CN103910962B - Polymethacrylate composition - Google Patents
Polymethacrylate composition Download PDFInfo
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- CN103910962B CN103910962B CN201310731422.1A CN201310731422A CN103910962B CN 103910962 B CN103910962 B CN 103910962B CN 201310731422 A CN201310731422 A CN 201310731422A CN 103910962 B CN103910962 B CN 103910962B
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- polymethacrylates
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- 229920000193 polymethacrylate Polymers 0.000 title claims abstract description 80
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 39
- 239000000155 melt Substances 0.000 claims abstract description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 52
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 32
- -1 acrylic ester Chemical class 0.000 claims description 29
- 150000002148 esters Chemical class 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical group CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 description 78
- 230000000052 comparative effect Effects 0.000 description 26
- 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 18
- 239000004926 polymethyl methacrylate Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 16
- 229920003023 plastic Polymers 0.000 description 14
- 239000004033 plastic Substances 0.000 description 14
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 13
- 230000004580 weight loss Effects 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 230000002079 cooperative effect Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert-Butyl hydroperoxide Substances CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000003405 preventing effect Effects 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- ORMDVQRBTFCOGC-UHFFFAOYSA-N (2-hydroperoxy-4-methylpentan-2-yl)benzene Chemical compound CC(C)CC(C)(OO)C1=CC=CC=C1 ORMDVQRBTFCOGC-UHFFFAOYSA-N 0.000 description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 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 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920005372 Plexiglas® Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 150000004978 peroxycarbonates Chemical class 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- CJVROGOPKLYNSX-UHFFFAOYSA-N (4-tert-butylcyclohexyl) carboxyoxy carbonate Chemical compound CC(C)(C)C1CCC(OC(=O)OOC(O)=O)CC1 CJVROGOPKLYNSX-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-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
- FIYMNUNPPYABMU-UHFFFAOYSA-N 2-benzyl-5-chloro-1h-indole Chemical compound C=1C2=CC(Cl)=CC=C2NC=1CC1=CC=CC=C1 FIYMNUNPPYABMU-UHFFFAOYSA-N 0.000 description 1
- HTCRKQHJUYBQTK-UHFFFAOYSA-N 2-ethylhexyl 2-methylbutan-2-yloxy carbonate Chemical compound CCCCC(CC)COC(=O)OOC(C)(C)CC HTCRKQHJUYBQTK-UHFFFAOYSA-N 0.000 description 1
- SKVOYPCECYQZAI-UHFFFAOYSA-N 2-ethylhexyl 2-methylbutan-2-ylperoxy carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)CC SKVOYPCECYQZAI-UHFFFAOYSA-N 0.000 description 1
- FKMUJSDGDJFLLO-UHFFFAOYSA-N 2-ethylhexyl hydrogen carbonate 2-hydroperoxy-2-methylpropane Chemical compound C(OCC(CCCC)CC)(O)=O.C(C)(C)(C)OO FKMUJSDGDJFLLO-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
- UKTZJXRJZBVHKL-UHFFFAOYSA-N 2h-benzotriazole Chemical compound C1=CC=C2NN=NC2=C1.C1=CC=C2NN=NC2=C1 UKTZJXRJZBVHKL-UHFFFAOYSA-N 0.000 description 1
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- NWZZFAQUBMRYNU-UHFFFAOYSA-N n-octadecylnonadec-18-en-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC=C NWZZFAQUBMRYNU-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000010458 rotten stone Substances 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CSKKAINPUYTTRW-UHFFFAOYSA-N tetradecoxycarbonyloxy tetradecyl carbonate Chemical compound CCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCC CSKKAINPUYTTRW-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polymethacrylate composition, which comprises (A) polymethacrylate, wherein the weight average molecular weight range of the polymethacrylate is 6.5 to 8.5 ten thousand, and the polymethacrylate composition contains 94 to 97 weight percent of methacrylate monomer units, 3 to 6 weight percent of acrylate monomer units and 0 to 1 weight percent of other copolymerizable monomer units; and include compounds of formula (I) as defined in the claims and specification; wherein the Melt Index (MI) of the polymethacrylate (A) is 8-17 g/10min measured at 230 ℃ and 3.8Kg, and the content of the compound represented by the formula (I) in the polymethacrylate composition is 50-350 ppm.
Description
[technical field]
The invention relates to a kind of polymethacrylates compositions, particularly relate to a kind of heat stability good
Good polymethacrylates compositions.
[background technology]
Polymethacrylates [poly methacrylate] is a polymer of many uses, machine-shaping
Property, physical property and engineering properties aspect all have good evaluation, and light transmittance is better than glass (reaching 92%),
Appearance of molded articles is good, is one of the most excellent macromolecule transparent material, have " lucite "
Title, through frequently as various optical elements or people's livelihood consumer goods, such as camera lens, eyeglass, car tail
Lamp, billboard etc..
Though polymethacrylates possesses above-mentioned excellent optical and processing forming, but heat stability
Slightly dislike not enough.The practice typically improving heat stable property is through the molecular weight improving resin, but molecular weight
Raising can cause mobility to reduce, and the resin of high molecular generally requires higher processing temperature, even without
The state that method is processed, such as, require to carry out extruding or during injection moulding in higher processing temperature, send out
The chance of heat deterioration is significantly increased.For improving the heat stability of polymethacrylates, it will usually pass through
Promote the mode of molecular weight, but molecular weight is too high can make again that mobility is poor causes following process to be difficult to.Base
In general polymethacrylates character of contradiction in the physical property such as mobility and heat stability, therefore how to make
Polymethacrylates has good mobility and heat stability simultaneously, is to be improved for this pole, field
Problem.
EP0322166 and US5045581 disclose using compound as shown in formula (I) and the like as
The antioxidant of polybutadiene rubber.Considering in polybutadiene rubber processing procedure, devolatilization temperature is gathered higher than solution
Close temperature, and mixing under oxygen-free environment xanthochromia situation may be had to occur, pass through with the change as shown in formula (I)
Compound can improve foregoing problems as the antioxidant of polybutadiene rubber.But aforementioned prior art is not
Disclose how that the structure of adjustment polymethacrylates forms part and takes mutually with the compound as shown in formula (I)
It is equipped with the thermal stability problems solving polymethacrylates.
Because above-mentioned, still need to develop a kind of heat stable property and more preferably and still there is certain fluidity and have and add
The polymethacrylates of work, carries out following process molding manufacture procedure and types of applications meeting industry
Demand.
[summary of the invention]
First purpose of the present invention, is i.e. providing a kind of good thermal stability and is still having the poly-first of processing characteristics
Base acrylate composition.
Then, polymethacrylates compositions of the present invention, comprise:
(A) polymethacrylates, weight average molecular weight scope is 6.5 ten thousand to 8.5 ten thousand, containing metering system
Acid esters system monomeric unit 94 to 97wt%, acrylic ester monomeric unit 3 to 6wt%, and
Other copolymerizable monomer unit 0 to 1wt%；And
(B) compound as shown in formula (I):
Wherein, should (A) polymethacrylates 230 DEG C, the melt index (MI) that records under 3.8Kg be
8～17g/10min, the content model of the compound shown in this formula (I) in this polymethacrylates compositions
Enclosing is 50 to 350ppm.
Polymethacrylates compositions of the present invention, wherein, should (A) polymethacrylates 230 DEG C,
The melt index (MI) recorded under 3.8Kg is 8～17g/10min, in this polymethacrylates compositions
In the content range of the compound shown in this formula (I) be 50 to 350ppm.
Polymethacrylates compositions of the present invention, wherein, the weight average of this polymethacrylates divides
Sub-weight range is 6.8 ten thousand to 8.3 ten thousand, containing methacrylate ester monomeric unit 94.5 to 95.5wt%,
Acrylic ester monomeric unit 4.5 to 5.5wt%, and other copolymerizable monomer unit 0 to 1wt%.
Polymethacrylates compositions of the present invention, wherein the compound shown in this formula (I) is in this poly-methyl-prop
The content range of alkene acid ester composite is 100 to 300ppm.
Polymethacrylates compositions of the present invention, wherein this methacrylate ester monomeric unit is methyl
N-octyl monomeric unit, methyl methacrylate monomer unit, n-BMA monomer
Unit, or aforesaid combination.
Polymethacrylates compositions of the present invention, wherein this acrylic ester monomeric unit be acrylic acid just
Own ester monomeric unit, methyl acrylate monomer units, ethyl acrylate monomer units, butyl acrylate list
Body unit, or octadecyl acrylate monomeric unit or aforesaid combination.
Second purpose of the present invention, is i.e. providing a kind of good thermal stability and is still having the poly-first of processing characteristics
Base acrylate composition.
Then, polymethacrylates compositions of the present invention, comprise:
(A) polymethacrylates, weight average molecular weight scope is 6.5 ten thousand to 12 ten thousand, containing metering system
Acid esters system monomeric unit 94 to 97wt%, acrylic ester monomeric unit 3 to 6wt%, and
Other copolymerizable monomer unit 0 to 1wt%；And
Compound as shown in formula (I):
Wherein, in this polymethacrylates compositions, the content range of the compound shown in this formula (I) is
80 to 300ppm.
Polymethacrylates compositions of the present invention, wherein the weight average at this polymethacrylates divides
When sub-weight range is 6.5 ten thousand to 7.2 ten thousand, the change shown in this formula (I) in this polymethacrylates compositions
The content range of compound is 80 to 180ppm, or 100 to 150ppm
Effect of the present invention is: through adjust structure composition in this polymethacrylates ratio and
The consumption of formula (I) compound in this polymethacrylates compositions so that this polymethacrylates combines
Thing has preferably heat stability and processability, it is adaptable to the processing procedures such as high temperature injection molding and high temperature extrusion.
[detailed description of the invention]
Polymethacrylates compositions of the present invention, comprises:
(A) polymethacrylates, weight average molecular weight scope is 6.5 ten thousand to 12 ten thousand, or 6.5 ten thousand to 8.5
Ten thousand, containing methacrylate ester monomeric unit 94 to 97wt%, acrylic ester monomeric unit
3 to 6wt%, and other copolymerizable monomer unit 0 to 1wt%；And
(B) compound shown in formula (I):
Wherein, should (A) polymethacrylates 230 DEG C, the melt index (MI) that records under 3.8Kg be
8～17g/10min, the content model of the compound shown in this formula (I) in this polymethacrylates constituent
Enclosing is 50 to 350ppm, preferably 80 to 300ppm, is more preferably 100 to 300ppm.Should
(A) polymethacrylates 230 DEG C, the melt index (MI) that records under 3.8Kg be 8～10g/10min,
In this polymethacrylates constituent, the content range of the compound shown in this formula (I) is 50 to 350
Ppm, preferably 100 to 300ppm, be more preferably 150 to 300ppm.Should (A) polymethyl
Acid esters 230 DEG C, the melt index (MI) that records under 3.8Kg be 11～17g/10min, at this poly-methyl
In acrylate constituent, the content range of the compound shown in this formula (I) is 50 to 200ppm, preferably
Ground is 80 to 180ppm, is more preferably 100 to 150ppm.More preferably, at polymethacrylates
Weight average molecular weight scope be 6.5 ten thousand to 7.2 ten thousand, when melt index is 11～17g/10min, poly-
In methacrylate compositions, the content range of the compound shown in formula (I) is 50 to 200ppm, relatively
It is 80 to 180ppm, most preferably 100 to 150ppm goodly.
It is preferred that be somebody's turn to do (A) polymethacrylates, it is by the methacrylate of 94.5 to 95.5wt%
It is monomer, the acrylic ester monomer of 4.5 to 5.5wt%, and optionally 0 to the 1wt% added
Other copolymerizable monomer are polymerized.
The concrete example of this methacrylate ester monomer is including but not limited to n octyl methacrylate, first
Base acrylic acid methyl ester., n-BMA etc., or aforementioned combination.
The concrete example of acrylic ester monomer including but not limited to: the most own ester of acrylic acid, acrylic acid methyl ester.,
Ethyl acrylate, butyl acrylate, octadecyl acrylate etc., or aforementioned combination.Aforementioned methyl-prop
Olefin(e) acid ester system's monomer and acrylic ester monomer can be selected one respectively and carry out combined polymerization, also can mix two kinds or
Two or more monomers are polymerized formation copolymer jointly.
The concrete example of these other copolymerizable monomer including but not limited to: acrylonitrile, styrene, maleic anhydride,
α-methyl styrene, and one of aforementioned combination.
Polymethacrylates obtained by aggregated includes methacrylate ester monomeric unit and acrylic acid
Ester system monomeric unit.What is called " monomeric unit " refers to aforesaid methacrylate ester monomer or third herein
Olefin(e) acid ester system's aggregated reaction of monomer and the repetitive structure that formed.
The weight average molecular weight scope of this polymethacrylates is 6.5 ten thousand to 8.5 ten thousand；It is preferred that
The weight average molecular weight scope of this polymethacrylates is 6.8 ten thousand to 8.3 ten thousand, or 6.8 ten thousand to 7.2
Ten thousand.
Should can prepare with solution or mass polymerization by (A) polymethacrylates, preferably exist at solvent
Under carry out polyreaction, to avoid when the viscosity of crude polymer is increased beyond a certain value, polyreaction
Unmanageable situation.The viscosity of this polymethacrylates is typically to represent with solid content, the use of solvent
Amount need to adjust to making the solid content of crude polymer less than 50wt%, preferably lower than 40wt%.
The boiling point of this solvent is the most close with the principal monomer boiling point carrying out polyreaction, such as, select and first
The solvent that base acrylate monomer boiling point is close, the mixture making this solvent and such monomer be formed has
The boiling spread of relatively narrower, can lower the chance being mixed into pollutant in the mixture of circulation loopback, exempt from
The monomer to circulation loopback and solvent mixture is gone to carry out the program of intermediate fractionation again.
It is thus preferable to, this solvent is to have the boiling point of 40 to 225 DEG C, be more preferably have 60 to
The boiling point of 150 DEG C.The concrete example of this solvent can be such as but not limited to: hexane, heptane, octane, benzene,
Toluene, xylol, o-Dimethylbenzene, meta-xylene, ethylbenzene, hexamethylene, cyclodecane, isobutyltrimethylmethane.,
And the hydro carbons of various low boiling or aromatic hydrocarbon solvent
(A) polyreaction of polymethacrylates is to cause by free radical, this radical initiator
There is no specific restriction, concrete example has: azo compound, such as 2,2 '-azodiisobutyronitrile
(2,2 '-Azobis-(isobutyronitrile), hereinafter referred to as AIBN), 2, double (the 2-methyl fourth of 2 '-azo
Nitrile) [2,2 '-Azobis-(2-methylbutyronitrile), hereinafter referred to as AMBN], 2,2 '-azo double (2,4-
Methyl pentane nitrile) [2,2 '-Azobis-(2,4-dimethylvaleronitrile), hereinafter referred to as ADVN] etc.；
Peroxidating two acyl (Diacyl peroxides) compounds, such as dilauroyl peroxide (Dilauroyl
Peroxide), peroxidating two-ten acyl (Decanoyl peroxide), dibenzoyl peroxide (Dibenzoyl
Peroxide, hereinafter referred to as BPO) etc.；Peroxidating dioxane (Dialkyl peroxides) compounds, as
2,5-dimethyl-2,5-di-t-butyl peroxyhexane
[2,5-Dimethyl-2,5-di-(t-butylperoxy) hexane], dicumyl peroxide (Dicumyl
Peroxide), double (tert-butylperoxyiso-propyl) benzene [1,3-Bis-(the t-butyl peroxy of 1,3-
Isopropyl) benzene] etc.；Peroxyester (Peroxyesters) compounds, as new in t-butyl peroxy penta
Acid esters (t-butylperoxypivalate), 2,5-dimethyl-2,5-bis-(2-ethylhexanoyl-peroxy) hexane
[2,5-Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane] etc.；Peroxycarbonates
(peroxycarbonates) compounds, such as t-amyl peroxy 2-ethylhexyl carbonate
(tert-Amylperoxy2-ethylhexyl carbonate), tert-butyl hydroperoxide 2-ethylhexyl carbonate
(tert-Butylperoxy2-ethylhexyl carbonate) etc.；Peroxy dicarbonate
(peroxydicarbonates) compounds, such as myristyl peroxy dicarbonate (Dimyristyl
Peroxydicarbonate), two (4-tert-butylcyclohexyl) peroxy dicarbonate
[Di (4-tert-butylcyclohexyl peroxydicarbonate) etc.；Peroxy ketal (Peroxyketal) class
Compound, such as 1,1-bis-(tert-butyl hydroperoxide)-3,3,5-3-methyl cyclohexanols
Alkane) [1,1-Di (tert-butylperoxy)-3,3,5-trimethylcyclohexane], the 2,2-bis-(4,4-bis-(tert-butyl group
Peroxidating) cyclohexyl) propane [2,2-Di (4,4-di (tert-butylperoxy) cyclohexyl) propane] etc.；Cross
Hydrogen oxide (Hydroperoxides) compounds, as tert-butyl hydroperoxide (t-Butyl hydroperoxide),
Isopropyl cumyl hydroperoxide (Isopropylcumyl hydroperoxide) etc.；Other still have 2,3-
Dimethyl-2,3-phenyl butane (2,3-Dimethyl-2,3-diphenyl-butane), potassium peroxydisulfate (Potassium
Persulfate), sodium peroxydisulfate (Sodium persulfate), Ammonium persulfate. (Ammonium persulfate) etc..
It is preferred that this initiator is 2,2 '-azo diisobutyl nitrile.With the total amount of the monomer mixture of feed-in it is
100 weight portion meters, the usage amount of this initiator can be 0.01 to 1 weight portion, preferably 0.03 to
0.5 weight portion, is more preferably 0.07 to 0.1 weight portion.
In the present invention, polyreaction can be carried out under room temperature, but for promoting polymerization speed, can be by anti-
Answering system to heat, general reaction temperature is about 5 to 200 DEG C, preferably reaction temperature be 20 to
130 DEG C, more preferably it is 30 to 100 DEG C.
The polymethacrylates compositions of the present invention can add the additive using other, example according to need
As: plasticizer, processing aid, ultra-violet stabilizer, UV absorbent, filler, reinforcing agent,
Toner, lubricant, antistatic additive, fire retardant, flame retardant, heat stabilizer, thermo-color preventing agent,
Coupling agent or other additive etc., above-mentioned additive is not limited in the polymerization, after polyreaction,
Condense before or extrude mixing during add.
Lubricant can be such as but not limited to: the metallic soaps of calcium stearate, magnesium stearate, lithium stearate etc.,
Ethylene distearyl amide, methylene distearyl amide, palmitamide, butyl stearate, stearic acid Petiolus Trachycarpi
The compound of ester, glycerol tristearate, behenic acid, stearic acid, stearyl alcohol etc., poly-second
Alkene wax, octocosoic acid wax, Brazil wax (Carnuba wax), pertroleum wax etc..Gather based on this (A)
The total amount of methacrylate is 100 weight portions, and the addition of lubricant is 0.03 to 5.0 weight portion.
In order to improve extrusion molding, hot formability, it is also possible to add such as the processing aid of acrylic ester,
Such as weight average molecular weight nucleocapsid (core-shell) formula processing aid more than 500,000.And ultraviolet
Light absorbers is such as but not limited to benzotriazole (Benzotriazole) based compound, benzophenone series chemical combination
Thing, cyanogen acrylic compounds etc.；UV stable is such as but not limited to retardance amine compound etc..
Total amount based on this (A) polymethacrylates is 100 weight portions, and the addition of aforementioned substances is 0.02
To 2.0 weight portions.
Antistatic additive can be such as but not limited to: the low molecule of tertiary amine based compound, quaternary ammonium salt based compound etc.
Based compound, or polyamide polyether, permanently charged the preventing property of 1,2 epoxy prapane polymer as chloro-in 3-
Macromolecular material.Filler can be such as but not limited to: calcium carbonate, tripoli, Muscovitum.Reinforcing agent can be such as
But it is not limited to: glass fibre, carbon fiber, various whisker (whisker) etc..Coloring agent can such as but not limit
In: titanium oxide, ferrum oxide, graphite, phthalocyanine dye.Heat stabilizer can be such as but not limited to: dibutyl
Stannum maleate, slag magnalium hydroxyl carbonate etc., and thermo-color preventing agent can be such as but not limited to:
Styrene-the anhydrous maleic acid copolymer of low-molecular-weight.
The purposes of polymethacrylates compositions of the present invention is not particularly limited, and it is applicable to injection
Molding, various products formeds, the extrusion molding of pressing mold molding (Compression moulding), blow prolong molding,
The finished product that thermoforming, vacuum forming and hollow molding are made, such as: keeper, film forming product etc.,
The demand such as high fluidity, high thermal stability can be reached according to formula allotment.
This polymethacrylates compositions can be by Brabender plastograph, Ban Baili mixing roll, kneading
The general mixed milling of-mixer, roller press, uniaxially or biaxially extruder etc. is machine-processed to be obtained.Generally mat squeezes
After going out the mixed millings such as machine, then the extrudate of extrusion is cooled down, is granulated.Polymethacrylates group
Compound usually carries out mixing at 160 to 280 DEG C, is preferable, again with the temperature of 180 to 250 DEG C
The mixed milling of each one-tenth point there is no special restriction sequentially.
The present invention will be described further with regard to following example, however, it should be noted that this embodiment is only
Illustrate and be used, and be not necessarily to be construed as the restriction of present invention enforcement.
＜ prepares (A) polymethyl methacrylate ＞
[preparation example 1]
By methyl methacrylate 92.5 weight portion, acrylic acid methyl ester. 7.5 weight portion, dodecyl sulfur
Alcohol 0.3 weight portion, 2, after 2 '-azodiisobutyronitrile 0.06 weight portion and the mixing of toluene 66 weight portion, even
Send into continuously and a reactive tank carries out continuous solution polymerization reaction.This reactive tank is to have heat kerosene circulation
Interlayer, reaction temperature maintains 100 DEG C, and pressure is 600torr.It is sufficiently stirred in reactive tank making each one-tenth
Point uniformly mixing, and after polymer solution is heated to 265 DEG C, under decompression, utilize continuous devolatilization to fill
Put after polymer solution devolatization, more extruded equipment makes bar, after cooled and pelletizing processes
Prepare (preparation example 1) polymethyl methacrylate plastic particles.
(preparation example 1) polymethyl methacrylate plastic particles contains methyl methacrylate monomer unit
94.5wt%, methyl acrylate monomer units 5.5wt%, weight average molecular weight is 110,000, melted finger
Number (MI)=1.5.
[preparation example 2]
The preparation method of preparation example 2 is roughly the same with preparation 1, and difference is that pan feeding ratio is methyl
Acrylic acid methyl ester. 95 weight portion, acrylic acid methyl ester. 5 weight portion, n-dodecyl mercaptan 0.4 weight portion,
2,2 '-azodiisobutyronitrile 0.08 weight portion.(preparation example 2) polymethyl methacrylate plastic particles contains
Methyl methacrylate monomer unit 97wt%, methyl acrylate monomer units 3wt%, weight average divides
Son amount is 6.5 ten thousand, melt index (MI)=10.
[preparation example 3]
The preparation method of preparation example 3 is roughly the same with preparation 1, and difference is that pan feeding ratio is methyl
Acrylic acid methyl ester. 93.5 weight portion, acrylic acid methyl ester. 6.5 weight portion, n-dodecyl mercaptan 0.45 weight
Amount part, 2,2 '-azodiisobutyronitrile 0.09 weight portion.(preparation example 3) polymethyl methacrylate particles
Son contains methyl methacrylate monomer unit 95.5wt%, methyl acrylate monomer units 4.5wt%,
Weight average molecular weight is 7.1 ten thousand, melt index (MI)=10.
[preparation example 4]
The preparation method of preparation example 4 is roughly the same with preparation 1, and difference is that pan feeding ratio is methyl
Acrylic acid methyl ester. 93 weight portion, acrylic acid methyl ester. 7 weight portion, n-dodecyl mercaptan 0.45 weight portion,
2,2 '-azodiisobutyronitrile 0.09 weight portion.(preparation example 4) polymethyl methacrylate plastic particles contains
Methyl methacrylate monomer unit 95wt%, methyl acrylate monomer units 5wt%, weight average divides
Son amount is 7.4 ten thousand, melt index (MI)=10.
[preparation example 5]
The preparation method of preparation example 5 is roughly the same with preparation 1, and difference is that pan feeding ratio is methyl
Acrylic acid methyl ester. 95 weight portion, acrylic acid methyl ester. 5 weight portion, n-dodecyl mercaptan 0.42 weight portion,
2,2 '-azodiisobutyronitrile 0.08 weight portion.(preparation example 5) polymethyl methacrylate plastic particles contains
Methyl methacrylate monomer unit 97wt%, methyl acrylate monomer units 3wt%, weight average divides
Son amount is 6.7 ten thousand, melt index (MI)=9.
[preparation example 6]
The preparation method of preparation example 6 is roughly the same with preparation 1, and difference is that pan feeding ratio is methyl
Acrylic acid methyl ester. 93.5 weight portion, acrylic acid methyl ester. 6.5 weight portion, n-dodecyl mercaptan 0.42 weight
Amount part, 2,2 '-azodiisobutyronitrile 0.085 weight portion.(preparation example 6) polymethyl methacrylate particles
Son contains methyl methacrylate monomer unit 95.5wt%, methyl acrylate monomer units 4.5wt%,
Weight average molecular weight is 7.5 ten thousand, melt index (MI)=9.
[preparation example 7]
The preparation method of preparation example 7 is roughly the same with preparation 1, and difference is that pan feeding ratio is methyl
Acrylic acid methyl ester. 93 weight portion, acrylic acid methyl ester. 7 weight portion, n-dodecyl mercaptan 0.43 weight portion,
2,2 '-azodiisobutyronitrile 0.086 weight portion.(preparation example 7) polymethyl methacrylate plastic particles contains
Methyl methacrylate monomer unit 95wt%, methyl acrylate monomer units 5wt%, weight average divides
Son amount is 7.9 ten thousand, melt index (MI)=9.
[preparation example 8]
The preparation method of preparation example 8 is roughly the same with preparation 1, and difference is that pan feeding ratio is methyl
Acrylic acid methyl ester. 93 weight portion, acrylic acid methyl ester. 7 weight portion, n-dodecyl mercaptan 0.4 weight portion,
2,2 '-azodiisobutyronitrile 0.08 weight portion.(preparation example 8) polymethyl methacrylate plastic particles contains
Methyl methacrylate monomer unit 95wt%, methyl acrylate monomer units 5wt%, weight average divides
Son amount is 8.2 ten thousand, melt index (MI)=8.
[preparation example 9]
The preparation method of preparation example 9 is roughly the same with preparation 4, and difference is that pan feeding ratio is positive ten
Dialkyl group mercaptan 0.47 weight portion, 2,2 '-azodiisobutyronitrile 0.09 weight portion.(preparation example 9) poly-methyl
Acrylic acid methyl ester. plastic particles contains methyl methacrylate monomer unit 95wt%, acrylic acid methyl ester. list
Body unit 5wt%, weight average molecular weight is 7.2 ten thousand, melt index (MI)=11.
[preparation example 10]
The preparation method of preparation example 10 is roughly the same with preparation 4, and difference is that pan feeding ratio is for just
Lauryl mercaptan 0.5 weight portion, 2,2 '-azodiisobutyronitrile 0.1 weight portion.(preparation example 10) poly-first
Base acrylic acid methyl ester. plastic particles contains methyl methacrylate monomer unit 95wt%, acrylic acid methyl ester.
Monomeric unit 5wt%, weight average molecular weight is 7.1 ten thousand, melt index (MI)=12.
[preparation example 11]
The preparation method of preparation example 11 is roughly the same with preparation 4, and difference is that pan feeding ratio is for just
Lauryl mercaptan 0.52 weight portion, 2,2 '-azodiisobutyronitrile 0.1 weight portion.(preparation example 11) poly-first
Base acrylic acid methyl ester. plastic particles contains methyl methacrylate monomer unit 95wt%, acrylic acid methyl ester.
Monomeric unit 5wt%, weight average molecular weight is 70,000, melt index (MI)=13.
[preparation example 12]
The preparation method of preparation example 12 is roughly the same with preparation 4, and difference is that pan feeding ratio is for just
Lauryl mercaptan 0.53 weight portion, 2,2 '-azodiisobutyronitrile 0.11 weight portion.(preparation example 12) gathers
Methyl methacrylate plastic particles contains methyl methacrylate monomer unit 95wt%, acrylic acid first
Ester monomeric unit 5wt%, weight average molecular weight is 6.95 ten thousand, melt index (MI)=14.
[preparation example 13]
The preparation method of preparation example 13 is roughly the same with preparation 4, and difference is that pan feeding ratio is for just
Lauryl mercaptan 0.55 weight portion, 2,2 '-azodiisobutyronitrile 0.11 weight portion.(preparation example 13) gathers
Methyl methacrylate plastic particles contains methyl methacrylate monomer unit 95wt%, acrylic acid first
Ester monomeric unit 5wt%, weight average molecular weight is 6.9 ten thousand, melt index (MI)=15.
[preparation example 14]
The preparation method of preparation example 14 is roughly the same with preparation 4, and difference is that pan feeding ratio is for just
Lauryl mercaptan 0.57 weight portion, 2,2 '-azodiisobutyronitrile 0.11 weight portion.(preparation example 14) gathers
Methyl methacrylate plastic particles contains methyl methacrylate monomer unit 95wt%, acrylic acid first
Ester monomeric unit 5wt%, weight average molecular weight is 6.85 ten thousand, melt index (MI)=16.
[preparation example 15]
The preparation method of preparation example 15 is roughly the same with preparation 4, and difference is that pan feeding ratio is for just
Lauryl mercaptan 0.59 weight portion, 2,2 '-azobis isobutyronitrile 0.12 weight portion.(preparation example 15) gathers
Methyl methacrylate plastic particles contains methyl methacrylate monomer unit 95wt%, acrylic acid first
Ester monomeric unit 5wt%, weight average molecular weight is 6.8 ten thousand, melt index (MI)=17.
＜ embodiment 1 to 30 and comparative example 1 to 8 ＞ prepare polymethylmethacrylacomposition composition
[embodiment 1]
By the polymethyl methacrylate of 10 kilograms of preparation examples 1, according to the kind shown in table 1 and amount ratio
Example adds antioxidant (B-1), i.e. formula (I) compound (Yiyi Industrial Co., Ltd., trade name
「HS-248P」).Mix at 230 DEG C with extruder (supplier: generation continent, model C M-PRA35) again
Merge extrusion granulator, it is thus achieved that a plexiglass compositions.
[embodiment 2 to 30]
The preparation method of embodiment 2 to 30 is roughly the same with embodiment 1, and difference is to use not
Polymethyl methacrylate and the consumption of change antioxidant (B-1) with preparation example.
The composition of embodiment 2 to 30 and consumption are recorded in table 1 in detail.
[comparative example 1]
Comparative example 1 is the polymethyl methacrylate taking preparation example 1.
[comparative example 2 to 7]
The practice of comparative example 2 to 7 is the most same as in Example 1, and difference is from using antioxidant
(B-2) (octadecyl-(3, the 5-double-tert-butyl group-4-hydroxyphenyl)-propionic ester, Yi Yi industrial corporation, trade name
「I1076」).The composition of comparative example 2 to 7 and consumption are recorded in table 1 in detail.
[comparative example 8]
Comparative example 8 is taken from the polymethyl methacrylate of preparation example 13.
＜ physical property measurement ＞
Respectively the polymethylmethacrylacomposition composition of embodiment 1 to 30 and comparative example 1 to 8 is carried out
Following Physical Property Analysis, result system is recorded in table 1 in detail.
1. melt index (representing mobility, melt index, be called for short MI) evaluating and measuring:
By the polymethylmethacrylacomposition composition of embodiment 1 to 30 and comparative example 1 to 8 respectively according to ASTM
D1238 specifies, tests with 230 DEG C × 3.8kg, unit: g/10min.
2.3% thermogravimetric weight loss temperature:
Take the embodiment 1 to 30 of 0.5 milligram and the plexiglass of comparative example 1 to 8
Composition molding product are sample, be respectively placed in thermogravimetric analyzer (Thermal Gravimetric Analysis,
Be called for short TGA) in be analyzed, analysis condition is as follows: in the environment of nitrogen, with heating rate
20 DEG C/min, temperature is risen to 600 DEG C from 100 DEG C, measure the temperature when 3% weight loss.
Note: "--" expression is not added with or does not contains." * " represents estimated value, and projectional technique is as follows: first with
Same MA=5%, the comparative example MI=9 (comparative example 7) of different molecular weight, MI=10 (comparative example 4),
MI=15 (comparative example 8) returns [the TGA value being not added with]=14* [molecular weight]+199.07, in the past
When stating formula to calculate other different molecular weights, un-added 3% thermogravimetric weight loss temperature, therefore MI=11, MI=12,
MI=13, MI=14, MI=16, MI=17, MI=8 calculate respectively 299.87 DEG C, 298.47 DEG C,
297.07℃、296.37℃、294.97℃、294.27℃、313.87℃.Again to calculate that temperature is as base
Accurate (un-added 3% thermogravimetric weight loss temperature) calculates additive efficiency.
As shown in Table 1, comparative example 1 and embodiment 1,2 select MI=1.5, molecular weight be 110,000 and
The polymethyl methacrylate of MA%=5.5.On the basis of comparative example 1, the poly-methyl-prop of comparative example 1
E pioic acid methyl ester compositions is not added with any antioxidant, and 3% thermogravimetric weight loss temperature is 335 DEG C, embodiment 1,
The polymethylmethacrylacomposition composition of 2 uses the compound (B-1) shown in the formula (I) of different amounts, implements
3% thermogravimetric weight loss temperature of example 1,2 is slightly increased to 340 DEG C, is converted into the efficiency (DEG C/10ppm) of additive
Be respectively 0.33 DEG C/10ppm, 0.17 DEG C/10ppm.
Comparative example 2～4 and embodiment 3～6 selection MI=10, molecular weight are 6.5～7.4 ten thousand and MA%=3～5
Polymethyl methacrylate.Comparative example 2～4 selects (B-2) antioxidant, comparative example 2～4 can see
Although going out through increasing molecular weight and the raising of MA%, 3% thermogravimetric weight loss temperature of comparative example 4
Improve the most limited.The compound (B-1) that embodiment 3～6 is shown through changing interpolation formula (I) into, its 3% heat
Heavily loss temperature has been promoted to the embodiment 1 of the low melt index of nearly high molecular.Compared to comparing
Example 4, embodiment 3～6 be converted into the efficiency (DEG C/10ppm) of additive be respectively 0.48 DEG C/10ppm,
0.85 DEG C/10ppm, 1.55 DEG C/10ppm, 1.26 DEG C/10ppm, the compound (B-1) shown in display formula (I)
Collocation weight average molecular weight scope is 6.5 ten thousand to 8.5, acrylic ester monomeric unit 3 to 6wt%
Polymethacrylates, its cooperative effect is obvious.Especially when addition is when less than 400ppm, by adding
From the point of view of adding the efficiency of agent (embodiment 5,1.55 DEG C/10ppm, 6,1.26 DEG C/10ppm of embodiment), its association
Become apparent from effect.
Comparative example 5～7 selects (B-2) antioxidant as comparative example 2～4, via increase molecular weight with
And the raising of MA%, 3% thermogravimetric weight loss temperature of comparative example 7 can via raising the most limited.Real
Executing the compound (B-1) that example 7～10 is shown through changing interpolation formula (I) into, its 3% thermogravimetric weight loss temperature is
It is promoted to the embodiment 1 of nearly high molecular low melt index.Compared to comparative example 7, embodiment 7～9
Be converted into the efficiency (DEG C/10ppm) of additive be respectively 0.85 DEG C/10ppm, 1.28 DEG C/10ppm,
1.5 DEG C/10ppm, 1.44 DEG C/10ppm, its cooperative effect is more preferably.Especially it is being less than when addition
During 250ppm (embodiment 8,9,10) by from the point of view of the efficiency of additive (embodiment 8,1.28 DEG C/10ppm,
Embodiment 9,1.5 DEG C/10ppm, 10,1.44 DEG C/10ppm of embodiment), its cooperative effect becomes apparent from.
Embodiment 11 prepares its 3% thermogravimetric weight loss temperature through improving molecular weight further to 8.2 ten thousand
Surmount high molecular but still maintain the embodiment 1 of low melt index.
For high fluidity, (melt index is 11～17g/10min, weight average in embodiment 12～30 display
When molecular weight ranges is 6.5 ten thousand to 7.2 ten thousand) polymethacrylates in order to improve its 3% thermogravimetric weight loss
Temperature, the optimum efficiency content range of the compound shown in required interpolation formula (I) is 120ppm.
In sum, polymethacrylates compositions of the present invention passes through collocation formula (I) compound, makes this gather
Methacrylate compositions weight average molecular weight scope is 6.8 ten thousand to 8.3 ten thousand, acrylic ester list
The polymethacrylates of body unit 4.5 to 5.5wt%, its cooperative effect becomes apparent from.Have preferably
Heat stability, therefore really can reach the purpose of the present invention.
Only as described above, only the preferred embodiments of the invention, when not limiting the present invention with this
The scope of enforcement, the most generally according to scope of the present invention patent and invention description content made simple etc.
Effect change and modification, be all still covered by the present invention within the scope of the patent.
Claims (9)
1. a polymethacrylates compositions, it is characterised in that comprise:
(A) polymethacrylates, weight average molecular weight scope is 6.8 ten thousand to 8.3 ten thousand, containing first
Base acrylic ester monomeric unit 94.5 to 95.5wt%, and acrylic ester monomeric unit 4.5 to
5.5wt%, and other copolymerizable monomer unit 0 to 1wt%；And
(B) compound shown in formula (I):
Wherein, should (A) polymethacrylates 230 DEG C, the melt index (MI) that records under 3.8Kg be
8～17g/10min, the content model of the compound shown in this formula (I) in this polymethacrylates compositions
Enclosing is 50 to 350ppm.
Polymethacrylates compositions the most according to claim 1, it is characterised in that this formula (I)
Shown compound is 100 to 300ppm at the content range of this polymethacrylates compositions.
Polymethacrylates compositions the most according to claim 1, it is characterised in that this methyl-prop
Olefin(e) acid ester system monomeric unit is n octyl methacrylate monomeric unit, methyl methacrylate monomer list
Unit, n-BMA monomeric unit, or aforesaid combination.
Polymethacrylates compositions the most according to claim 1, wherein this acrylic ester list
Body unit is acrylic acid the most own ester monomeric unit, methyl acrylate monomer units, acrylic acid ethyl ester monomer list
Unit, Butyl Acrylate Monomer unit, octadecyl acrylate monomeric unit, or aforesaid combination.
Polymethacrylates compositions the most according to claim 1, wherein, should (A) poly-methyl
Acrylate 230 DEG C, the melt index (MI) that records under 3.8Kg be 11～17g/10min, gather at this
In methacrylate compositions, the content range of the compound shown in this formula (I) is 100 to 150ppm.
6. a polymethacrylates compositions, comprises:
Polymethacrylates, weight average molecular weight scope is 6.8 ten thousand to 8.3 ten thousand, containing methyl-prop
Olefin(e) acid ester system monomeric unit 94.5 to 95.5wt%, acrylic ester monomeric unit 4.5 to 5.5wt%,
And other copolymerizable monomer unit 0 to 1wt%；And
Compound as shown in formula (I):
Wherein, in this polymethacrylates compositions, the content range of the compound shown in this formula (I) is
80 to 300ppm.
Polymethacrylates compositions the most according to claim 6, wherein this methacrylate
Be monomeric unit be methyl methacrylate monomer unit, this acrylic ester monomeric unit is acrylic acid first
Ester monomeric unit.
The most according to claim 6, polymethacrylates compositions, wherein at weight averaged molecular
When weight range is 6.8 ten thousand to 7.2 ten thousand, the chemical combination shown in this formula (I) in this polymethacrylates compositions
The content range of thing is 80 to 180ppm.
The most according to claim 6, polymethacrylates compositions, wherein at this polymethyl
When the weight average molecular weight scope of acid esters is 6.8 ten thousand to 7.2 ten thousand, this polymethacrylates compositions
In the content range of the compound shown in this formula (I) be 100 to 150ppm.
Applications Claiming Priority (4)
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| TW101151129 | 2012-12-28 | ||
| TW101151129 | 2012-12-28 | ||
| TW102148054A TWI496797B (en) | 2012-12-28 | 2013-12-24 | Poly methyl acrylate composition |
| TW102148054 | 2013-12-24 |
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| CN105778377A (en) * | 2016-05-11 | 2016-07-20 | 南京京锦元科技实业有限公司 | Glass fiber reinforced polyacrylic resin composite material |
| JP6955332B2 (en) * | 2016-11-17 | 2021-10-27 | シェルルブリカンツジャパン株式会社 | Lubricating oil composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5045581A (en) * | 1987-12-26 | 1991-09-03 | Sumitomo Chemical Company, Limited | Butadiene polymer composition containing phenolic compound and phosphorus-containing compound |
| CN101565532A (en) * | 2008-04-22 | 2009-10-28 | 奇美实业股份有限公司 | Resin composition of rubber modified (methyl) acrylic ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2952414A1 (en) * | 1979-12-27 | 1981-07-02 | Siemens AG, 1000 Berlin und 8000 München | COLORING AND RECORDING AGENTS |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5045581A (en) * | 1987-12-26 | 1991-09-03 | Sumitomo Chemical Company, Limited | Butadiene polymer composition containing phenolic compound and phosphorus-containing compound |
| CN101565532A (en) * | 2008-04-22 | 2009-10-28 | 奇美实业股份有限公司 | Resin composition of rubber modified (methyl) acrylic ester |
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