelerator may include a guanidine compound, an imidazole compound, a quaternary onium salt, a tertiary phosphine compound, an alkali metal salt of a weak acid, and the like. Examples of the guanidine compound include 1,3-diphenyl guanidine, di-o-tolyl guanidine, and the like. Examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, and the like. Examples of the quaternary onium salt include tetra-n-butyl ammonium bromide, octadecyl tri-n-butyl ammonium bromide, and the like.
상기 다가 제3급 아민 화합물로서는 트리에틸렌 디아민, 1,8-디아자-비사이클로［5.4.0］운데센-7 등을 들 수 있다. 제3급 포스핀 화합물로서는 트리페닐 포스핀, 트리 p-트릴포스핀 등을 들 수 있다. 약산의 알칼리 금속염으로서는 나트륨 또는 칼륨의 인산염, 탄산염 등의 무기 약산염 혹은 스테아린산염, 라우릴산염등의 유기 약산염을 들 수 있다.As the above polyvalent tertiary amine compounds, triethylene diamine, 1,8-diaza-bicyclo[5.4.0]undecene-7, etc. can be mentioned. As the tertiary phosphine compounds, triphenyl phosphine, tri p-triylphosphine, etc. can be mentioned. As the alkali metal salts of weak acids, inorganic weak acid salts such as sodium or potassium phosphate or carbonate, or organic weak acid salts such as stearate or laurate can be mentioned.
상기 가교 촉진제의 사용 함량은 아크릴계 공중합체 100 중량부에 대하여, 0.1 중량부 내지 20 중량부, 0.2 중량부 내지 15 중량부, 또는 0.3 중량부 내지 10 중량부일 수 있으며, 이 범위 내에서 가교 속도를 적절히 유지할 수 있고, 가교물의 인장강도가 우수한 효과가 있다.The amount of the crosslinking accelerator used may be 0.1 to 20 parts by weight, 0.2 to 15 parts by weight, or 0.3 to 10 parts by weight, based on 100 parts by weight of the acrylic copolymer. Within this range, the crosslinking speed can be appropriately maintained, and the tensile strength of the crosslinked product is excellent.
본 발명에 따른 아크릴계 공중합체 배합물은 필요에 따라 보강재, 노화 방지제, 광안정제, 가소제, 윤활제, 점착제, 윤활제, 난연제, 방미제, 대전 방지제, 착색제 등의 첨가제가 더 포함될 수 있다.The acrylic copolymer blend according to the present invention may further contain additives such as reinforcing agents, anti-aging agents, light stabilizers, plasticizers, lubricants, adhesives, lubricants, flame retardants, anti-fungal agents, antistatic agents, and colorants, as needed.
본 발명에 따른 아크릴계 공중합체 배합물의 배합은 롤 혼합, 밴 배리 혼합, 스크류 혼합, 용액 혼합 등의 적당의 혼합 방법이 채택할 수 있고, 구체적인 예로 롤 혼합 방법으로 실시될 수 있다. 배합 순서는 특별히 제한되지 않지만 열로 반응이나 분해하기 어려운 성분을 충분히 혼합한 후, 열로 반응하기 쉬운 성분 혹은 분해하기 쉬운 성분으로서 예를 들어 가교제 등을 반응이나 분해가 일어나지 않는 온도에서 단시간에 혼합하면 좋다. 본 발명에 따른 아크릴계 공중합체 배합물은 롤로 혼련할 때 롤로의 고무의 부착 정도가 적고 작업성이 우수한 효과가 있다.The mixing of the acrylic copolymer blend according to the present invention can be carried out by adopting an appropriate mixing method such as roll mixing, Van Barry mixing, screw mixing, solution mixing, etc., and as a specific example, it can be carried out by a roll mixing method. The mixing order is not particularly limited, but after sufficiently mixing components that are difficult to react or decompose with heat, it is preferable to mix components that are easy to react with heat or are easy to decompose, such as crosslinking agents, at a temperature at which no reaction or decomposition occurs, for a short period of time. The acrylic copolymer blend according to the present invention has the effect of having a low degree of rubber adhesion to the roll and excellent workability when kneaded with a roll.
또한, 본 발명에 따른 아크릴계 공중합체 배합물의 성형 방법은 압축 성형, 사출 성형, 트랜스퍼 성형 혹은 압출성형 등으로 실시될 수 있다. 또한 가교 방법은 가교물의 형상 등에 따라 선택하면 좋고 성형과 가교를 동시에 수행하는 방법, 성형 후에 가교를 하는 방법 등으로 실시될 수 있다. 본 발명에 아크릴계 공중합체 배합물은 상기 구성을 가지는 아크릴계 공중합체를 이용하기 때문에, 성형 시 아크릴계 공중합체의 유동성이 우수하고, 성형 시 버 발생 정도도 낮을 뿐만 아니라, 얻어진 성형체의 성형 정밀도가 높은 효과가 있다.In addition, the molding method of the acrylic copolymer blend according to the present invention can be performed by compression molding, injection molding, transfer molding, or extrusion molding. In addition, the crosslinking method can be selected depending on the shape of the crosslinked product, and can be performed by a method of performing molding and crosslinking at the same time, a method of performing crosslinking after molding, etc. Since the acrylic copolymer blend of the present invention uses an acrylic copolymer having the above-described configuration, the fluidity of the acrylic copolymer is excellent during molding, the degree of burr generation during molding is low, and the molding precision of the obtained molded body is high.
본 발명에 따른 아크릴계 공중합체 배합물은 가열함으로써 가교물로 제조할 수 있으며, 본 발명의 아크릴계 공중합체 배합물은 가교되면, 성형 또는 압출 공정을 통해 원하는 형상으로 형성하거나 이와 동시에 또는 후속적으로 경화시킴으로써 물품을 제조할 수 있다. The acrylic copolymer blend according to the present invention can be manufactured into a crosslinked product by heating, and once the acrylic copolymer blend of the present invention is crosslinked, it can be formed into a desired shape through a molding or extrusion process, or can be manufactured into a product by curing simultaneously with or subsequently thereto.
또한, 상기 제조된 물품은, 엔진 마운트용 고무, 트랜스미션 씰(seal), 크랭크 샤프트 씰 등 다양한 자동차 부품으로 사용될 수 있다.In addition, the manufactured product can be used as various automobile parts such as rubber for engine mounts, transmission seals, and crankshaft seals.
이하, 실시예에 의하여 본 발명을 더욱 상세하게 설명하고자 한다. 그러나, 하기 실시예는 본 발명을 예시하기 위한 것으로 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 통상의 기술자에게 있어서 명백한 것이며, 이들 만으로 본 발명의 범위가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to illustrate the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and technical idea of the present invention, and the scope of the present invention is not limited to these examples alone.
<< 실시예Example >>
실시예Example 11
<아크릴계 공중합체 조성물 제조><Manufacture of acrylic copolymer composition>
중합 반응기에 부틸 아크릴레이트 32 중량%, 에틸 아크릴레이트 50 중량% 및 2-메톡시 에틸아크릴레이트 15 중량%, 비닐 클로로 아세테이트 3 중량%로 구성되는 주단량체 혼합물과 상기 주단량체 혼합물 100 중량부에 대하여 소듐 라우릴 설페이트 3 중량부, 소듐 메타비 설파이트 0.5 중량부, 큐멘 하이드로 퍼옥사이트 0.01 중량부, 소듐 포름알데하이드 설폭시레이트 0.01 중량부, 알파-메틸스티렌 다이머(α-methylstyrene dimer) 0.002 중량부, 물 400 중량부를 넣은 후 40 ℃의 온도에서 중합을 개시하였다. A main monomer mixture consisting of 32 wt% of butyl acrylate, 50 wt% of ethyl acrylate, 15 wt% of 2-methoxy ethyl acrylate, and 3 wt% of vinyl chloro acetate and, relative to 100 wt% of the main monomer mixture, 3 wt% of sodium lauryl sulfate, 0.5 wt% of sodium metabisulfite, 0.01 wt% of cumene hydroperoxide, 0.01 wt% of sodium formaldehyde sulfoxylate, 0.002 wt% of α-methylstyrene dimer, and 400 wt% of water were added, and polymerization was initiated at a temperature of 40°C.
중합 전환률이 93%에 이르렀을 때 중합을 정지시켰다. 그 후 산화방지제, 나트륨 스테아레이트 2 중량부를 첨가하고 65 ℃의 온도에 응집제를 첨가한 수상에서 응집하여 아크릴계 공중합체 조성물을 수득하였다.When the polymerization conversion reached 93%, the polymerization was stopped. Thereafter, 2 parts by weight of an antioxidant, sodium stearate, was added, and the mixture was coagulated in an aqueous phase containing a coagulant at a temperature of 65°C to obtain an acrylic copolymer composition.
<아크릴계 공중합체 배합물 제조><Manufacture of acrylic copolymer blend>
상기 아크릴계 공중합체 조성물 100 중량부를 Haake mixer를 통해 30 rpm으로 50 ℃에서 30 초간 교반한 후 카본블랙 50 중량부, 스테아릭에시드 1 중량부, 산화방지제 2 중량부, 2,4,6-트리머캅토-s-트리아진(상품명: RF-3752) 1 중량부, 징크 디부틸디티오카바메이트(상품명: Nocceler BZ) 2 중량부를 투입하고 50 ℃에서 360 초 배합한 후 롤밀 장비를 통해 배합된 아크릴계 공중합체 배합물을 얻었다.100 parts by weight of the above acrylic copolymer composition was stirred at 30 rpm at 50°C for 30 seconds using a Haake mixer, then 50 parts by weight of carbon black, 1 part by weight of stearic acid, 2 parts by weight of an antioxidant, 1 part by weight of 2,4,6-trimercapto-s-triazine (trade name: RF-3752), and 2 parts by weight of zinc dibutyldithiocarbamate (trade name: Nocceler BZ) were added and mixed at 50°C for 360 seconds, and then an acrylic copolymer mixture was obtained by mixing using a roll mill device.
실시예Example 22
상기 실시예 1에서, 아크릴계 공중합체 조성물 제조시, 나트륨 스테아레이트 2 중량부 대신 칼륨 스테아레이트 2 중량부 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In the above Example 1, when preparing an acrylic copolymer composition, the same method as Example 1 was performed, except that 2 parts by weight of potassium stearate was added instead of 2 parts by weight of sodium stearate.
실시예Example 33
상기 실시예 1에서, 아크릴계 공중합체 조성물 제조시, 알파-메틸스티렌 다이머 0.002 중량부 대신 0.004 중량부 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In the above Example 1, when preparing an acrylic copolymer composition, the same method as Example 1 was performed except that 0.004 part by weight of alpha-methylstyrene dimer was added instead of 0.002 part by weight.
실시예Example 44
상기 실시예 1에서, 아크릴계 공중합체 조성물 제조시, 알파-메틸스티렌 다이머 0.002 중량부 대신 0.005 중량부 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In the above Example 1, when preparing an acrylic copolymer composition, the same method as Example 1 was performed, except that 0.005 part by weight of alpha-methylstyrene dimer was added instead of 0.002 part by weight.
실시예Example 55
상기 실시예 1에서, 아크릴계 공중합체 조성물 제조시, 알파-메틸스티렌 다이머 0.002 중량부 대신 0.01 중량부 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In the above Example 1, when preparing an acrylic copolymer composition, the same method as in the above Example 1 was performed, except that 0.01 part by weight of alpha-methylstyrene dimer was added instead of 0.002 part by weight.
비교예Comparative example 11
상기 실시예 1에서, 아크릴계 공중합체 조성물 제조시, 알파-메틸스티렌 다이머를 투입하지 않은 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In the above Example 1, the same method as in the above Example 1 was performed, except that alpha-methylstyrene dimer was not added when producing an acrylic copolymer composition.
비교예Comparative example 22
상기 실시예 1에서, 아크릴계 공중합체 조성물 제조시, 알파-메틸스티렌 다이머 0.002 중량부 대신 0.0005 중량부 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In the above Example 1, when preparing an acrylic copolymer composition, the same method as Example 1 was performed except that 0.0005 part by weight of alpha-methylstyrene dimer was added instead of 0.002 part by weight.
비교예Comparative example 33
상기 실시예 1에서, 아크릴계 공중합체 조성물 제조시, 알파-메틸스티렌 다이머 0.002 중량부 대신 0.05 중량부 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In the above Example 1, when preparing an acrylic copolymer composition, the same method as in the above Example 1 was performed, except that 0.05 part by weight of alpha-methylstyrene dimer was added instead of 0.002 part by weight.
비교예Comparative example 44
상기 실시예 1에서, 아크릴계 공중합체 조성물 제조시, 나트륨 스테아레이트를 투입하지 않은 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In the above Example 1, the same method as in the above Example 1 was performed, except that sodium stearate was not added when preparing the acrylic copolymer composition.
비교예Comparative example 55
상기 실시예 1에서, 아크릴계 공중합체 조성물 제조시, 나트륨 스테아레이트 2 중량부 대신 0.1 중량부 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In the above Example 1, when preparing an acrylic copolymer composition, the same method as Example 1 was performed except that 0.1 part by weight of sodium stearate was added instead of 2 parts by weight.
비교예Comparative example 66
상기 실시예 1에서, 아크릴계 공중합체 조성물 제조시, 나트륨 스테아레이트 2 중량부 대신 10 중량부 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.In the above Example 1, when preparing an acrylic copolymer composition, the same method as Example 1 was performed except that 10 parts by weight of sodium stearate was added instead of 2 parts by weight.
<실험예 > < Experimental example >
실험예Experimental example 11
상기 실시예 1 내지 5 및 비교예 1 내지 6으로부터 제조된 아크릴계 공중합체 조성물의 무늬점도, 및 상기 실시예 1 내지 5 및 비교예 1 내지 6으로부터 제조된 아크릴계 공중합체 배합물의 내유성, 가교 속도 및 배합 작업성을 하기와 같은 방법으로 측정하였고, 그 결과를 하기 표 1 및 2에 기재하였다.The patterned viscosity of the acrylic copolymer compositions prepared from Examples 1 to 5 and Comparative Examples 1 to 6, and the oil resistance, crosslinking speed, and mixing workability of the acrylic copolymer blends prepared from Examples 1 to 5 and Comparative Examples 1 to 6 were measured by the following methods, and the results are shown in Tables 1 and 2 below.
* 무늬 점도(ML1+4, 100 ℃): MV-2000(ALPHA Technologies 社)를 이용하여 100 ℃에서 Rotor Speed 2±0.02 rpm, Large Rotor를 사용하여 측정하였으며, 이때 사용된 시료는 실온(23±3 ℃)에서 30분 이상 방치한 후 27±3 g을 채취하여 다이 캐비티(Die cavity) 내부에 채워 놓고 Platen을 작동시켜 4분 동안 측정하였다.* Pattern viscosity (ML1+4, 100 ℃): It was measured using MV-2000 (ALPHA Technologies) at 100 ℃, Rotor Speed 2±0.02 rpm, Large Rotor. The sample used was left at room temperature (23±3 ℃) for more than 30 minutes, 27±3 g was collected, filled inside the die cavity, and the Platen was operated for measurement for 4 minutes.
* 신장률 및 인장강도: 아크릴계 공중합체 배합물을 160 ℃에 30 분간 1차 가황시키고 얻어진 1차 가교물을 180 ℃에서 60 분간 가황시켰다. 얻어진 가황된 아크릴 고무는 JIS K6251에 준거하여, 덤벨 형상 3 호형의 시험편으로 제작하였고, 이를 사용하여 신장률과 인장강도 측정을 실시하였다.* Elongation and tensile strength: An acrylic copolymer blend was first vulcanized at 160°C for 30 minutes, and the obtained first cross-linked product was vulcanized at 180°C for 60 minutes. The obtained vulcanized acrylic rubber was produced into a dumbbell-shaped No. 3 test piece in accordance with JIS K6251, and the elongation and tensile strength were measured using this.
* 내유성 시험: 상기 신장률 및 인장강도 측정과 동일한 방법으로 덤벨 형상의 시험편을 제작하였다. 제작된 시험편을 시험용 액체 500mL에 넣어, 시험편이 모두 액체 중에 침지되도록 설치하였다. 이를 오븐에 넣고, 155 ℃에서 168시간 동안 가열을 행하였다. 한편, 시험용 액체로는 5W-30 오일을 사용하였다.* Oil resistance test: Dumbbell-shaped test pieces were made using the same method as the above-mentioned elongation and tensile strength measurements. The manufactured test pieces were placed in 500 mL of test liquid, and the test pieces were installed so that they were all immersed in the liquid. This was placed in an oven and heated at 155°C for 168 hours. Meanwhile, 5W-30 oil was used as the test liquid.
가열 후, 시험용 시험편을 꺼내 시험용 액체를 닦아낸 후 체적을 측정하여, 초기 체적과의 체적 변화율 △V(%)을 계산하였고, 상기 신장률 및 인장강도 측정과 동일하게 측정하여 신장 변화율 △EB(%) 및 인장강도 변화율 △TS(%)을 확인하였다. 상기 세 가지 변화율이 모두 작은 편이, 내유성이 우수하다.After heating, the test specimen was taken out, the test liquid was wiped off, and the volume was measured to calculate the volume change rate △V(%) from the initial volume. In addition, the change rate of elongation △EB(%) and the change rate of tensile strength △TS(%) were confirmed by measuring in the same manner as the above elongation and tensile strength measurements. The smaller the above three change rates, the better the oil resistance.
*가교 속도(CRI, Cure rate index): 100/(Tc90-ts2)*Cure rate index (CRI): 100/(Tc90-ts2)
여기서 Tc90은 배합 후 롤밀 공정을 거친 아크릴계 공중합체 배합물을 이동 금형 유압계(Moving die rheometer) 측정 시 최종 토크 값의 90% 토크 값이 되었을 때의 시간(min)이고, ts2는 초기 토크 값에서 2 상승했을 때의 시간(min)이다.Here, Tc90 is the time (min) when the torque value of the acrylic copolymer blend that went through the roll mill process after mixing becomes 90% of the final torque value as measured by a moving die rheometer, and ts2 is the time (min) when the torque value increases by 2 from the initial torque value.
* 배합 작업성(10 점): 아크릴계 공중합체 배합물 제조 후, 카본블랙과 기타 첨가제 및 아크릴계 공중합체 조성물의 배합정도를 표면의 거침정도 및 잔류 첨가제 양을 육안으로 확인하고 10점법을 통해 평가하였다. 배합이 우수할수록 10점에 가깝게 평가하였다.* Blending workability (10 points): After manufacturing the acrylic copolymer blend, the blending degree of carbon black, other additives, and acrylic copolymer composition was visually checked for surface roughness and residual additive amount, and evaluated using the 10-point method. The closer the blending was to 10 points, the better the score.
<거침정도 및 잔류 첨가제 평가 기준><Evaluation criteria for roughness and residual additives>
1점: 아크릴계 공중합체 조성물이 첨가제들로 인해 변색조차 되지 않음1 point: The acrylic copolymer composition does not even discolor due to additives.
3점: 배합 이후 잔류 첨가제가 아크릴계 공중합체 조성물과 접착이 되지 않음3 points: After mixing, residual additives do not adhere to the acrylic copolymer composition.
5점: 잔류 첨가제가 손에 묻어남5 points: Residual additives remain on hands
7점: 잔류 첨가제가 손에 묻어나지 않으나, 국부적인 광택이 보임7 points: No residual additives left on hands, but localized gloss is visible
10점: 잔류 첨가제가 육안으로 보이지 않고, 국부적인 광택이 안보임10 points: No residual additives visible to the naked eye, no localized gloss
(ML1+4, 100 ℃)Patterned dot
(ML1+4, 100 ℃)
(ML1+4, 100 ℃)Patterned dot
(ML1+4, 100 ℃)
상기 표 1을 참조하면, 적정 범위의 금속 스테아레이트 및 알파-메틸스티렌 다이머를 포함한 실시예 1 내지 5는 내유성, 가교 속도 및 배합 작업성이 우수한 것을 확인할 수 있다. 특히, 실시예 1 내지 5 중에서도 알파-메틸스티렌 다이머의 사용 함량이 주단량체 혼합물 100 중량부에 대하여 0.004 중량부 이하인 실시예 1 내지 3은 상기 0.004 중량부를 초과하는 실시예 4 및 5보다 내유성이 우수함을 확인할 수 있다.Referring to Table 1 above, it can be confirmed that Examples 1 to 5 including appropriate ranges of metal stearate and alpha-methylstyrene dimer have excellent oil resistance, crosslinking speed, and mixing workability. In particular, among Examples 1 to 5, it can be confirmed that Examples 1 to 3, in which the usage content of alpha-methylstyrene dimer is 0.004 part by weight or less with respect to 100 parts by weight of the main monomer mixture, have better oil resistance than Examples 4 and 5, in which the usage content exceeds 0.004 part by weight.
반면, 상기 표 2를 참조하면, 본 발명에 따른 알파-메틸스티렌 다이머를 포함하지 않은 비교예 1은 신장률, 가교 속도 및 배합 작업성이 동시에 저하되었고, 금속 스테아레이트를 포함하지 않은 비교예 4는 내유성 및 가교 속도 특성이 동시에 저하됨을 확인할 수 있다.On the other hand, referring to Table 2 above, it can be confirmed that Comparative Example 1, which does not include alpha-methylstyrene dimer according to the present invention, simultaneously deteriorates in elongation, crosslinking speed, and mixing workability, and Comparative Example 4, which does not include metal stearate, simultaneously deteriorates in oil resistance and crosslinking speed characteristics.
또한, 본 발명에 따른 금속 스테아레이트 및 알파-메틸스티렌 다이머를 모두 포함하더라도, 알파-메틸스티렌 다이머의 사용 함량이 적정 범위보다 적은 비교예 2는 신장률, 가교 속도 및 배합 작업성이 동시에 저하되었고, 금속 스테아레이트의 사용 함량이 적정 범위보다 적은 비교예 5는 내유성 및 가교 속도 개선의 효과가 미미하여서 실시예들에서 확인할 수 있는 효과 개선을 기대할 수 없었으며, 반대로 알파-메틸스티렌 다이머의 사용 함량이 적정 범위보다 많은 비교예 3은 내유성 및 가교 속도 특성이 저하되었을 뿐만 아니라, 인장강도 측면에서도 불리하였고, 금속 스테아레이트의 사용 함량이 적정 범위보다 많은 비교예 6은 가교 속도 및 배합 작업성이 저하될 뿐만 아니라, 신장률 및 인장강도 측면에서도 불리함을 확인할 수 있다. 이를 통하여 비교예들은 가교속도, 내유성 및 배합 작업성이 실시예 대비 열위임을 알 수 있었다.In addition, even though both the metal stearate and alpha-methylstyrene dimer according to the present invention were included, Comparative Example 2, in which the amount of alpha-methylstyrene dimer used was less than the appropriate range, simultaneously deteriorated in elongation, crosslinking speed, and mixing workability, and Comparative Example 5, in which the amount of metal stearate used was less than the appropriate range, had minimal effects on improving oil resistance and crosslinking speed, so that it was not possible to expect the improved effects that could be seen in the Examples, and on the contrary, Comparative Example 3, in which the amount of alpha-methylstyrene dimer used was more than the appropriate range, not only did the oil resistance and crosslinking speed characteristics deteriorate, but it was also disadvantageous in terms of tensile strength, and Comparative Example 6, in which the amount of metal stearate used was more than the appropriate range, not only did the crosslinking speed and mixing workability deteriorate, but it was also disadvantageous in terms of elongation and tensile strength. Through this, it could be seen that the Comparative Examples were inferior to the Examples in crosslinking speed, oil resistance, and mixing workability.
Claims (10)
상기 아크릴계 공중합체는 주단량체 유래 반복단위 및 알파-메틸스티렌 다이머(α-methylstyrene dimer) 유래부를 포함하되,
상기 주단량체 유래 반복단위는, (메타)아크릴산 알킬 에스테르 단량체 유래 반복단위, (메타)아크릴산 알콕시 알킬 에스테르 단량체 유래 반복단위 및 가교성 단량체 유래부를 포함하고,
상기 아크릴계 공중합체는, 상기 알파-메틸스티렌 다이머 유래부를 상기 주단량체 유래 반복단위 전체 100 중량부에 대하여 0.001 내지 0.01 중량부로 포함하며,
상기 금속 스테아레이트 또는 이의 염은 상기 주단량체 유래 반복단위 전체 100 중량부에 대하여 0.5 내지 5 중량부로 포함되는 아크릴계 공중합체 조성물.Containing an acrylic copolymer and a metal stearate or a salt thereof,
The above acrylic copolymer comprises a repeating unit derived from a main monomer and a portion derived from an α-methylstyrene dimer,
The above-mentioned main monomer-derived repeating unit includes a (meth)acrylic acid alkyl ester monomer-derived repeating unit, a (meth)acrylic acid alkoxy alkyl ester monomer-derived repeating unit, and a crosslinking monomer-derived portion,
The above acrylic copolymer contains 0.001 to 0.01 parts by weight of the alpha-methylstyrene dimer-derived portion relative to 100 parts by weight of the total repeating unit derived from the main monomer.
An acrylic copolymer composition, wherein the metal stearate or salt thereof is contained in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the total repeating unit derived from the main monomer.
상기 아크릴계 공중합체는, 상기 알파-메틸스티렌 다이머 유래부를 상기 주단량체 유래 반복단위 전체 100 중량부에 대하여 0.001 내지 0.004 중량부로 포함하는 아크릴계 공중합체 조성물.In the first paragraph,
The above acrylic copolymer is an acrylic copolymer composition containing 0.001 to 0.004 parts by weight of the alpha-methylstyrene dimer-derived portion relative to 100 parts by weight of the total repeating unit derived from the main monomer.
상기 금속 스테아레이트는 나트륨 스테아레이트, 칼륨 스테아레이트, 마그네슘 스테아레이트, 칼슘 스테아레이트, 아연 스테아레이트, 리튬 스테아레이트 및 알루미늄 스테아레이트로 이루어진 군에서 선택되는 1종 이상인 아크릴계 공중합체 조성물.In the first paragraph,
An acrylic copolymer composition wherein the metal stearate is at least one selected from the group consisting of sodium stearate, potassium stearate, magnesium stearate, calcium stearate, zinc stearate, lithium stearate, and aluminum stearate.
상기 아크릴계 공중합체는, 상기 가교성 단량체 유래부를 상기 주단량체 유래 반복단위 전체 함량에 대하여 0.1 내지 20 중량%로 포함하는 아크릴계 공중합체 조성물.In the first paragraph,
The above acrylic copolymer is an acrylic copolymer composition containing 0.1 to 20 wt% of the crosslinkable monomer-derived portion based on the total content of repeating units derived from the main monomer.
상기 가교성 단량체는 비닐클로로아세테이트, 비닐벤질클로라이드, 2-클로로아크릴산에틸 및 2-클로로에틸비닐에테르로 이루어진 군에서 선택되는 1종 이상인 아크릴계 공중합체 조성물.In the first paragraph,
An acrylic copolymer composition wherein the crosslinking monomer is at least one selected from the group consisting of vinylchloroacetate, vinylbenzyl chloride, ethyl 2-chloroacrylate, and 2-chloroethylvinyl ether.
상기 아크릴계 공중합체 조성물의 무늬 점도(ML1+4, 100 ℃)는 10 내지 70인 아크릴계 공중합체 조성물.In the first paragraph,
An acrylic copolymer composition having a patterned viscosity (ML1+4, 100° C.) of 10 to 70.
상기 주단량체 혼합물에 알파-메틸스티렌 다이머를 투입하고 중합하여 아크릴계 공중합체를 수득하는 단계; 및
상기 아크릴계 공중합체에 금속 스테아레이트 또는 이의 염을 첨가한 후 응집하는 단계를 포함하는 청구항 1의 아크릴계 공중합체 조성물의 제조방법. A step of preparing a main monomer mixture comprising a (meth)acrylic acid alkyl ester monomer, a (meth)acrylic acid alkoxy alkyl ester monomer and a crosslinking monomer;
A step of adding alpha-methylstyrene dimer to the above main monomer mixture and polymerizing it to obtain an acrylic copolymer; and
A method for producing an acrylic copolymer composition according to claim 1, comprising the step of adding a metal stearate or a salt thereof to the acrylic copolymer and then coagulating the same.
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