CN113968937A - 热固性生物基浇注料,由此制造的模制体以及制造这种模制体的方法 - Google Patents
热固性生物基浇注料,由此制造的模制体以及制造这种模制体的方法 Download PDFInfo
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- CN113968937A CN113968937A CN202110830275.8A CN202110830275A CN113968937A CN 113968937 A CN113968937 A CN 113968937A CN 202110830275 A CN202110830275 A CN 202110830275A CN 113968937 A CN113968937 A CN 113968937A
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- Prior art keywords
- acrylate
- methacrylate
- diacrylate
- vegetable
- dimethacrylate
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 7
- 238000005266 casting Methods 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000000178 monomer Substances 0.000 claims abstract description 68
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 235000013311 vegetables Nutrition 0.000 claims abstract description 22
- 239000011256 inorganic filler Substances 0.000 claims abstract description 19
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 19
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000005395 methacrylic acid group Chemical group 0.000 claims abstract description 13
- 229920000728 polyester Polymers 0.000 claims abstract description 9
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 5
- 229920000193 polymethacrylate Polymers 0.000 claims abstract description 5
- 229920005862 polyol Polymers 0.000 claims abstract description 5
- 150000003077 polyols Chemical class 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 19
- -1 hydroxyethyl caprolactone acrylate Chemical compound 0.000 claims description 19
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 15
- 125000004386 diacrylate group Chemical group 0.000 claims description 12
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 11
- 241000196324 Embryophyta Species 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- RHNJVKIVSXGYBD-UHFFFAOYSA-N 10-prop-2-enoyloxydecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCOC(=O)C=C RHNJVKIVSXGYBD-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 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 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 5
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 5
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 4
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- CLHPBURJMZXHFZ-UHFFFAOYSA-N (1,2,2-trimethylcyclohexyl) prop-2-enoate Chemical compound CC1(C)CCCCC1(C)OC(=O)C=C CLHPBURJMZXHFZ-UHFFFAOYSA-N 0.000 claims description 2
- IQGIEMYBDGDBMR-UHFFFAOYSA-N (3-methyl-5-prop-2-enoyloxypentyl) prop-2-enoate Chemical compound C=CC(=O)OCCC(C)CCOC(=O)C=C IQGIEMYBDGDBMR-UHFFFAOYSA-N 0.000 claims description 2
- FQKSRGCBHCFRTN-UHFFFAOYSA-N (4-nonylphenyl) prop-2-enoate Chemical class CCCCCCCCCC1=CC=C(OC(=O)C=C)C=C1 FQKSRGCBHCFRTN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- QFXBYZKQOKCTQA-UHFFFAOYSA-N (carbamoylamino) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ONC(N)=O QFXBYZKQOKCTQA-UHFFFAOYSA-N 0.000 claims description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 claims description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical class CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 2
- LRZPQLZONWIQOJ-UHFFFAOYSA-N 10-(2-methylprop-2-enoyloxy)decyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCOC(=O)C(C)=C LRZPQLZONWIQOJ-UHFFFAOYSA-N 0.000 claims description 2
- XWQPYRZLNKQZFP-UHFFFAOYSA-N 11-methyldodecyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCCCCOC(=O)C(C)=C XWQPYRZLNKQZFP-UHFFFAOYSA-N 0.000 claims description 2
- SOBZYRBYGDVKBB-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO.OCC(CO)(CO)CO SOBZYRBYGDVKBB-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 claims description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 claims description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 2
- BRRVXFOKWJKTGG-UHFFFAOYSA-N 3,3,5-trimethylcyclohexanol Chemical compound CC1CC(O)CC(C)(C)C1 BRRVXFOKWJKTGG-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- CMVNWVONJDMTSH-UHFFFAOYSA-N 7-bromo-2-methyl-1h-quinazolin-4-one Chemical compound C1=CC(Br)=CC2=NC(C)=NC(O)=C21 CMVNWVONJDMTSH-UHFFFAOYSA-N 0.000 claims description 2
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 claims description 2
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 claims description 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 claims description 2
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 2
- ISRJTGUYHVPAOR-UHFFFAOYSA-N dihydrodicyclopentadienyl acrylate Chemical compound C1CC2C3C(OC(=O)C=C)C=CC3C1C2 ISRJTGUYHVPAOR-UHFFFAOYSA-N 0.000 claims description 2
- GVEOXTFJKNAQEL-UHFFFAOYSA-N dodecan-4-yl prop-2-enoate Chemical class CCCCCCCCC(CCC)OC(=O)C=C GVEOXTFJKNAQEL-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 229940074076 glycerol formal Drugs 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- KVILQFSLJDTWPU-UHFFFAOYSA-N heptadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCOC(=O)C=C KVILQFSLJDTWPU-UHFFFAOYSA-N 0.000 claims description 2
- HJSMBDKULYJQKM-UHFFFAOYSA-N hexacosan-13-yl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCC(OC(=O)C(C)=C)CCCCCCCCCCCC HJSMBDKULYJQKM-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920006150 hyperbranched polyester Polymers 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 2
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 2
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 claims description 2
- KUZUWYWVINGZKL-UHFFFAOYSA-N octan-2-yl 2-methylprop-2-enoate Chemical compound CCCCCCC(C)OC(=O)C(C)=C KUZUWYWVINGZKL-UHFFFAOYSA-N 0.000 claims description 2
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 claims description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 2
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 claims description 2
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
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- E03C1/12—Plumbing installations for waste water; Basins or fountains connected thereto; Sinks
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Mechanical Engineering (AREA)
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- Manufacturing & Machinery (AREA)
- Polymerisation Methods In General (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
一种热固性生物基浇注料,包括:(a)由若干种单官能丙烯酸单体和/或甲基丙烯酸单体构成的混合物,其中一种或多种单体源自回收材料,且一种或多种单体为植物或动物来源的单体,(b)一种或多种植物或动物来源的多官能丙烯酸生物单体和/或甲基丙烯酸生物单体,(c)一种或多种聚合物或者共聚物,选自源自回收材料或者植物来源或者动物来源的聚丙烯酸酯、聚甲基丙烯酸酯、多元醇、聚酯,(d)天然来源的无机填料粒子,其中所述单官能丙烯酸单体和/或甲基丙烯酸单体以及所述多官能丙烯酸生物单体和/或甲基丙烯酸生物单体的比例为10‑40wt%,所述聚合物或者共聚物的比例为1‑16wt%,以及,所述无机填料粒子的比例为44‑89wt%。
Description
技术领域
本发明涉及一种热固性生物基浇注料,适于制造模制体,该模制体由其中嵌入有填料粒子的聚合浇注料形成的聚合物基质组成。本发明还涉及一种由所述浇注料制造的模制体,其形式例如为厨房水槽、盥洗台、工作台面、浴缸或者淋浴盆或者工作台面,其中所述聚合浇注料形成生物复合材料,其成分为嵌入有填料粒子的聚合物基质。
本发明的生物复合材料或本发明的模制体的具体制造方式为:首先将无机填料粒子分散在在由回收的和生物基的单官能及多官能单体构成的混合物中的至少一种生物(共)聚合物和/或回收(共)聚合物溶液中,制成本发明的浇注料,随后将所述浇注料注入模具,填充铸模型腔,并且借助热通过单官能生物单体与多官能生物单体的热诱导聚合,根据型腔形状将所述材料固定。
背景技术
众所周知,利用例如聚合浇注料制造厨房水槽。这种厨房水槽故而具有聚合物基质,在此聚合物基质中嵌入有填料粒子,用以实现期望的特性。可以使用适当的可交联的聚合物制造浇注料,其中使用石油化学来源的聚合物,即基于石油的聚合物。通过这种方式制造的厨房水槽具有极佳的机械特性,并且在较大的温度范围内具备热稳定性。尽管如此,尤其是出于可持续性(环境保护和节约资源)方面的原因,使用这类聚合物是不利的。
发明内容
因此,基于所述问题,本发明提供了一种有所改进的浇注料。
为解决所述问题,本发明提供了一种热固性生物基浇注料,包括:
(a)由若干单官能丙烯酸单体和/或甲基丙烯酸单体构成的混合物,其中一种或多种单体由回收材料制成,且一种或多种单体为植物或动物来源的单体,
(b)一种或多种植物或动物来源的多官能的丙烯酸生物单体和/或甲基丙烯酸生物单体,
(c)一种或多种聚合物或者共聚物,选自源自回收材料或者植物来源或者动物来源的聚丙烯酸酯、聚甲基丙烯酸酯、多元醇、聚酯,
(d)天然来源的无机填料粒子,
其中所述单官能丙烯酸单体和/或甲基丙烯酸单体以及所述多官能丙烯酸生物单体和/或甲基丙烯酸生物单体的比例为10-40wt%,所述聚合物或者共聚物的比例为1-16wt%,以及所述无机填料粒子的比例为44-89wt%。
本发明的浇注料的特征在于,特别是就使用的发生交联的物质而言,所述浇注料绝大部分由生物材料或天然材料构成。根据本发明,使用由不同的单官能单体构成的混合物。根据本发明,使用的单官能丙烯酸单体和甲基丙烯酸单体的混合物部分由回收材料构成并且部分由植物或者动物来源的单体构成,其中至少一种单体源自回收材料,并且至少一种单体为生物基的,即为植物或动物来源。亦即,除了回收的成分以外,在本文中几乎不使用以石油化学方式获得的聚合物,但所述回收的成分视情况而定也由回收的生物基材料构成。在任何情况下,在回收的单官能单体成分的范畴内均不使用基于石油化学的新材料。仅将植物或动物来源的单体用作多官能单体。但凡使用植物或动物来源的单体,不论是单官能还是多官能的单体,均可称之为“生物单体”,其中生物单体为生物聚合物的单体。术语“多官能”包括双官能、三官能和更高度官能的生物单体。
使用的聚合物或者共聚物优选同样为纯粹的植物或动物来源,亦即,这些物质也并非石油化学来源。然而,作为使用植物/动物来源的物质的替代方案,在本文中也可以使用由回收材料构成的聚合物或者共聚物。尽管该种材料大多为石油化学来源,但不使用新材料,而是再利用现有的、回收的材料,这从环境角度看来也是有利的。通过使用生物单体和回收材料,在本发明的浇注料内,甚至于在粘合剂中,将迄今为止使用的基于石油化学的物质完全替换成可持续性材料。当然,优选也使用纯植物或动物来源的聚合物或共聚物,故在此情形下,除了回收的单官能单体成分以外,得到完全由天然材料构成的浇注料,因为如前文所述,所述填料也纯粹为天然来源。因此,用本发明的浇注料制造的模制体为生物模制体,其主要由生物材料即天然材料构成。通过用源自可再生资源的填料粒子和交联材料制造生物复合材料(Bio-Verbundwerkstoffs)或生物复合型材料(Bio-Kompositwerkstoffs),减少以石油化学方式制造的材料的消耗,进而减少石油消耗,并且对环境产生积极影响。
在本文中,植物或动物来源的单官能丙烯酸生物单体和/或甲基丙烯酸生物单体,植物或动物来源的多官能丙烯酸生物单体和/或甲基丙烯酸生物单体,以及选自植物或动物来源的聚丙烯酸酯、聚甲基丙烯酸酯、多元醇、聚酯的生物基聚合物或共聚物,是指依据IUPAC Recommendations 2012,Pure Appl.Chem.第84卷,第2期,第377-410页,2012,“Terminology for biorelated polymers and applications(IUPAC Recommendations2012)”(http://publications.iupac.org/pac/pdf/2012/pdf/8402x0377.pdf)的物质,据此,根据第381页的定义,术语“biobased”(即“生物基”)被定义为“Composed or derivedin whole or in part of biological products issued from the biomass(includingplant,animal,and marine or forestry materials”(完全或部分地由产生自生物质(含植物、动物以及海洋或森林材料)的生物产物组成或衍生),亦即,生物基(植物或动物)初级产物或起始材料的使用也实现对应的生物基的、即具有植物或动物来源的单体或聚合物或共聚物的制造。
尽管使用主要是天然的材料来制造浇注料或模制体,即例如厨房水槽,然而出人意料地,该模制体呈现极佳的机械特性,部分甚至优于已知的采用以石油化学方式获得的交联材料制造的浇注料或模制体,特别是就抗冲击性或耐刮擦性而言。
通过用高品质的单官能以及多官能的生物丙烯酸酯单体和生物甲基丙烯酸酯单体制造诸如厨房水槽、盥洗台、浴缸、淋浴盆和工作台面的生物复合材料模制体,能够实现将高技术性能要求与产物中的较高Bio Renewable Carbon Content(BRC)(可再生碳所占比例或生物基碳含量)相结合。有大量不同的生物性资源可供用于制造单官能和多官能的生物丙烯酸酯单体和生物甲基丙烯酸酯单体,如植物油、动物脂肪、木材。生物单体中的BRC可达至多90%。
所述用生物复合材料制造的模制体由无机填料的混合物构成,所述无机填料通过所述单官能和多官能的单体的交联聚合过程嵌入聚合物基质,并且因使用再生的原料而实现较大的可持续性效应。
根据本发明,单官能单体与多官能单体的重量比应为2:1至80:1,优选为4:1至70:1,特别是为5:1至60:1。
使用的单官能单体的形式可以是回收丙烯酸酯或者植物或动物来源的生物基丙烯酸酯。它们可以选自:丙烯酸正丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸叔丁酯、丙烯酸异丁酯、丙烯酸异癸酯、二氢二环戊二烯基丙烯酸酯、乙基二乙二醇丙烯酸酯、丙烯酸十七酯、丙烯酸4-羟丁酯、丙烯酸2-羟乙酯、羟乙基己内酯丙烯酸酯、聚己内酯丙烯酸酯、丙烯酸羟丙酯、丙烯酸十二酯、丙烯酸十八酯、丙烯酸叔丁酯、2(2-乙氧基)乙基丙烯酸酯、丙烯酸四氢糠酯、2-苯氧基乙基丙烯酸酯、乙氧化4-苯基丙烯酸酯、三甲基环己基丙烯酸酯、辛基癸基丙烯酸酯、丙烯酸十三酯、乙氧化4-壬基酚丙烯酸酯、丙烯酸异冰片酯、环三羟甲基丙烷缩甲醛丙烯酸酯、乙氧化4-十二烷基丙烯酸酯、聚酯丙烯酸酯、丙烯酸十八酯、超支化聚酯丙烯酸酯、三聚氰胺丙烯酸酯、硅酮丙烯酸酯、环氧丙烯酸酯。
此外,使用的单官能单体的形式可以是回收甲基丙烯酸酯或者植物或动物来源的生物基甲基丙烯酸酯。它们可以选自:甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸二十二酯、乙烯基聚乙二醇甲基丙烯酸酯、甲基丙烯酸环己酯、甲基丙烯酸异癸酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸十二酯、甲基丙烯酸十八酯、十八烷基聚乙二醇甲基丙烯酸酯、甲基丙烯酸异十三酯、甲基丙烯酸脲基酯、甲基丙烯酸四氢糠酯、苯氧基乙基甲基丙烯酸酯、3,3,5-三甲基环己醇甲基丙烯酸酯、甲基丙烯酸异冰片酯、甲氧基聚乙二醇甲基丙烯酸酯、甲基丙烯酸缩水甘油酯、己基乙基甲基丙烯酸酯、甘油缩甲醛甲基丙烯酸酯、十二烷基十四烷基甲基丙烯酸酯、C17,4-甲基丙烯酸酯。
使用的多官能生物单体的形式可以是生物基丙烯酸酯,即植物或动物来源的丙烯酸酯。它们可以选自:1,6-己二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、聚丁二烯二丙烯酸酯、3-甲基-1,5-戊二醇二丙烯酸酯、乙氧化双酚A-二丙烯酸酯、二丙二醇二丙烯酸酯、乙氧化己二醇二丙烯酸酯、1,10-癸二醇二丙烯酸酯、酯二醇二丙烯酸酯、烷氧化二丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、丙氧化新戊二醇二丙烯酸酯、季戊四醇四丙烯酸酯、三羟甲基丙烷三丙烯酸酯、二-三羟甲基丙烷四丙烯酸酯、三(2-羟乙基)异氰脲酸酯三丙烯酸酯、二-季戊四醇五丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、丙氧化三羟甲基丙烷三丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、丙氧化甘油基三丙烯酸酯、脂族聚氨酯二丙烯酸酯、脂族聚氨酯六丙烯酸酯、脂族聚氨酯三丙烯酸酯、芳族聚氨酯二丙烯酸酯、芳族聚氨酯三丙烯酸酯、芳族聚氨酯六丙烯酸酯、聚酯六丙烯酸酯、环氧化大豆油二丙烯酸酯。
此外,使用的多官能生物单体的形式可以是生物基甲基丙烯酸酯,即植物或动物来源的甲基丙烯酸酯。它们可以选自:三乙二醇二甲基丙烯酸酯、乙二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、1,10-癸二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、乙氧化双酚A二甲基丙烯酸酯、三环癸烷二甲醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯。
根据本发明,单官能或多官能丙烯酸酯和/或甲基丙烯酸酯与特别是选自聚丙烯酸酯、聚甲基丙烯酸酯、多元醇或聚酯的聚合物或者共聚物的重量比应为90:10至60:40,优选为85:15至70:30。
所述无机填料粒子也为天然来源、即生物来源,而非以合成方式制造。这些无机填料粒子可以选自SiO2、Al2O3、TiO2、ZrO2、Fe2O3、ZnO、Cr2O5、碳、金属或者金属合金,其中也可以采用两种或两种以上不同填料粒子类型的混合物。混合比例可以是任意的。
其中,无机填料粒子应具有0.010至8000μm、优选0.05至3000μm、并且特别是0.1至1300μm的粒度。此外,无机填料粒子应具有1.0至1000的长宽比(单个粒子的长度:宽度)。
为了易于加工,应以一定方式调节获得的浇注料的粘度,使得能够借助适合的注射装置在压力下以将模具的型腔完全填满的方式将浇注料注入模具。
除所述浇注料以外,本发明还涉及一种由本发明的浇注料制造的模制体。由于所述浇注料含有生物单体、生物聚合物和生物共聚物,故所述模制体为生物复合体、即例如生物复合厨房水槽或诸如此类。
其中可以制造不同的模制体类型。据此,所述模制体可以是厨房水槽、淋浴盆、盥洗台、浴缸、工作台面、或者是地面面板、墙壁面板或者天花板面板,其中这并非详尽列举。
如前文所述,事实表明,尽管使用生物基起始材料(其构成浇注料),获得的模制体仍具有极佳的特性,特别是机械特性。模制体的聚合生物复合材料应具有2至5mJ/mm2的抗冲击强度,以及具有-30至300℃的热稳定性。
本发明的一个前述优点在于,通过使用一种、两种或两种以上单官能生物单体,能够根据产物要求改变最终产物、即成品模制体的热特性、机械特性和表面特性。例如可以通过添加具有良好柔性的生物甲基丙烯酸十二酯单体来改善抗冲击性。
生物复合材料中生物甲基丙烯酸十二酯的浓度优选为约0.5至约10wt%,特别是0.7至5.0wt%。已发现,少量的柔性的生物甲基丙烯酸十二酯便能改善抗冲击性。
本发明的另一前述优点在于,例如通过添加具有较高热稳定性的生物甲基丙烯酸异冰片酯单体,能够改善成品模制体的耐热性。
生物甲基丙烯酸异冰片酯在生物复合材料中的浓度优选为约1.0至约20wt%,特别是2.0至17.0wt%。已发现,少量的生物甲基丙烯酸异冰片酯便能改善耐刮擦性。
本发明的另一优点在于,例如通过添加具有改善的耐候性的生物丙烯酸异冰片酯单体,能够改善耐老化性。生物丙烯酸异冰片酯在生物复合材料中的浓度优选为约1.0至约10wt%,特别是2.0至7.0wt%。已发现,少量的生物丙烯酸异冰片酯便能改善耐老化性。
本发明的另一优点在于,例如通过添加生物(1,10-癸二醇二丙烯酸酯)双官能单体,改善耐化学性。生物(1,10-癸二醇二丙烯酸酯)在生物复合材料中的浓度优选为约0.15至约10wt%,特别是0.3至5.0wt%。已发现,少量的生物(1,10-癸二醇二丙烯酸酯)便能改善耐化学性。
本发明的另一优点在于,例如通过添加生物(丙氧化(3)甘油三丙烯酸酯)三官能单体,基于极佳的填料润湿,改善填料分散性。生物(丙氧化(3)甘油三丙烯酸酯)在生物复合材料中的浓度优选为约0.1至约5wt%,特别是0.3至2.0wt%。已发现,少量的生物(丙氧化(3)甘油三丙烯酸酯)便能改善填料在基质中的分布,并且改善热特性和机械特性。
本发明的另一优点在于,例如通过添加具有较高耐磨强度的生物聚乙二醇二甲基丙烯酸酯双官能单体,能够改善成型体的生物复合材料的耐磨强度。生物聚乙二醇二甲基丙烯酸酯在生物复合材料中的浓度优选为约0.1至约10wt%,特别是0.3至5.0wt%。已发现,少量的生物聚乙二醇二甲基丙烯酸酯便能改善耐磨强度。
本发明的另一优点在于,通过添加具有较高耐刮擦性的生物二季戊四醇五丙烯酸酯多官能单体,能够改善模制体的耐刮擦性。生物二季戊四醇五丙烯酸酯在生物复合材料中的浓度优选为约0.1至约7wt%,特别是0.3至5.0wt%。已发现,少量的生物二季戊四醇五丙烯酸酯便能改善耐刮擦性。
使用的无机填料的形式可为:SiO2,具体形式为石英粒子、方英石微粒、热解二氧化硅、充气二氧化硅、二氧化硅纤维、二氧化硅纤丝、硅酸盐粒子(如层状硅酸盐);Al2O3粒子,TiO2粒子,Fe2O3粒子,ZnO粒子,Cr2O5粒子,炭黑粒子,碳纳米管粒子,石墨粒子或者石墨烯粒子。
为了实现无机填料在聚合物基质中的极佳的稳定分散,所述单体混合物可以为了实现适合的粘度而包含源自回收或生物基资源的聚合物和/或共聚物的生物基成分组合。
本发明还涉及一种制造前述类型的模制体的方法,其中使用同样在前文中述及的类型的浇注料,所述浇注料被送入模具,并且在所述模具中在与室温相比更高的温度下聚合,随后将聚合模制体脱模和冷却。
其中,聚合期间的温度应介于60–140℃之间,优选介于75–130℃之间,特别是介于80-110℃之间。
此外,所述浇注料为了发生聚合而留在模具中的保持时间应介于15–50min之间,优选介于20–45min之间,特别是介于25-35min之间。
由所述热固性生物基浇注料制造模制体是多阶段工艺,其包括以下阶段:
-制造聚合物基质组分;
-将无机填料分散在聚合物基质中;
-厨房水槽、盥洗台、浴缸、工作台面的交联聚合。
具体实施方式
下面给出数个试验示例,用以详细说明本发明的浇注料、本发明的模制体和本发明的方法。
示例1:
用不同的单官能单体制造聚合物基质组分
使用的组分:
(a)单官能单体:
单官能生物基单体:
甲基丙烯酸异冰片酯(IBOMA,Evonik Performance Materials GmbH),甲基丙烯酸十二酯(LMA,Arkema France),丙烯酸异冰片酯(IBOA;Miwon Specialty Chemical Co.,Ltd),甲基丙烯酸乙酯(BCH Brühl Chemikalien Handel GmbH)
单官能的回收单体:
单官能的回收的甲基丙烯酸酯单体(rec.-MMA,Monómeros del Vallés,S.L.)
(b)多官能单体:
1,10-(癸二醇二丙烯酸酯)(Arkema France)
(c)聚合物:
丙烯酸玻璃精细研磨料XP 85(回收的PMMA,Kunststoff-und Farben-GmbH)和Aqualon EC-N100 0100(生物基乙基纤维素,Ashland Industrie Deutschland GmbH)
(d)填料:
SiO2[80%石英,粒度0.06–0.3mm(Dorfner GmbH);20%石英粉,粒度0.1–0.70μm(Quarzwerke GmbH)和TiO2粒子(Crystal International B.V.)
(e)添加剂:
生物基分散添加剂(0.1%)(BYK Chemie GmbH)和触变添加剂(0.1%)(BYKChemie GmbH)
用于制造聚合物基质的组合物是通过将丙烯酸玻璃精细研磨料XP 85(回收的PMMA,Kunststoff-und Farben-GmbH)和Aqualon EC-N100 0100(充当生物聚合物的生物基乙基纤维素,Ashland Industrie Deutschland GmbH)溶解在由表1中的单官能单体:甲基丙烯酸异冰片酯(Evonik Performance Materials GmbH),甲基丙烯酸十二酯(LMA,ArkemaFrance),丙烯酸异冰片酯(Miwon Specialty Chemical Co.,Ltd),甲基丙烯酸乙酯(BCHBrühl Chemikalien Handel GmbH)构成的混合物中来制造。将反应混合物加热至40℃,用以持续100min地加速溶解,直至得到澄清溶液。为了对基质组分进行比较,制备该组合物并汇总于表1中:
表1:
单官能单体 | 样品1 | 样品2 | 样品3 |
回收的甲基丙烯酸甲酯 | 62 | 50 | 35 |
甲基丙烯酸十二酯 | 38 | 38 | |
丙烯酸异冰片酯 | 28 | ||
甲基丙烯酸异冰片酯 | 0 | 12 | 12 |
甲基丙烯酸乙酯 | 25 |
表1中的所有样品均用作丙烯酸玻璃精细研磨料XP 85和Aqualon EC-N100 011(95:5)的溶剂,其比例为80:20,用以增加反应物质的粘度(从120至155cPs,BrookfieldViscometer DVI Prime),随后添加20wt%的生物(1,10-癸二醇二丙烯酸酯)(ArkemaFrance)。
将样品1-3中的添加有生物(1,10-DDDA)的丙烯酸玻璃精细研磨料XP85和AqualonEC-N100 011的混合物中的澄清溶液用于分散无机填料混合物(70wt%),所述无机填料混合物包含95wt%的SiO2[80%石英,粒度0.06–0.3mm(Dorfner GmbH),20%石英粉,粒度0.1–0.70μm(Quarzwerke GmbH)]和5%的TiO2粒子(Crystal International B.V.)。此外还添加生物基分散添加剂(0.1%)(BYK Chemie)和触变添加剂(0.1%)(BYK ChemieGmbH)。将如此制造的浇注料搅拌20分钟(Dispermat AE-3M,VMA-Getzmann GmbH)。用所述浇注料制造形式为厨房水槽的模制体,具体方式为,将浇注料注入模具,并且在110℃下进行为时35分钟的聚合。
由样品1–3制成的厨房水槽的机械特性和热特性。
表2:
特性 | 样品1 | 样品2 | 样品3 | 比较水槽 |
抗冲击性mJ/mm<sup>2</sup> | 3.2 | 2.7 | 2.9 | 2.3 |
耐刮擦性 | + | + | + | + |
泰伯磨损,μg | 10 | 15 | 14 | 12 |
热阻* | + | + | + | + |
耐温变性** | + | + | + | + |
为了测量抗冲击性,从水槽切出12个尺寸为80x 6mm的试样。在ZwickRoell HIT P设备上实施测量。
为了测量耐刮擦性,切出一个试样(100x 100mm),并对刮擦前后的表面形貌进行测量(Mitutoyo Surftest SJ 500P)。
针对泰伯磨损试验,切出一个试样(100x 100mm),并且在Elcometer 1720上实施磨损试验。
*所述方法基于测试规范DIN EN 13310,其中将温度为180℃的待测物为时20min地置于厨房水槽的中心处,在水槽的表面上不留下可见的变化。
**所述方法基于测试规范DIN EN 13310,其中以1000个冷水-热水循环对水槽进行处理。热水(T=90℃)为时90秒地流入水槽,随后暂缓30秒,随后冷水(T=15℃)在接下来的90秒流入。通过为时30秒的暂缓结束这个循环。
用于比较水槽的复合材料是根据专利申请案DE 38 32 351A1使用石油化学来源的有机化合物制造。
如表格所示,所有试验示例的测得的特性均至少相当于由非生物基组分(涉及单体和聚合物)构成的已知的比较水槽的特性,并且在多数情形下甚至优于比较水槽。就样品1-3而言,尤其是抗冲击性部分地显著改善。
示例2:
用不同的多官能单体制造聚合物基质组分
使用的组分:
(a)单官能单体:
回收的MMA和生物基LMA,比例62:38(回收的甲基丙烯酸酯单体(rec.-MMA,Monómeros del Vallés,S.L.)和充当生物单体的甲基丙烯酸十二酯(LMA,Arkema France))
(b)多官能单体:
1,10-(癸二醇二丙烯酸酯),丙氧化(3)甘油三丙烯酸酯(Arkema France),聚乙二醇二甲基丙烯酸酯(Arkema France)和环氧化大豆油二丙烯酸酯(Miwon SpecialtyChemical Co.,Ltd)
(c)聚合物:
丙烯酸玻璃精细研磨料XP 85(回收的PMMA(Kunststoff-und Farben GmbH)和Aqualon EC-N100 0100(乙基纤维素,Ashland Industrie Deutschland GmbH)
(d)填料:
SiO2[80%石英,粒度0.06–0.3mm(Dorfner GmbH);20%石英粉,粒度0.1–0.70μm(Quarzwerke GmbH)和TiO2粒子(Crystal International B.V.)
(e)添加剂:
生物基分散添加剂(0.1%)(BYK Chemie GmbH)和触变添加剂(0.1%)(BYKChemie GmbH)
用于制造聚合物基质的组合物是通过将丙烯酸玻璃精细研磨料XP 85(回收PMMA(Kunststoff-und Farben GmbH)和Aqualon EC-N100 0100(乙基纤维素,AshlandIndustrie Deutschland GmbH)溶解在由回收的MMA与LMA这些单官能单体以62:38的比例构成的混合物中来制造。将反应混合物加热至40℃,用以持续150min地加速溶解,随后添加多官能单体:1,10DDDA,丙氧化(3)甘油三丙烯酸酯(Arkema France),聚乙二醇二甲基丙烯酸酯(PEG-DMA,Arkema France),环氧化大豆油二丙烯酸酯(Miwon Specialty ChemicalCo.,Ltd),从而得到用于形成聚合物基质的组合物。为了对基质组分进行比较,用不同的多官能单体制造组合物并汇总于表3中。多官能单体的浓度以相对单官能单体的量的wt%给出:
表3:
多官能生物单体 | 样品4 | 样品5 | 样品6 |
1.10-癸二醇二丙烯酸酯 | 14 | ||
丙氧化(3)甘油三丙烯酸酯 | 14 | 5 | |
聚乙二醇二甲基丙烯酸酯 | 10 | 10 | |
环氧化大豆油二丙烯酸酯 | 5 |
由样品4–6制成的厨房水槽的机械特性和热特性
表4:
特性 | 样品4 | 样品5 | 样品6 | 比较水槽 |
抗冲击性mJ/mm<sup>2</sup> | 3.1 | 3.5 | 2.8 | 2.3 |
耐刮擦性 | + | + | + | + |
泰伯磨损,μg | 15 | 11 | 18 | 12 |
热阻* | + | + | + | + |
耐温变性** | + | + | + | + |
如表4中的测量值所示,在这些试验示例内,模制体同样部分呈现出显著改善的机械特性,尤其是在抗冲击性和耐刮擦性方面。亦即,通过使用生物基起始材料,不仅实现从环境角度出发的有益改进,也实现模制体的特别是机械特性的改善。
示例3:
用不同的回收聚合物或者生物聚合物制造聚合物基质组分
使用的组分:
(a)单官能单体:
回收的MMA和生物基LMA,比例62:38(回收的甲基丙烯酸酯单体(rec.MMA,Monómeros del Vallés,S.L.)和甲基丙烯酸十二酯(LMA,Arkema France))
多官能生物单体:
生物(1,10-癸二醇二丙烯酸酯)(Arkema France)和丙氧化(3)甘油三丙烯酸酯(Arkema France),比例14:14。
(b)聚合物:
回收的聚合物和生物聚合物和生物共聚物:回收的PMMA(Kunststoff-undFarben-GmbH),蓖麻油聚合物(D.O.G Deutsche Oelfabrik Ges.f.chem.Erz.mbH&Co.KG)
(d)填料:
SiO2[80%石英,粒度0.06–0.3mm(Dorfner GmbH);20%石英粉,粒度0.1–0.70μm(Quarzwerke GmbH)和TiO2粒子(Crystal International B.V.)
(e)添加剂:
生物基分散添加剂(0.1%)(BYK Chemie)和触变添加剂(0.1%)(BYK Chemie)
用于制造聚合物基质的组合物是通过将回收聚合物和/或生物聚合物和/或生物共聚物(回收PMMA(Kunststoff-und Farben-GmbH),蓖麻油聚合物(D.O.G DeutscheOelfabrik Ges.f.chem.Erz.mbH&Co.KG))溶解在由rec.MMA与LMA这些单官能单体以68:32的比例构成的混合物中来制造。将反应混合物加热至40℃,用以持续100min地加速溶解,随后以14:14的比例添加生物(1,10-癸二醇二丙烯酸酯)(Arkema France)和丙氧化(3)甘油三丙烯酸酯(Arkema France),从而得到用于形成聚合物基质的组合物。为了对基质组分进行比较,用不同的回收聚合物和生物聚合物制造组合物并汇总于表5中。生物聚合物的浓度以相对单官能单体的量的wt%给出:
表5:
聚合物 | 样品7 |
回收PMMA | 19 |
蓖麻油聚合物 | 5 |
按照在示例1中描述的方法制造厨房水槽。
由样品7制成的厨房水槽的机械特性和热特性。
表6:
Claims (14)
1.一种热固性生物基浇注料,包括:
(a)由若干种单官能丙烯酸单体和/或甲基丙烯酸单体构成的混合物,其中一种或多种单体源自回收材料,且一种或多种单体为植物或动物来源的单体,
(b)一种或多种植物或动物来源的多官能丙烯酸生物单体和/或甲基丙烯酸生物单体,
(c)一种或多种聚合物或者共聚物,选自源自回收材料或者植物来源或者动物来源的聚丙烯酸酯、聚甲基丙烯酸酯、多元醇、聚酯,
(d)天然来源的无机填料粒子,
其中所述单官能丙烯酸单体和/或甲基丙烯酸单体以及所述多官能丙烯酸生物单体和/或甲基丙烯酸生物单体的比例为10-40wt%,所述聚合物或者共聚物的比例为1-16wt%,以及所述无机填料粒子的比例为44-89wt%。
2.根据权利要求1所述的浇注料,其中单官能单体与多官能单体的重量比为2:1至80:1,优选为4:1至70:1,特别是为5:1至60:1。
3.根据权利要求1或2所述的浇注料,其中所述单官能单体选自回收丙烯酸酯和植物或动物来源的丙烯酸酯,即丙烯酸正丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸叔丁酯、丙烯酸异丁酯、丙烯酸异癸酯、二氢二环戊二烯基丙烯酸酯、乙基二乙二醇丙烯酸酯、丙烯酸十七酯、丙烯酸4-羟丁酯、丙烯酸2-羟乙酯、羟乙基己内酯丙烯酸酯、聚己内酯丙烯酸酯、丙烯酸羟丙酯、丙烯酸十二酯、丙烯酸十八酯、丙烯酸叔丁酯、2(2-乙氧基)乙基丙烯酸酯、丙烯酸四氢糠酯、2-苯氧基乙基丙烯酸酯、乙氧化4-苯基丙烯酸酯、三甲基环己基丙烯酸酯、辛基癸基丙烯酸酯、丙烯酸十三酯、乙氧化4-壬基酚丙烯酸酯、丙烯酸异冰片酯、环三羟甲基丙烷缩甲醛丙烯酸酯、乙氧化4-十二烷基丙烯酸酯、聚酯丙烯酸酯、丙烯酸十八酯、超支化聚酯丙烯酸酯、三聚氰胺丙烯酸酯、硅酮丙烯酸酯、环氧丙烯酸酯,以及选自回收甲基丙烯酸酯和植物或动物来源的甲基丙烯酸酯,即甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸二十二酯、乙烯基聚乙二醇甲基丙烯酸酯、甲基丙烯酸环己酯、甲基丙烯酸异癸酯、甲基丙烯酸酯2-乙基己酯、甲基丙烯酸十二酯、甲基丙烯酸十八酯、十八烷基聚乙二醇甲基丙烯酸酯、甲基丙烯酸异十三酯、甲基丙烯酸脲基酯、甲基丙烯酸四氢糠酯、苯氧基乙基甲基丙烯酸酯、3,3,5-三甲基环己醇甲基丙烯酸酯、甲基丙烯酸异冰片酯、甲氧基聚乙二醇甲基丙烯酸酯、甲基丙烯酸缩水甘油酯、己基乙基甲基丙烯酸酯、甘油缩甲醛甲基丙烯酸酯、十二烷基十四烷基甲基丙烯酸酯、C17,4-甲基丙烯酸酯。
4.根据前述权利要求中任一项所述的浇注料,其中所述多官能生物单体选自植物或动物来源的丙烯酸酯,即1,6-己二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、聚丁二烯二丙烯酸酯、3甲基-1,5-戊二醇二丙烯酸酯、乙氧化双酚A-二丙烯酸酯、二丙二醇二丙烯酸酯、乙氧化己二醇二丙烯酸酯、1,10-癸二醇二丙烯酸酯、酯二醇二丙烯酸酯、烷氧化二丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、丙氧化新戊二醇二丙烯酸酯、季戊四醇四丙烯酸酯、三羟甲基丙烷三丙烯酸酯、二-三羟甲基丙烷四丙烯酸酯、三(2-羟乙基)异氰脲酸酯三丙烯酸酯、二-季戊四醇五丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、丙氧化三羟甲基丙烷三丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、丙氧化甘油三丙烯酸酯、脂族聚氨酯二丙烯酸酯、脂族聚氨酯六丙烯酸酯、脂族聚氨酯三丙烯酸酯、芳族聚氨酯二丙烯酸酯、芳族聚氨酯三丙烯酸酯、芳族聚氨酯六丙烯酸酯、聚酯六丙烯酸酯、环氧化大豆油二丙烯酸酯,以及选自植物或动物来源的多官能甲基丙烯酸酯,即三乙二醇二甲基丙烯酸酯、乙二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、1,10-癸二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、乙氧化双酚A-二甲基丙烯酸酯、三环癸烷二甲醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯。
5.根据前述权利要求中任一项所述的浇注料,其中所述单官能和多官能丙烯酸酯和/或甲基丙烯酸酯与所述聚合物或共聚物的重量比为90:10至60:40,优选为85:15至70:30。
6.根据前述权利要求中任一项所述的浇注料,其中所述无机填料粒子选自SiO2、Al2O3、TiO2、ZrO2、Fe2O3、ZnO、Cr2O5、碳、金属或金属合金。
7.根据前述权利要求中任一项所述的浇注料,其中所述无机填料粒子具有0.010至8000μm、优选0.05至3000μm、并且特别是0.1至1300μm的粒度。
8.根据前述权利要求中任一项所述的浇注料,其中所述无机填料粒子具有1.0至1000的长宽比(单个粒子的长度:宽度)。
9.根据前述权利要求中任一项所述的浇注料,其中所述浇注料具有一定粘度,从而能够注入模具。
10.一种模制体,使用前述权利要求中任一项所述的浇注料制造。
11.根据权利要求10所述的模制体,其中所述模制体为厨房水槽、淋浴盆、盥洗台、浴缸、工作台面,或者为地面面板、墙壁面板或者天花板面板。
12.一种制造如权利要求10或11所述的模制体的方法,其中使用如权利要求1至9中任一项所述的浇注料,将所述浇注料送入模具,并且在所述模具中在与室温相比更高的温度下使浇注料聚合,随后将聚合模制体脱模和冷却。
13.根据权利要求12所述的方法,其中所述聚合期间的温度介于60–140℃之间、优选介于75–130℃之间、特别是介于80–110℃之间。
14.根据权利要求12或13所述的方法,其中所述浇注料为了发生聚合而保持在所述模具中的保持时间介于15–50min之间、优选介于20–45min之间、特别是介于25-35min之间。
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