CN106432999A - 抗冲击丙烯酸掺杂物 - Google Patents
抗冲击丙烯酸掺杂物 Download PDFInfo
- Publication number
- CN106432999A CN106432999A CN201610860637.7A CN201610860637A CN106432999A CN 106432999 A CN106432999 A CN 106432999A CN 201610860637 A CN201610860637 A CN 201610860637A CN 106432999 A CN106432999 A CN 106432999A
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- China
- Prior art keywords
- polymer
- acrylic acid
- acrylic
- impact
- doped compositions
- Prior art date
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 41
- 239000000956 alloy Substances 0.000 title abstract description 9
- 229910045601 alloy Inorganic materials 0.000 title abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 56
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 33
- 239000004609 Impact Modifier Substances 0.000 claims abstract description 27
- 238000012986 modification Methods 0.000 claims description 35
- 230000004048 modification Effects 0.000 claims description 35
- 239000011258 core-shell material Substances 0.000 claims description 27
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000004575 stone Substances 0.000 claims description 22
- 239000004925 Acrylic resin Substances 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 18
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 230000005855 radiation Effects 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 8
- 239000004626 polylactic acid Substances 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000005022 packaging material Substances 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 description 27
- 229920000178 Acrylic resin Polymers 0.000 description 16
- -1 alkyl methacrylate Chemical compound 0.000 description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 12
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 9
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 230000006750 UV protection Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 description 2
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 241001274660 Modulus Species 0.000 description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229920006218 cellulose propionate Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 150000003504 terephthalic acids Chemical class 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- ULYIFEQRRINMJQ-UHFFFAOYSA-N 3-methylbutyl 2-methylprop-2-enoate Chemical group CC(C)CCOC(=O)C(C)=C ULYIFEQRRINMJQ-UHFFFAOYSA-N 0.000 description 1
- NUXLDNTZFXDNBA-UHFFFAOYSA-N 6-bromo-2-methyl-4h-1,4-benzoxazin-3-one Chemical compound C1=C(Br)C=C2NC(=O)C(C)OC2=C1 NUXLDNTZFXDNBA-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000623 Cellulose acetate phthalate Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- JSLMNNPQKHONFW-UHFFFAOYSA-N benzene naphthalene-1-carboxylic acid Chemical compound C1(=CC=CC2=CC=CC=C12)C(=O)O.C1=CC=CC=C1 JSLMNNPQKHONFW-UHFFFAOYSA-N 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229940081734 cellulose acetate phthalate Drugs 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical group CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 208000028173 post-traumatic stress disease Diseases 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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Abstract
本发明涉及一种丙烯酸类聚合物,该丙烯酸类聚合物以一种或多种硬核的核/壳式抗冲击改性剂改性并且与一种或多种低熔体粘度的聚合物掺混。由掺混形成的掺杂物具有良好的抗冲击特性、良好的熔体可处理性、高模量、高表面硬度、以及出色的化学攻击耐性。
Description
分案申请说明
本申请系申请日为2010年11月05日、国际申请号为PCT/US2010/055592、进入中国国家阶段后的国家申请号为201080050948.8、题为“抗冲击丙烯酸掺杂物”的发明专利申请的分案申请。
发明领域
本发明涉及一种丙烯酸类聚合物,该丙烯酸类聚合物以一种或多种硬核的核/壳式抗冲击改性剂改性并且与一种或多种低熔体粘度的聚合物掺混。由这种掺混形成的掺杂物具有良好的抗冲击特性、良好的熔体可处理性、高模量、高表面硬度、以及出色的化学攻击耐受性。
发明背景
丙烯酸类组合物和由其形成的制品因其澄清、无色、表面光泽、出色的可处理性、良好的抗刮擦性和UV降解抗性而公知。它们还因其低抗冲击强度或脆性而公知。已经变为行业标准的是在丙烯酸配制品中加入韧化剂或抗冲击改性剂,以改进它们的机械特性。
一类聚合物抗冲击改性剂是连续聚合的丙烯酸类组合物,包括一个内核层、一个或多个中间层、以及一个外层的层,虽然这些“层”可以进行某些混和。如在US3661994中说明的,这些被称为“核/壳”聚合物,其中该内核层或一个中间层是由橡胶聚合物制成的,并且外层的层(也被称为壳层)由一种与丙烯酸类聚合物基底兼容的玻璃性聚合物组成。在橡胶内核层的情况下,抗冲击改性剂典型地受到较低的模量和较差的UV抗性的影响,这对抗冲击改性的丙烯酸配制品是有害的。如在US 4521568和US2003/0216510中说明的,更令人希望的是由一个硬的玻璃性内核层、以及一个或多个橡胶中间层组成的核/壳聚合物来对一种丙烯酸类聚合物进行抗冲击改性而同时维持高的模量和良好的UV抗性。
抗冲击改性的丙烯酸树脂配制品是公知的。抗冲击改性的丙烯酸树脂配制品的一个问题是,加入该核/壳改性剂通过增大总体的熔体粘度而损害了聚合物基底的熔体可处理性。改进抗冲击改性的丙烯酸树脂配制品的熔体可处理性的一种已知的方式是降低丙烯酸类聚合物基底的分子量,这是通过使用一种低分子量的丙烯酸类聚合物或者通过结合一种低分子量的丙烯酸类聚合物添加剂。然而,这种手段典型地使最终树脂配制品的其他物理特性退化,如其对化学攻击的耐受性。存在的一种希望是改进抗冲击改性的丙烯酸树脂配制品的熔体可处理性同时很少或不使其他物理特性退化。
出人意料地,已经发现,加入与丙烯酸类聚合物可混溶、半混溶或相容的特定低熔体粘度的聚合物,增大了一种抗冲击改性的丙烯酸树脂的熔体可处理性而同时保持或改进了其他物理特性,如对化学攻击的耐受性。聚乳酸是这类低熔体粘度的聚合物的一个例子。硬核的核/壳抗冲击改性剂是优选的丙烯酸抗冲击改性剂。
已经用丙烯酸类聚合物来改性聚乳酸(PLA),以改进聚乳酸的特性。US2007/0179218说明了一种PLA与0.1%到15%丙烯酸共聚物的掺混物,并且优选地具有一种核/壳抗冲击改性剂。
还已经用丙烯酸类聚合物改性剂来改性PLA基底,以改进PLA的耐热性、耐冲击性和机械特性。US 2007/0276090和US 2009/0018237说明了一种PLA基底、丙烯酸类聚合物、和具有软内核层的核/壳式抗冲击改性剂的掺混物。不幸的是,软核的核/壳式抗冲击改性剂受到较低的模量和较差的UV抗性的影响,并且因此使用它们作为抗冲击改性剂显著降低了产品的总体模量和耐气候性,远大于硬核的核/壳抗冲击改性剂。
发明概述
本发明涉及一种抗冲击改性的丙烯酸类掺杂组合物,该组合物包括:
a)100份的一种抗冲击改性的丙烯酸树脂,该树脂包含15到95重量百分比的丙烯酸类聚合物以及85到5重量百分比的一种或多种核/壳抗冲击改性剂,该核/壳抗冲击改性剂具有Tg大于0℃的一个内核层以及一个或多个壳层、以及一个或多个Tg小于0℃的弹性体中间层。
b)5至150份的一种或多种低熔体粘度的聚合物;
其中在该掺杂组合物中抗冲击改性剂的重量百分比是从5到60重量百分比。
本发明进一步涉及一种用于降低抗冲击改性的丙烯酸树脂的熔体流动粘度的方法,该方法包括将基于总掺杂组合物的从5到60重量百分比的一种或多种低熔体粘度的聚合物进行混合的步骤。优选该抗冲击改性剂是一种硬核的核/壳式抗冲击改性剂。
发明详细说明
本发明涉及一种抗冲击改性的丙烯酸树脂组合物,该组合物具有一种或多种与这种丙烯酸类聚合物相容、半相容、或可混溶的低熔体粘度的聚合物。本发明的抗冲击改性剂具有一种带有硬核层的核/壳结构。这种组合物具有良好的抗冲击特性、良好的熔体可处理性、高模量、高表面硬度、以及出色的化学攻击耐受性。
抗冲击改性的丙烯酸树脂
本发明的掺杂组合物含有大于40重量百分比、优选大于70重量百分比、且更优选大于80重量百分比的一种抗冲击改性的丙烯酸树脂。在该抗冲击改性的丙烯酸树脂中抗冲击改性剂的水平是从按重量计5%到85%并且优选按重量计从10%到50%。
“丙烯酸类聚合物”,如此处所使用,是指包括由甲基丙烯酸烷基酯和丙烯酸烷基酯的单体形成的聚合物、共聚物、以及三聚物,以及它们的混合物。甲基丙烯酸烷基酯单体优选是甲基丙烯酸甲酯,它可以组成从百分之50到百分之100的单体混合物。0到50百分比的其他丙烯酸酯和甲基丙烯酸酯单体或其他烯键式不饱和单体包括但不限于苯乙烯、α-甲基苯乙烯、丙烯腈、并且交联剂也可能以低水平存在于该单体混合物中。在该单体混合物中有用的其他甲基丙烯酸酯以及丙烯酸酯单体包括但不限于丙烯酸甲酯、丙烯酸乙酯以及甲基丙烯酸乙酯、丙烯酸丁酯以及甲基丙烯酸丁酯、甲基丙烯酸异辛酯以及丙烯酸异辛酯、丙烯酸月桂酯以及甲基丙烯酸月桂酯、丙烯酸硬脂基酯以及甲基丙烯酸硬脂基酯、丙烯酸异冰片酯以及甲基丙烯酸异冰片酯、丙烯酸甲氧乙酯以及甲基丙烯酸甲氧乙酯、丙烯酸2-乙氧乙酯以及甲基丙烯酸2-乙氧乙酯、丙烯酸二甲氨基乙酯以及甲基丙烯酸二甲氨基乙酯单体。烷基(甲基)丙烯酸类例如甲基丙烯酸以及丙烯酸对于该单体混合物可以是有用的。最优选地,该丙烯酸类聚合物是一种具有70-99.5重量百分比的甲基丙烯酸甲酯单元以及从0.5到30重量百分比的一种或多种C1-8直链或支链丙烯酸烷基酯单元的共聚物。
在一个实施方案中,该丙烯酸类聚合物具有根据凝胶渗透色谱法测量的在50,000与500,000g/mol之间、优选从75,000到150,000之间的重均分子量。该丙烯酸类聚合物的分子量分布是单峰的或多峰的,并且多分散性指数高于1.5。
在另一个实施方案中,该丙烯酸类聚合物具有根据凝胶渗透色谱法测量的高于500,000g/mol、优选高于1,000,000g/mol的重均分子量。该丙烯酸类聚合物的分子量分布是单峰的或多峰的,并且多分散性指数高于4。
在另一个实施方案中,该丙烯酸类聚合物包括两种或更多种在上述两个实施方案中说明的聚合物的一个掺混物。
在另一个实施方案中,该丙烯酸类聚合物的一部分被交联到具有0.5微米与1000微米之间粒径的聚合物颗粒中。
低熔体粘度的聚合物
在掺杂组合物中的低熔体粘度的聚合物必须是与该掺杂组合物的丙烯酸类聚合物相容的、半混溶的、或可混溶的。该低熔体粘度的聚合物和丙烯酸类聚合物应当能够以一定比例掺混,使得在不分离成可区别的多个本体相的情况下产生一种单一的紧密混合物。如在此使用的,“低熔体粘度的聚合物”是指通过ASTM D1238在230℃/10.4kg的力下测量具有大于10g/10分钟的熔体流速的聚合物。
本发明的低熔体粘度的聚合物不包括丙烯酸聚合物。本发明的低熔体粘度的聚合物包括聚酯、纤维素酯、聚氧化乙烯、聚丙二醇、聚乙二醇、聚丙二醇、苯乙烯-丙烯腈共聚物、聚氯乙烯、聚乙酸乙烯酯、聚乙烯醇、乙烯-乙酸乙烯酯共聚物、烯烃-丙烯酸酯共聚物、烯烃-丙烯酸酯-马来酸酐共聚物、以及马来酸酐-苯乙烯-乙酸乙烯酯共聚物。
有用的聚酯类包括但不限于:聚(对苯二酸丁二酯),聚(对苯二酸乙二酯),聚对苯二酸乙二醇酯(polyethylene terephthalate glycol),聚乳酸。优选的聚酯是聚乳酸。
有用的纤维素酯类包括但不限于:乙酸纤维素,三乙酸纤维素,丙酸纤维素,乙酸丙酸纤维素,乙酸丁酸纤维素,以及乙酸苯二甲酸纤维素。
在一个实施方案中,该低熔体粘度的聚合物具有根据凝胶渗透色谱法测量的比该聚合物的缠结分子量更高的重均分子量。
在另一个实施方案中,低熔体粘度聚合物的水溶性低于本发明的丙烯酸类聚合物的水溶性。
本发明的低熔体粘度聚合物组成了总掺杂组合物的5到60重量百分比、优选从9到40重量百分比。
抗冲击改性剂
本发明的抗冲击改性剂是一种多层的(multi-stage)、顺序生产的聚合物,该聚合物具有由一个硬核层、一个或多个中间弹性体层、以及一个硬壳层组成的至少三层的一种核/壳式颗粒结构。一种硬核层的存在提供了在良好的抗冲击强度、高模量和优异的UV耐受性之间所希望的平衡,这种平衡是无法用拥有软核层的核/壳式改性剂实现的。该抗冲击改性剂在该掺杂组合物中是以基于总组合物从5到60重量百分比、优选10到45、更优选从20到40重量百分比的水平存在。
硬核层(Tg>0℃,优选Tg>20℃)典型地是一种单一组成的聚合物,但是也可以包括少量低Tg种子(硬核层在其上形成)的一种组合。例如,本发明中将会包括分散到硬核层中的5%的少量核种子作为一个硬核层,只要该组合的行为与硬核层相同。该硬核层可以选自满足Tg要求的任何热塑性塑料。优选地,该硬核层主要是由甲基丙烯酸酯单元、丙烯酸酯单元、苯乙烯单元、或它们的混合物组成。甲基丙烯酸酯单元包括但不限于:甲基丙烯酸甲酯,甲基丙烯酸乙酯,甲基丙烯酸正丙酯,甲基丙烯酸异丙酯,甲基丙烯酸正丁酯,甲基丙烯酸异丁酯,甲基丙烯酸仲丁酯,甲基丙烯酸叔丁酯,甲基丙烯酸戊酯,甲基丙烯酸异戊酯,甲基丙烯酸正己酯,甲基丙烯酸环己酯,甲基丙烯酸2-乙基己酯,甲基丙烯酸十五烷酯,甲基丙烯酸十二烷酯,甲基丙烯酸异冰片酯,甲基丙烯酸苯酯,甲基丙烯酸苄酯,甲基丙烯酸苯氧乙基酯,甲基丙烯酸2-羟乙基酯,和甲基丙烯酸2-甲氧乙基酯。丙烯酸酯单元包括但不限于:丙烯酸甲酯,丙烯酸乙酯,丙烯酸正丙酯,丙烯酸异丙酯,丙烯酸正丁酯,丙烯酸异丁酯,丙烯酸仲丁酯,丙烯酸叔丁酯,丙烯酸戊酯,丙烯酸异戊酯,丙烯酸正己酯,丙烯酸环己酯,丙烯酸2-乙基己酯,丙烯酸十五烷酯,丙烯酸十二烷酯,丙烯酸异冰片酯,丙烯酸苯酯,丙烯酸苄酯,丙烯酸苯氧乙基酯,丙烯酸2-羟乙基酯,和丙烯酸2-甲氧乙基酯。优选的是,该丙烯酸烷基酯是选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯和丙烯酸辛酯。苯乙烯单元包括苯乙烯及其衍生物,例如但不限于:α-甲基苯乙烯,和对甲基苯乙烯。在一个实施方案中,硬核层是全丙烯酸(all-acrylic)的。
这个或这些中间层是弹性体,具有小于0℃、且优选小于-20℃的Tg。优选的弹性体包括丙烯酸烷基酯类、二烯类、苯乙烯类的聚合物和共聚物,以及它们的混合物。优选该软的中间层主要是由丙烯酸酯单元组成。在形成软区段中有用的丙烯酸酯单元包括但不限于:丙烯酸甲酯,丙烯酸乙酯,丙烯酸正丙酯,丙烯酸异丙酯,丙烯酸正丁酯,丙烯酸异丁酯,丙烯酸仲丁酯,丙烯酸叔丁酯,丙烯酸戊酯,丙烯酸异戊酯,丙烯酸正己酯,丙烯酸环己酯,丙烯酸2-乙基己酯,丙烯酸十五烷酯,丙烯酸十二烷酯,丙烯酸异冰片酯,丙烯酸苯酯,丙烯酸苄酯,丙烯酸苯氧乙基酯,丙烯酸2-羟乙基酯,和丙烯酸2-甲氧乙基酯。优选的是,该丙烯酸烷基酯是选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯和丙烯酸辛酯。有用的二烯类包括但不限于异戊二烯和丁二烯。有用的苯乙烯类包括但不限于α-甲基苯乙烯和对甲基苯乙烯。
该壳层可以由一个或多个壳层组成,具有Tg>0℃、更优选Tg>20℃。该壳层可以是与该硬核层相同或不同的组成。
优选地,该多层聚合物是一种三层组合物,其中所存在的这些层在按重量计10%到40%、优选10%到20%的范围内的第一层(a),40%到70%、优选50%到60%的第二中间层(b),以及10%到50%、优选20%到40%的最终层(c),所有的百分比都基于该三层聚合物颗粒的总重量。
在一个实施方案中,该核层是一种交联的聚甲基丙烯酸甲酯-丙烯酸乙酯共聚物,该中间层是一种交联的聚丙烯酸丁酯-苯乙烯共聚物,并且外壳是一种聚甲基丙烯酸甲酯-丙烯酸乙酯共聚物。
这种多层聚合物可以通过用于制备多层的、顺序生产的聚合物的任何已知工艺来生产,例如通过在一种预先形成的聚合物产品存在的情况下将一种后续层的单体混合物进行乳液聚合。在本说明中,术语“顺序地乳液聚合的”或“顺序地乳液生产的”是指在水性分散体或乳液中制备的、并且其中顺序的单体填料被聚合到其上,或者在预成型的胶乳存在下通过一种预先的单体填料和层的聚合来制备。在这种类型的聚合中,将后一层附接到前一层上并与前一层紧密相关联。
在一个优选实施方案中,核/壳式颗粒的折射率与由丙烯酸类聚合物与低熔体粘度聚合物制成的基底的总折射率相匹配。匹配是指该核/壳式颗粒的折射率应当是在基底聚合物掺混物的0.03单位之内并且优选是在0.02单位之内。
这种抗冲击改性的丙烯酸树脂可以进一步包括典型地在丙烯酸配制品中存在的其他添加剂,包括但不限于:稳定剂、增塑剂、填充剂、着色剂、颜料、抗氧化剂、抗静电剂、表面活性剂、调色剂、折射率匹配剂、具有特定光衍射或光反射特性的添加剂、以及分散助剂。
在一个实施方案中,提供了一种添加剂以帮助防止掺杂物在暴露于辐射(如高水平的UV辐射或伽马辐射)时的降解。有用的辐射稳定剂包括但不限于聚(乙二醇)、聚(丙二醇)、乳酸丁酯、以及羧酸如乳酸、草酸、乙酸,或者它们的混合物。
在另一个实施方案中,提供了一种添加剂以实现该掺杂物以特定的光衍射或光反射特征进行特定的光处理。有用的添加剂包括但不限于具有在0.5微米与1000微米之间的粒径的聚合物的或无机的球形颗粒。在一个优选的实施方案中,添加剂的折射率是与该基底聚合物的折射率不同的,以便获得高于10%的雾度。
掺杂物
丙烯酸类聚合物、低熔体粘度聚合物、以及核/壳式抗冲击改性剂可以按任何顺序且通过任何本领域已知的手段进行掺混。例如,这些组分可以在熔融之前进行干混,或者直接熔融掺混到一起(例如在一个挤出机中),或者在一种适当的溶剂中密切地混合。
特性
这种组合物具有良好的抗冲击特性、良好的熔体可处理性、高模量、高表面硬度、以及优秀的化学攻击耐受性。这些特性使得该组合物对于由典型方法(如挤出、吹气模制、注塑模制、或热成型)将制品熔体处理成片、膜、棒、管、型材或最终物品而言是优异的。可以将它们用在许多应用中,如在汽车、医疗装置、表面产品、照明物、电子产品、光学显示器、光学透镜、太阳能面板、各种流体(例如水基和非水基的生物基材料的溶液)的传输、军用和安全/防御应用、消费品和日用产品外壳、器械、架子、POP显示器、墙壁覆盖物、包装应用(例如防篡改产品、如化妆品容器的容器类)。该组合物还可以被挤出或电纺成纤维而用于如织物、光纤、和光处理的应用。该组合物还可以用作一种基于溶液的配制品的一个组分(如涂层中的粘合剂)。
将低熔体粘度聚合物加入到抗冲击改性的丙烯酸树脂中增大了该掺杂组合物的熔体流速,而对物理特性(如抗冲击改性的丙烯酸树脂的机械特性和化学耐受性)很少或没有有害影响。在某些情况下,将低熔体粘度聚合物加入到该抗冲击改性的丙烯酸类聚合物中改进了某些物理特性,如抗冲击强度。根据ASTM D1238在230℃/10.4kg的力下,与未以低熔体粘度聚合物改性的抗冲击改性的丙烯酸相比,带有低熔体粘度聚合物的该掺杂物的熔体流速至少高10%、优选至少高20%、更优选至少高30%。
与低熔体粘度的丙烯酸类聚合物相比,将本发明的低熔体粘度聚合物加入到抗冲击改性的丙烯酸树脂中增大了化学耐受性,例如对醇类和类脂的耐受性。如根据ASTMD543-实验B所测量的,与将本发明的低熔体粘度聚合物用一种低熔体粘度丙烯酸类聚合物替代的相同组合物相比,本发明的抗冲击改性的丙烯酸掺杂物对醇类和类脂的耐受性至少高10%。
实例
实例1:
通过熔体挤出制备了三种材料。材料FM1是97重量百分比的甲基丙烯酸甲酯和3重量百分比的丙烯酸乙酯的一种共聚物,具有150,000g/mol的重均分子量。材料FM2是由按重量计60份的材料1与按重量计40份的一种核-壳式抗冲击改性剂(包含一个硬核层的四层结构)组成的。材料FM3类似于材料2,其中13wt%的聚(甲基丙烯酸甲酯)组分被一种聚(乳酸)组分替代,该材料具有220,000g/mol的重均分子量和20%的结晶度。这些材料的熔体粘度是通过根据ASTM 1238测量这些材料的熔体流速(MFR)来确定的。这些数据展示出,向PMMA共聚物中加入一种核-壳式抗冲击改性剂降低了熔体流速并且因此损害了树脂的熔体可处理性。然而,使用聚乳酸作为对抗冲击改性的丙烯酸树脂的添加剂显著增大了熔体流速。还测量了这些材料的机械强度,并且它们显示出向抗冲击改性的丙烯酸树脂中加入聚乳酸对材料的机械强度没有负面影响。
表1
实例2:
通过熔体挤出制备了两种材料,并且将其模制成具有0.125英尺厚度的塑料基板。第一材料是来自实例1的材料FM3。第二材料FM4是与材料FM3相同的配制品,进一步包括0.5%的乳酸丁酯。将这些塑料基板暴露于40千格雷的伽马辐射并且在伽马辐射之前和之后测量这些部件的黄度指数。如在表2中所示,材料中乳酸丁酯的存在显著降低了暴露于伽马辐射后的变黄作用。
表2
材料 | 伽马辐射之前的黄度指数 | 伽马辐射之后的黄度指数 |
FM3 | 0.6 | 10.25 |
FM4 | 0.6 | 3.56 |
实例3:
通过熔体挤出制备了两种材料。材料FM5是一种掺混物,它包括按重量计50份的、具有150,000g/mol的重均分子量的一种97重量百分比的甲基丙烯酸甲酯和3重量百分比的丙烯酸乙酯的共聚物,按重量计40份的一种核-壳式抗冲击改性剂(包括一个硬核层的四层结构),以及按重量计10份的、具有220,000g/mol重均分子量和20%结晶度的一种聚(乳酸)均聚物。材料FM6类似于材料FM5,其中该按重量计10份的聚(乳酸)由按重量计10份的一种共聚物所替代,该共聚物是69重量百分比的甲基丙烯酸甲酯和31重量百分比的甲基丙烯酸丁酯并具有43,000g/mol的重均分子量(来自现有技术的参比,对比实例)。根据ASTM D543-程序B测量了这两种材料对70%水性异丙醇的耐受性。在0.75%的恒定应力下将拉伸棒退火、调节、暴露于化学物(湿贴(wet patch)法)6小时。测量并报告了断裂时的拉伸伸长率的保留值。如在表3中所示,材料FM5的机械强度的保留值比材料FM6高35%。
表3
实例4:
通过多步乳液聚合制成了两种核-壳抗冲击改性剂并将其喷雾干燥成粉末。(本发明的)改性剂1是一种四层的硬核的核/壳颗粒,核层由PMMA组成,两个中间壳层由聚丙烯酸丁酯制成,而一个外部壳由PMMA制成。改性剂2(来自现有技术的参比,对比实例)是一个两层的软核的核/壳颗粒,该核层由聚丙烯酸丁酯制成,壳由PMMA制成。
将40份的改性剂1或改性剂2与50份的聚(甲基丙烯酸甲酯)和10份的聚(乳酸)熔融掺混,以生产抗冲击改性的树脂FM7或FM8。聚(甲基丙烯酸甲酯)是97重量百分比的甲基丙烯酸甲酯和3重量百分比的丙烯酸乙酯的一种共聚物,具有150,000g/mol的重均分子量。聚(乳酸)是具有220,000g/mol的重均分子量和20%的结晶度的一种均聚物。如在表4中示出的,与使用一种硬核的核/壳抗冲击改性剂(改性剂1)相比,使用一种软核的核/壳抗冲击改性剂(改性剂2)导致了该产品的显著更低的拉伸模量。
表4
材料 | 改性剂 | 拉伸模量(psi) |
FM7 | 改性剂1(硬核层) | 230,000 |
FM8 | 改性剂2(软核层) | 170,000 |
Claims (11)
1.一种抗冲击改性的丙烯酸掺杂组合物,包括:
a)100份的一种抗冲击改性的丙烯酸树脂组合物,该树脂组合物由以下成分组成:
1)15到95重量百分比的重均分子量为75000-500000的单一丙烯酸类聚合物,其中所述丙烯酸类聚合物是从70到99.5重量百分比的甲基丙烯酸甲酯单体单元和从0.5到30重量百分比的一种或多种丙烯酸C1-8烷基酯单体单元组成的共聚物;以及
2)85到5重量百分比的一种或多种硬核核/壳抗冲击改性剂,该抗冲击改性剂具有Tg大于0℃的一个核层和一个或多个壳层、以及一个或多个Tg小于0℃的弹性体中间层;
b)占所述抗冲击改性的丙烯酸掺杂组合物的9到40重量百分比的一种或多种与该丙烯酸类聚合物相容的聚乳酸(PLA),其中,该PLA聚合物具有通过ASTM D1238在230℃/10.4kg的力下测量的大于10g/10分钟的熔体流速;
c)选自下组的辐射稳定剂,该组由以下各项组成:聚(乙二醇),聚(丙二醇),乳酸丁酯,羧酸,及它们的混合物,
其中该抗冲击改性剂在该掺杂组合物中的重量百分比是从5到60重量百分比;如根据ASTM D543-实验B所测量的,与将所述PLA聚合物用一种低熔体粘度丙烯酸类共聚物替代的相同组合物相比,该丙烯酸掺杂组合物对醇类和类脂的耐受性至少高10%。
2.如权利要求1所述的抗冲击改性的丙烯酸掺杂组合物,其中所述丙烯酸类聚合物具有一种单峰的或多峰的分子量分布和大于1.5的多分散指数。
3.如权利要求1所述的抗冲击改性的丙烯酸掺杂组合物,其中所述丙烯酸类聚合物的一部分被交联到具有在0.5微米与1000微米之间粒径的聚合物颗粒中。
4.如权利要求1所述的抗冲击改性的丙烯酸掺杂组合物,其中所述核/壳聚合物包括Tg大于20℃的一个核层和一个壳层、以及一个具有小于-20℃的Tg的中间弹性体层。
5.如权利要求1所述的抗冲击改性的丙烯酸掺杂组合物,其中在230℃在10.4kg的力下,该熔体流速与在相同条件下的没有该低熔体粘度聚合物的相同组合物相比高出至少10%。
6.如权利要求1所述的抗冲击改性的丙烯酸掺杂组合物,其中根据ASTM D1003测量的透光率是大于80%,并且其中透射雾度是低于10%。
7.如权利要求1所述的抗冲击改性的丙烯酸掺杂组合物,其中如根据ASTM D543-实验B所测量的,与所述低熔体粘度聚合物用一种低熔体粘度丙烯酸类聚合物替代的相同组合物相比,该丙烯酸掺杂组合物对醇类和类脂的耐受性至少高10%。
8.如权利要求1所述的抗冲击改性的丙烯酸掺杂组合物,进一步包括选自下组的添加剂,该组由以下各项组成:稳定剂、增塑剂、填充剂、着色剂、抗氧化剂、抗静电剂、表面活性剂、调色剂、折射率匹配添加剂、具有特定光衍射或光反射特征的添加剂、以及分散助剂。
9.如权利要求8所述的抗冲击改性的丙烯酸掺杂组合物,其中所述具有特定光衍射或光反射特征的添加剂是具有在0.5微米与1000微米之间的粒径的一种聚合物球体颗粒。
10.一种包括权利要求1所述的抗冲击改性的丙烯酸掺杂组合物的制品。
11.权利要求10所述的制品,其中所述制品包括片、膜、棒、型材、管、汽车零件、医疗装置、防护帽层、照明产品、电子器件、太阳能面板、光学透镜、流体传输装置、消费产品外壳、墙壁覆盖物、包装材料或容器、电纺成的纤维、或涂层中的粘合剂。
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US20120164364A1 (en) | 2012-06-28 |
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