CA2026383A1 - Impact modified thermoplastic polyurethane-polyester molding materials and preparation thereof - Google Patents
Impact modified thermoplastic polyurethane-polyester molding materials and preparation thereofInfo
- Publication number
- CA2026383A1 CA2026383A1 CA 2026383 CA2026383A CA2026383A1 CA 2026383 A1 CA2026383 A1 CA 2026383A1 CA 2026383 CA2026383 CA 2026383 CA 2026383 A CA2026383 A CA 2026383A CA 2026383 A1 CA2026383 A1 CA 2026383A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- thermoplastic polyurethane
- meth
- parts
- polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000012778 molding material Substances 0.000 title claims abstract description 46
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 35
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 33
- 229920000728 polyester Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 70
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 63
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 23
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000005977 Ethylene Substances 0.000 claims abstract description 19
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 12
- 229920001971 elastomer Polymers 0.000 claims abstract description 9
- 239000000806 elastomer Substances 0.000 claims abstract description 9
- -1 polybutylene terephthalate Polymers 0.000 claims description 32
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 28
- 229940093470 ethylene Drugs 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 150000002009 diols Chemical class 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000005968 oxazolinyl group Chemical group 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 3
- 229920003225 polyurethane elastomer Polymers 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract description 2
- 229920001281 polyalkylene Polymers 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 32
- 239000000306 component Substances 0.000 description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 229940117927 ethylene oxide Drugs 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 229920001897 terpolymer Polymers 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 230000000875 corresponding effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000012763 reinforcing filler Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- DISUAGIHWSSUGM-UHFFFAOYSA-N 1-isocyanato-4-[2-(4-isocyanatophenyl)ethyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CCC1=CC=C(N=C=O)C=C1 DISUAGIHWSSUGM-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical class C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000007977 PBT buffer Substances 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229940117969 neopentyl glycol Drugs 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 description 1
- CYVMBANVYOZFIG-ZCFIWIBFSA-N (2r)-2-ethylbutane-1,4-diol Chemical compound CC[C@@H](CO)CCO CYVMBANVYOZFIG-ZCFIWIBFSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- IVQOFBKHQCTVQV-UHFFFAOYSA-N 2-hydroxy-2,2-diphenylacetic acid 2-(diethylamino)ethyl ester Chemical compound C=1C=CC=CC=1C(O)(C(=O)OCCN(CC)CC)C1=CC=CC=C1 IVQOFBKHQCTVQV-UHFFFAOYSA-N 0.000 description 1
- AAAWJUMVTPNRDT-UHFFFAOYSA-N 2-methylpentane-1,5-diol Chemical compound OCC(C)CCCO AAAWJUMVTPNRDT-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 241001274660 Modulus Species 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- UIQWBVPFHHQZHH-UHFFFAOYSA-N OOOOOOOOOOOOOO Chemical compound OOOOOOOOOOOOOO UIQWBVPFHHQZHH-UHFFFAOYSA-N 0.000 description 1
- LYXFCGCYJQCSRL-UHFFFAOYSA-N OOSO Chemical compound OOSO LYXFCGCYJQCSRL-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 101100463797 Rattus norvegicus Pgrmc1 gene Proteins 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical group NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- PCVVBHUFWPHCAL-UHFFFAOYSA-N butane-1,4-diol;terephthalic acid Chemical compound OCCCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 PCVVBHUFWPHCAL-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 239000004202 carbamide Chemical group 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000004989 dicarbonyl group Chemical group 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 239000012971 dimethylpiperazine Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- MSVGHYYKWDQHFV-BQYQJAHWSA-N ditert-butyl (e)-but-2-enedioate Chemical compound CC(C)(C)OC(=O)\C=C\C(=O)OC(C)(C)C MSVGHYYKWDQHFV-BQYQJAHWSA-N 0.000 description 1
- MSVGHYYKWDQHFV-FPLPWBNLSA-N ditert-butyl (z)-but-2-enedioate Chemical compound CC(C)(C)OC(=O)\C=C/C(=O)OC(C)(C)C MSVGHYYKWDQHFV-FPLPWBNLSA-N 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical group OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- CLZOHDKRJJFTSA-UHFFFAOYSA-N n'-[2,3-di(propan-2-yl)phenyl]methanediimine Chemical compound CC(C)C1=CC=CC(N=C=N)=C1C(C)C CLZOHDKRJJFTSA-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- SZEGKVHRCLBFKJ-UHFFFAOYSA-N n-methyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNC SZEGKVHRCLBFKJ-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical class CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- HHJJPFYGIRKQOM-UHFFFAOYSA-N sodium;oxido-oxo-phenylphosphanium Chemical compound [Na+].[O-][P+](=O)C1=CC=CC=C1 HHJJPFYGIRKQOM-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
- 28 - O.Z. 0050/41134 Abstract of the Disclosure: Impact modified thermoplastic polyurethane-polyester molding materials containing, based on 100 parts by weight of (A) to (C), A) from 30 to 90 parts by weight of at least one thermoplastic polyurethane elastomer, B) from 5 to 65 parts by weight of at least one thermo-plastic polyester, preferably a polyalkylene tereph-thalate, and C) from 5 to 30 parts by weight of at least one ethylene copolymer preferably based on Ca) ethylene Cb) at least one alkyl (meth)acrylate having from 1 to 8 carbon atoms in a linear or branched alkyl moiety, but not tert-butyl (meth)-acrylate, and Cc) at least one further monomer which contains a group which is reactive toward the thermo-plastic polyurethane elastomer (A) or the thermoplastic polyester (B) and D) from 0 to 63 % by weight of at least one fibrous or particulate filler and E) from 0 to 10 % by weight of at least one assistant, the weight percentages being based on the weight of (A) to (C), are prepared by homogenizing the formative components at 190-250°C.
Description
:- ` ` 2026383 O.Z. 0050/41134 mpact modLfied thermopla~tic polyurethane-~olYe~ter molding material~ and ~reparation thereo~
The present invention relates to Lmpact modified thermoplastic polyurethane-polyester molding materials which contain A) at least one thermoplastic polyurethane elastomer, hereinafter abbreviated to TPU, B) at least one thermoplastic polyester, hereinafter abbreviated to PES, and C) at least one ethylene copolymer advantageously based on Ca) ethylene, Cb) at least one alkyl (meth)acrylate having from 1 to 8 carbon atoms in a linear or branched alkyl moiety, but not tert-butyl ~meth)-acrylate, and Cc) at least one further monomer which contains a group which is reactive toward the TPU (A) or PES (B), and optionally D) fillers and/or E) assistant~.
Thermoplastic molding materials from TPU and PES
are known.
Materials of improved low temperature impact toughnes~ as described in ~E-A-26 46 647 (GB 1 513 197) consist of an intimate mixture of from 50 to 75 part~ by weight of TPU and from 25 to 50 % by weight of a poly-butylene terephthalate, also known as PBT. CA-A-l 111 984 likewise de~cribes TPU/PBT materials which, however, based on the total weight, con~ist of from 5 to 95 ~ by weight of TPU and from 95 to 5 % by weight of PBT. The~e TPU/PBT molding materials, however, have the disadvantage of inadequate notched impact strength and insufficient multiaxial toughness, in particular at low temperatures.
TPU mixtures which contain processing aids and are composed of from 40 to 100 % by weight of TPU, from 0 to 60 % by weight of a thermoplastic polymer selected 202~83 - 2 - O.Z. OOgO/41134 from the group consisting of polycarbonates, polyoxy-methylenes, acrylonitrile-butadiene-styrene graftcopoly-mers, PBT, polyethylene terephthalate and mixture~
thereof, and from 0.5 to 10 % by weight, based on the S total weight of TPU and the other thermoplastic polymer, of a polyacrylate-based processing aid selected from the group consisting of a methyl methacrylate homopolymer, a methyl methacrylate/n-butyl methacrylate or methyl methacrylate/ethyl acrylate copolymer and a terpolymer of methyl methacrylate, n-butyl acrylate and styrene are known from US-A-4 179 479. However, these materials based on TPU, PBT or polyethylene terephthalate and the essen-tially linear (meth)acrylate homopolymer or copolymer possess unsatisfactory toughness at low temperatures and are difficult to process.
It is an ob~ect of the present invention to remove the aforementioned disadvantages as completely as possible and to develop TPU/PES molding materials which possess a distinctly improved low temperature toughness and are easy to process into shaped articles.
We have found, surprisingly, that this ob~ect is achieved by introducing at least one ethylene copolymer (C) having a specific structure into TPU/PES molding materials of defined composition.
The present invention accordingly provides impact modified thermoplastic polyurethane-polyester molding materials which contain or preferably consist of, based on 100 parts by weight of (A) to (C), A) from 30 to 90 parts by weight, preferably from 40 to 80 parts by weight, of at least one TPU (A), B) from 5 to 65 parts by weight, preferably from 10 to 60 parts by weight, of at least one P~S (B) and C) from 5 to 30 parts by weight, preferably from 8 to 25 parts by weight, of at least one ethylene copoly-mer (C) and also, ba~ed on the total weight of (A) to (C), D) from 0 to 60 % by weight, preferably from 2 to 50 %
20263~3 - 3 - O.Z. 0050/41134 by weiqht, of at least one fibrous or particulate filler and E) from 0 to 10 % by weight, preferably from 0 to 5 by weight, of at least one assistant.
The present invention further provides a proce~
for preparing the TPU/PES molding materials accordLng to the present invention by homogenizing the formative components at 190-250C in a suitable mixing apparatus.
As mentioned, the TPU/PES molding materials according to the present invention have very good low temperature toughness. The increased fluidity also appreciably improves their processibility, so that the molding materials are easily convertible into shaped articles by the in~ection molding technique. Further lS advantageous properties are for example: short cycle times in the production of shaped articles, their good demoldability and excellent resistance to organic sol-vents.
The TPUs (A) usable for preparing the TPU/PES
molding materials according to the present invention correspond to the prior art and can be prepared by reacting a) organic, preferably aromatic, diisocyanates, in particular 4,4'-diphenylmethane diisocyanate, with b) polyhydroxy compounds, preferably e~sentially linear polyhydroxy compounds, having molecular weights of from 500 to 8000, in particular polyalkylene glycol polyadipate~ having from 2 to 6 carbon atoms in the alkylene moiety and molacular weights of from 500 to 6000 or hydroxyl-containing polytetrahydrofuran having a molecular weight of from 500 to 8000, and c) diol~ a~ chain extender~ having molecular weights of from 60 to 400, in particular 1,4-butanediol, in the presence of d) catalystY and optionally e) aids and/or f) additive~
The present invention relates to Lmpact modified thermoplastic polyurethane-polyester molding materials which contain A) at least one thermoplastic polyurethane elastomer, hereinafter abbreviated to TPU, B) at least one thermoplastic polyester, hereinafter abbreviated to PES, and C) at least one ethylene copolymer advantageously based on Ca) ethylene, Cb) at least one alkyl (meth)acrylate having from 1 to 8 carbon atoms in a linear or branched alkyl moiety, but not tert-butyl ~meth)-acrylate, and Cc) at least one further monomer which contains a group which is reactive toward the TPU (A) or PES (B), and optionally D) fillers and/or E) assistant~.
Thermoplastic molding materials from TPU and PES
are known.
Materials of improved low temperature impact toughnes~ as described in ~E-A-26 46 647 (GB 1 513 197) consist of an intimate mixture of from 50 to 75 part~ by weight of TPU and from 25 to 50 % by weight of a poly-butylene terephthalate, also known as PBT. CA-A-l 111 984 likewise de~cribes TPU/PBT materials which, however, based on the total weight, con~ist of from 5 to 95 ~ by weight of TPU and from 95 to 5 % by weight of PBT. The~e TPU/PBT molding materials, however, have the disadvantage of inadequate notched impact strength and insufficient multiaxial toughness, in particular at low temperatures.
TPU mixtures which contain processing aids and are composed of from 40 to 100 % by weight of TPU, from 0 to 60 % by weight of a thermoplastic polymer selected 202~83 - 2 - O.Z. OOgO/41134 from the group consisting of polycarbonates, polyoxy-methylenes, acrylonitrile-butadiene-styrene graftcopoly-mers, PBT, polyethylene terephthalate and mixture~
thereof, and from 0.5 to 10 % by weight, based on the S total weight of TPU and the other thermoplastic polymer, of a polyacrylate-based processing aid selected from the group consisting of a methyl methacrylate homopolymer, a methyl methacrylate/n-butyl methacrylate or methyl methacrylate/ethyl acrylate copolymer and a terpolymer of methyl methacrylate, n-butyl acrylate and styrene are known from US-A-4 179 479. However, these materials based on TPU, PBT or polyethylene terephthalate and the essen-tially linear (meth)acrylate homopolymer or copolymer possess unsatisfactory toughness at low temperatures and are difficult to process.
It is an ob~ect of the present invention to remove the aforementioned disadvantages as completely as possible and to develop TPU/PES molding materials which possess a distinctly improved low temperature toughness and are easy to process into shaped articles.
We have found, surprisingly, that this ob~ect is achieved by introducing at least one ethylene copolymer (C) having a specific structure into TPU/PES molding materials of defined composition.
The present invention accordingly provides impact modified thermoplastic polyurethane-polyester molding materials which contain or preferably consist of, based on 100 parts by weight of (A) to (C), A) from 30 to 90 parts by weight, preferably from 40 to 80 parts by weight, of at least one TPU (A), B) from 5 to 65 parts by weight, preferably from 10 to 60 parts by weight, of at least one P~S (B) and C) from 5 to 30 parts by weight, preferably from 8 to 25 parts by weight, of at least one ethylene copoly-mer (C) and also, ba~ed on the total weight of (A) to (C), D) from 0 to 60 % by weight, preferably from 2 to 50 %
20263~3 - 3 - O.Z. 0050/41134 by weiqht, of at least one fibrous or particulate filler and E) from 0 to 10 % by weight, preferably from 0 to 5 by weight, of at least one assistant.
The present invention further provides a proce~
for preparing the TPU/PES molding materials accordLng to the present invention by homogenizing the formative components at 190-250C in a suitable mixing apparatus.
As mentioned, the TPU/PES molding materials according to the present invention have very good low temperature toughness. The increased fluidity also appreciably improves their processibility, so that the molding materials are easily convertible into shaped articles by the in~ection molding technique. Further lS advantageous properties are for example: short cycle times in the production of shaped articles, their good demoldability and excellent resistance to organic sol-vents.
The TPUs (A) usable for preparing the TPU/PES
molding materials according to the present invention correspond to the prior art and can be prepared by reacting a) organic, preferably aromatic, diisocyanates, in particular 4,4'-diphenylmethane diisocyanate, with b) polyhydroxy compounds, preferably e~sentially linear polyhydroxy compounds, having molecular weights of from 500 to 8000, in particular polyalkylene glycol polyadipate~ having from 2 to 6 carbon atoms in the alkylene moiety and molacular weights of from 500 to 6000 or hydroxyl-containing polytetrahydrofuran having a molecular weight of from 500 to 8000, and c) diol~ a~ chain extender~ having molecular weights of from 60 to 400, in particular 1,4-butanediol, in the presence of d) catalystY and optionally e) aids and/or f) additive~
- 4 ~ O.Z. 0050/41134 at elevated temperatures.
The TPU-forming components (a) to (d) and option-ally (e) and/or (f) may be described in detail as follows:
a) Suitable organic diisocyanate~ (a) are for example aliphatic, cycloaliphatic and preferably aromatic diisocyanateR. Specific examples are: aliphatic diiso-cyanates such as 1,6-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylene dii~ocyanate, ~-ethyl-1,4-butylene diisocyanate and mixtures of at least two ofsaid aliphatic diisocyanates, cycloaliphatic diisocyan-ates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, l-methyl-2,4-cyclohexane diisocyanate and l-methyl-2,6-cyclohexane dii~ocyanate and the correspond-ing isomeric mixtures, 4,4'-, 2,4'- or 2,2~-dicyclohexyl-methane diisocyanate and the correQponding isomeric mixtures and preferably aromatic diisocyanates such a~
2,4-toluylene diisocyanate, mixtures of 2,4- and 2,6-toluylene diisocyanate, 4,4'-, 2,4'- and 2,2'-diphenyl-methane diisocyanate, mixtures of 2,4'- and 4,4~-di-phenylmethane diisocyanate, urethane-modified liquid 4,4~- and/or 2,4'-diphenylmethane diisocyanates, 4,4'-diisocyanato-1,2-diphenylethane, mixtures of 4,4'-, 2,4'-and 2,2~-diisocyanato-1,2-diphenylethane, preferably those having a 4,4'-diisocyanato-1,2-diphenylethane content of at least 95 % by weight, and 1,5-naphthylene diisocyanate. Preference is given to using diphenyl-methane diisocyanate i omer mixture~ having a 4,4'-diphenylmethane diisocyanate content of greater ~han 96 %
by weight and in particular essentially pure 4,4'-di-phenylmethane diisocyanate.
The organic diisocyanates may be replaced to a minor extent, for example in an amount of up to 3 mol %, preferably up to 1 mol %, based on the organic diisocyan-ate, by a trifunctional or more highly functional poly-isocyanate, the amount of which, however, must be limited in such a way a~ to produce a still thermoplastic poly-2026~3 O.Z. 0050/41134 urethane. A ma~or amount of such tri- or more highly functional isocyanates is advantageously balanced by the inclusion of less than difunctional compounds having reactive hydrogen atoms, in order that excessive chemical crosslinking of the polyurethane may be avoided. Example~
of more than difunctional isocyanates are mixtures of diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates, so-called crude MDI, and liquid 4,4~-and/or 2,4'-diphenylmethane diisocyanate modified with isocyanurate, urea, biuret, allophanate, urethane and/or carbodiimide groups.
Suitable monofunctional compounds having a reactive hydrogen atom which are also usable as molecular weight regulators are for example: monoamines such as butylamine, dibutylamine, octylamine, stearylamine, N-methylstearylamine, pyrrolidone, piperidine and cyclo-hexylamine and monoalcohols such as butanol, amyl alcohol, 1-ethylhexanol, octanol, dodecanol, cyclohexanol and ethylene glycol monoethyl ether.
b) Preferred polyhydroxy co~pounds (b) having molecular weights of from 500 to 8000 are polyetherols and in particular polyesterols. However, it is also possible to u~e other hydroxyl-containing polymers containing ether or ester group~ as bridge members, for example polyacetals, such as polyoxymethylenes and in particular water-insoluble formals, eg. polybutanediol formal and polyhexanediol formal, and polycarbonates, in particular those formed from diphenyl carbonate and 1,6-hexanediol, prepared by transesterification. The poly-hydroxy compound~ must be at least predominantly linear,ie. difunctional within ths meaning of the i~ocyanate reaction. The polyhydroxy compound~ mentioned may be used as individual components or in the form of mixtures.
Suitable polyetherols can be prepared from one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene moiety in a conventional manner, for example by anionic polymerization with alkali metal hydroxide~, 20263~3 - 6 - O.Z. OOSO/41134 such as sodium hydroxide or pota3sium hydroxide, or alkali metal alcoholates, ~uch as sodium methoxide, sodium ethoxide, potassium ethoxide or potassium isoprop-oxide, as catalysts and in the presence of at least one initiator molecule which contains 2 or 3, preferably 2 reactive hydrogen atoms, or ~y cationic polymerization with Lewi~ acids, such as antimony pentachloride, boron fluoride etherate, etc. or bleaching earth, as catalysts.
Preferred alkylene oxides are for example tetra-hydrofuran, 1,3-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and in particular ethylene oxide and 1,2-propylene oxide. The alkylene oxides may be used indi-vidually, alternately in succession or as mixtures.
Suitable initiator molecules are for example: water, organic dicarboxylic acids, such as succinic acid, adipic acid and/or glutaric acid, alkanolamines, such as ethan-olamine, N-alkylalkanolamines, N-alkyldialkanolamines, eg. N-methyl- and N-ethyl-diethanolamine, and preferably dihydric alcohols which may contain ether linkages, eg.
ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butane-diol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, 2-methyl-1,5-pentanediol and 2-ethyl-1,4-butanediol. The initiator molecules may be used individually or as mixtures.
Preference is given to using polyetherols from 1,2-propylene oxide and ethylene oxide in which more than 50 %, preferably from 60 to 80 ~, of the OH groups are primary hydroxyl groups and where at lea~t some of the ethylene oxide units are present a~ a terminal block.
Such polyethero}~ can be obtained by, for example, polymerizing onto the initiator molecule fir~t the 1,2-propylene oxide and then the ethylene oxide, or first the entire 1,2-propylene oxide mixed with ~ome of the ethyl-ene oxide and then the remainder of the ethylene oxide, or step by step first some of the ethylene oxide, then the entire 1,2-propylene oxide and then the remainder of tha ethylene oxide.
202~3~3 - 7 - O.Z. 0050/41134 Other preferred possibilitie~ are the hydroxyl-containing polymerization products of tetrahydrofuran.
The essentially linear polyetherols have mole-cular weights of from 500 to 8000, preferably from 600 to 6000, in particular from 800 to 3500, the polyoxytetra-methylene glycols preferably having molecular weights of from 500 to 2800. They can be used not only individually but also in the form of mixtures with one another.
Suitable polyesterols may be prepared for example from dicarboxylic acids of from 2 to 12, preferably from 4 to 6, carbon atoms and polyhydric alcohols. Suitable dicarboxylic acids are for example: aliphatic dicar-boxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and ~ebacic acid, and aromatic dicarboxylic acids, such a~ phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, for example in the form of a mixture of succinic acid, glutaric acid and adipic acid. To prepare the poly-esterols it may be advantageous to use instead of the dicarboxylic acids the corresponding dicarboxylic acid derivatives, such as dicarboxylic monoesters or diesters having from 1 to 4 carbon atoms in the alcohol moiety, dicarboxylic anhydrides or dicarbonyl dichlorides.
Examples of polyhydric alcohol~ are glycols of from 2 to 10, preferably from 2 to 6, carbon atoms, such as ethyl-ene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-di-methylpropane-1,3-diol, 1,3-propanediol and dipropylene glycol. Depending on the properties which are desired, the polyhydric alcohols may be used alone or optionally mixed with one another.
It i8 also possible to use esters of carbonic acid with the diols mentioned, in particular those having from 4 to 6 carbon atoms, such as 1,4-butanediol and/or 1,6-hexanediol, condensation products of ~-hydroxycar-boxylic acids, eg. w-hydroxycaproic acid, and preferably - 8 - o.z 0050/41134 polymer~zation produ~tY of lactones, for example ~ubsti-tuted or unsubstituted ~-caprolactone~.
Preferred polyesterols are ethanediol poly-adipates, 1,4-butanediol polyadipates, ethanediol/1,4-butanediol polyadipates, 1,6-hexanediol/neopentylglycol polyadipates, 1,6-hexanediol/1,4-butanediol polyadipates and polycaprolactones.
The polyesterols have molecular weights of from 500 to 6000, preferably from 800 to 3500.
c) Suitable chain extenders (c) having molecular weights of from 60 to 400, preferably from 60 to 300, are preferably aliphatic diols of from 2 to 12 carbon atoms, preferably of 2, 4 or 6 carbon atoms, eg. ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and in particular 1,4-butanediol. However, it is also pos-sible to use diesters of terephthalic acid with glycols of from 2 to ~ carbon atoms, eg. bisethylene glycol terephthalata, 1,4-butanediol terephthalate, and hydroxy-alkylene ethers of hydroquinone, eg. 1,4-di-(~-hydroxy-ethyl)-hydroquinone, and also polytetramethylene glycols having molecular weights of from 162 to 378.
To ~et the hardne3s and the melt flow index, the formative components can be varied within relatively wide molar ratios bearing in mind that the hardness and melt viscosity increase with an increasing level of chain extenders (c) while the melt flow index decrea3es.
To prepare relatively soft TPUs (A), for example those having a Shore A hardnes~ of less than 95, prefer-ably from 95 to 75, it is advantageous for exhmple to use the es~entially difunctional polyhydroxy compounds (b) and the diols (c) in a molar ratio of from 1:1 to 1:5, preferably from 1:1.5 to 1:4.5, 80 that the resulting mixture3 of (b) and (c) have a hydroxy equivalent weight of greater than 200, in particular from 230 to 450, while harder TPU8 (A), for example those having a Shore A
hardnes~ of greater than 98, preferably from 55 to 75 Shore D, are prepared u~ing molar ratios of (b):(c) _ g _ O.Z. 0050/41134 within the range from 1:5.5 to 1:15, preferably from 1:6 to 1:12, so that the re~ulting mixtures of (b) and (c) have a hydroxy equivalent weight of from 110 to 200, preferably from 120 to 180.
d) Suitable catalysts, in particular for the reac-tion between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the formative components (b) and (c), are the customary tertiary amines, such as triethyl-amine, dimethylcyclohexylamine, N-msthylmorpholine, N,N~-dimethylpiperazine, diazabicyclo[2.2.2]octane and the like, and in particular organic metal compounds such as titanic esters, iron compounds, tin compounds, eg. ~in diacetate, tin dioctanoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate and the like.
The catalysts are customarily u~ed in amounts of from 0.001 to 0.1 part by weight per 100 parts by weight of the mixture of polyhydroxy compounds (b) and diols (c).
In addition to catalysts, the formative compo-nents may also contain aids (e) and/or additives (f).
Examples are lubricants, inhibitors, stabili~ers against hydrolysis, light, heat or discoloration, flame retar-dants, dyes, pigments, inorganic and/or organic fillers and reinforcing agents.
The aids (e) and/or additives (f) may be intro-duced into the formative components or into the reaction mixture for preparing the ~PUs (A). Alternatively, the aids (e) and/or additives (f), which may be identical to the assistant (E), may be mixed with the TPU (A), the PES
(B) and/or the ethylene copolymer (C) and then melted, or they are incorporated directly into the melt of com-ponents (A), (B) and (C). The latter method is also adopted in particular for incorporating the fibrous and/or particulate fillers (D).
Whera, in what follows, no details are provided concerning the usable aids or additives, they can be gathered from the relevant technical literature, for - 10 - O.Z. 0050/41134 example J.H. Saunders and K.C. Frisch's monograph, High Polymers, volume XVI, Polyurethanes, parts 1 and 2 (Interscience Publishers 1962 and 1964 respectively), Kunststoff-Handbuch, volume 7, Polyurethane~, 1st and 2nd editions (Carl Hanser Verlag 1966 and 1983 respectively), or DE-A-2,901,774.
To prepare the TPUs (A), the formative components (a), (b) and (c) are made to react in the presence of a catalyst (d) and in the presence or absence of aids (e) and/or additives (f) in such amounts that the equivalence ratio of the diisocyanate NCO groups to the total number of hydroxyl groups of components (b) and (c) is from 0.95 to 1.10:1, preferably 0.98 to 1.08:1, in particular approximately 1.0 to 1.05:1.
The TPUs (A) which are usable according to the present invention and which customarily contain from 8 to 20 % by weight, preferably from 8 to 16 % by weight, based on the total weight, of urethane groups and have a melt flow index at 210C of from 500 to 1, preferably from 100 to 1, can be prepared by the extruder technique or preferably the belt technique by batchwi~e or con-tinuous mixing of formative components (a) to (d) and optionally (e) and/or (f~, fully reacting the mixture in an extruder or on a support belt at from 60 to 250C, preferably at from 70 to 150C, and then granulating the resulting TPUs (A). It may be advantageous to heat the resulting TPU (A) at from 80 to 120C, preferably at from 100 to 110C, for a period of from 1 to 24 hour3 before further processing into the TPU/PES molding materials according to the present invention.
The TPUs (A) are, as mentioned, preferably prepared by the belt technique. To this end, the forma-tive components (a) to (d) and optionally (e) and/or (f) are continuously mixed with the aid of a mixing head at above the melting point of formative components (a) to (c). The reaction mixture is discharged onto a support, preferably a conveyor belt, for example a metal belt, and 202~383 ~ O.Z. 0050/41134 i~ passed at 1-20 m/min, preferably 4-10 m~min, through a hot zone from 1 to 20 m, preferably from 3 to 10 m, in length. The temperature in the hot zone is 60-200C, preferably 80-180C. Depending on the diisocyanate content of the reaction mixture, the reacSion is con-trolled by cooling or heating in such a way that at least 90 %, preferably at least 98 %, of the isocyanate groups of the diisocyanates react and the reaction mixture solidifies at the chosen reaction temperature. Owing to the free isocyanate groups in the solidified reaction product, which based on the total weight are within the range from O.OS to 1 % by weight, preferably from 0.1 to 0.5 % by weight, the TPUs (A) obtained have a very low melt vi~cosity or a high melt flow index.
B) Formative component (B) of the TPU/PES molding materials according to the present invention comprises, as mentioned, an amount, based on 100 parts by weight of (A), (B) and (C), of from 5 to 65 parts by weight, preferably from 10 to 60 parts by weight, in particular 12 to 50 parts by weight, of one or more thermoplastic polye~ters. Polyesters ~uitable for this purpose are described in the literature. They contain in the ~olycon-den~ate main chain at least one aromatic ring derived from an aromatic dicarboxylic acid. The aromatic ring may also be sub~tituted, for example by halogen, eg. chlorine or bromine, or/and by linear or branched alkyl, prefer-ably of from l to 4 carbon atoms, in particular of 1 or 2 carbon atoms, eg. methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl or tert-butyl.
The polyesters can be prepared by polycondens-ation of aromatic dicarboxylic acids or mixture~ of aromatic and aliphatic and/or cycloaliphatic dicarboxylic acids and the corresponding ester-forming derivatives, for example dicarboxylic anhydrides, monoester~ and/or diester~ having advantageously not more than 4 carbon atoms in the alcohol moiety, with aliphatic dihydroxy compounds at elevated temperature~, for example at from 20263~3 - 12 - O.Z. 0050/41134 160 to 260C, in the presence or absence of e~terifica-tion catalysts.
The preferred aromatic dicarboxylic acids are the naphthalenedicarboxylic acids, i~ophthalic acid and in particular terephthalic acid or mixtures of these dicarb-oxylic acids. Ifmixtures of aromatic and (cyclo)aliphatic dicarboxylic acids are used, up to 10 mol ~ of the aromatic dicarboxylic acids may be replaced by aliphatic and/or cycloaliphatic dicarboxylic acids of advantage-ously 4-14 carbon atoms, eg. succinic, adipic, azelaic, sebacic or dodecanedioic acid and/or cyclohexanedicar-boxylic acid.
The preferred aliphatic dihydroxy compounds are alkanediols of from 2 to 6 carbon atoms and cycloalkane-diols of from 5 to 7 carbon atom~. Specific examples of preferred aliphatic dihydroxy compounds are 1,2-ethane-diol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol and 1,4-cyclohexanediol and mixtures of at least two of said diols.
Particularly suitable PES's (B) are specifically the polyalkylene terephthalates of alkanediols of from 2 to 6 carbon atom~, 80 that polye~hylene terephthalate and in particular polybutylene terephthalate are preferred.
The relative vi~cosity of the PES's (B) is in 2S general within the range from 1.2 to 1.8, measured in a 0.5 ~ strength by weight solution in 1:1 w/w phenol/o-dichlorobenzene at 25C.
C) The TPU/PES molding materials according to the present invention contain one or more ethylene copolymers (C) for improving the impect toughnes~, in particular at low temperatures, and increasing the fluidity as addi-tional formative component in an amount, based on 100 parts by weight of the molding materials consisting of (A), (B) and (C~, of from 5 to 30 parts by weight, especially from 8 to 30 parts by weight, in particular from 10 to 25 parts by weight.
Suitable ethylene copolymers (C) are 202~c~83 - 13 - O.Z. 0050/41134 advantageously ba~ed on Ca) ethylene, Cb) at least one alkyl (meth)acrylate having from 1 to 8 carbon atoms in a linear or branched alkyl moiety, but not tert-butyl (meth)acrylate, and Cc) at least one further monomer which contain~ a ~roup which is reactive towards the TPU (A) or PES (B).
Preference is given to using those ethylene copolymers (C) which based on the total weight contain in polymerized form:
Ca) ethylene units in an amount of from 50 to 98% by weight, preferably from 60 to 95% by weight, Cb) alkyl (meth)acrylate units in an amount of 1 to 45%
by weight, preferably from 10 to 35% by weight, and Cc) an amount of a further comonomer (Cc) having a group which is reactive toward TPU (A) or PES (B) ranging from 0.1 to 40~ by weight, preferably from l to 40%
by weight, in particular from 2 to 20% by weight.
Ca) Ethylene as monomer is sufficiently well known in polymer chemistry enough to make further remarks redundant.
Cb) The (meth)acrylic e~ters used as acrylates and/or methacrylate~ (Cb) having from 1 to 8 carbon atoms, preferably from 2 to 8 carbon atoms, in a linear or branched alkyl moiety are those where, in the ready-prepared ethylene copolymer (C), the ester groups of the polymerizable (meth)acrylate units react essen-tially not at all or only to a minor extent with the TPU (A) or PES (B) under the reaction conditions of formin~ TPU/PES molding material~. Specific examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl and n-octyl acrylates and methacrylates. The alkyl (meth)acrylates can be used indi~idually or in the form of mixtures. Preference is gi~en to using n-butyl and/or 2-ethylhexyl (meth)acrylate.
Cc) Suitable comonomerC (Cc) are olefinically 2026 38~`
- 14 - O.Z. 0050/41134 unsaturated monomers which are copolymerizable with ethylene and alkyl (meth)acrylates and contain a reactive group which, in the ready-prepared ethylene copolymer (C), reacts with the TPU (A) or PES (B) under the reaction conditions for forming TPU/PES
molding materials, the reaction taking place to such an extent that, after the reaction has ended, the degree o~ coupling to the TPU (A) and PES (B) i5 greater than 0.01, preferably within the range from 0.03 to 1, in particular from 0.05 to 0.8, the degree of coupling being defined here as the ratio of ethylene copolymer (C) not extractable with toluene from the TPU/PES molding material to the total amount of ethylene copolymer (C) used.
Examples of groups which are reactive with TPU (A) or PES (B) are sulfo, sulfonyl, oxazoline and epoxy groups, preferably carboxyl, tert~butyl carboxylate and carboxylic anhydride groups.
Suitable comonomers (Cc) for preparing the ethylene copolymers (C) are for example olefinically unsaturated monocarboxylic acids, eg. acrylic acid and methacrylic acid and the corresponding tert-butyl esters, eg. tert-butyl (meth)acrylate, olefinically unsaturated dicarboxylic acids, eg. fumaric acid and maleic acid, and the corresponding mono- and/or di-tert-butyl esters, eg.
mono- and di-tert-butyl fumarate and mono- or di-tert-butyl maleate, olefinically unsaturated dicarboxylic anhydride~, eg. maleic anhydride, sulfo- or sulfonyl-containing olefinically unsaturated monomers, eg. p-styrene~ulfonicacid,2-(meth)acrylamido-2-methylpropene-sulfonic acid or 2-sulfonyl (meth)acrylate, oxazolinyl-containing olefinically unsaturated monomers, eg. vinyl oxazolines and vinyl oxazoline derivatives, and olefini-cally unsaturated monomers which contain epoxy groups, eg. glycidyl (meth)acrylate or allyl glycidyl ether.
Particularly preferred comonomers (Cc) are acrylic acid, methacrylic acid, tert-butyl (meth)acrylate '~02~83 - 15 - O.Z. 0050/41134 and/or in particular maleic anhydride and also glycidyl methacrylate.
Said comonomers (Cc), like the alkyl (meth)acryl-ates, can be used individually or in the form of mixtures for preparing the ethylene copolymer (C).
The ethylene copolymers (C) can be prepared in a conventional manner, preferably by random copolymeriza-tion under high pressure, for example at from 200 to 4000 bar, and at elevated temperature, for example within the range from approximately 120 to 300C. Appropriate techniques are described in literature and patent publi-cation~.
~ he melt flow index of suitable ethylene copoly-mers (C) is advantageously within the range from 1 to 80 g/10 min, preferably from 2 to 25 g/10 min (measured at 190C under a load of 2.16 kg in accordance with German Standard Specification DIN 53 735).
The impact modified thermoplastic TPU/PES molding materials according to the present invention may in addition to the e ~ential components (A), (B) and (C) optionally also contain fibrous and/or particulate fillers (D) and/or assistant3 (E).
D) The proportion of filler (D) is customarily from 0 to 60 % by weight, preferably from 2 to 50 % by weight, in particular from 5 to 30 % by weight, based on the total weight of components (A) to (C).
Suitable particulate fillers are for example:
organic fillers, such a~ carbon black, chlorinated polyethylenes and melamine, and inorganic fillers such as wollastonite, calcium carbonate, magnesium carbonate, amorphous silica, calcium ~ilicate, calcium metasilicate, quartz powder, talc, kaolin, mica, feldspar, glass spheres, silicon nitride, boron nitride and mixtures thereof.
Particularly suitable reinforcing fillers which are therefore preferred are fiber~, for example carbon fibers and in particular gla~s fiber~, with or without an 202~38'~
- 16 - O.Z. 0050/41134 adhesion promoting or/and size finish. Suitable glas~
fibers, which are also for example in the form of glass weaves, mats, webs and/or preferably glass filament rovings or chopped glass filament formed from low-alkali E-glasses from 5 to 200 ~m, preferably from 6 to 15 ~m, in diameter, generally have a mean fiber length of from O.05 to 1 mm, preferably from 0.1 to 0.5 mm, after incorporation into the TPU/PES molding materials.
Of the aforementioned particulate or fibrous reinforcing fillers, glass fibers in particular are advantageous, in particular when a high heat resistance or very high stiffness is required.
E) As mentioned, the TPU/PES molding materials according to the present invention may also contain assistants (E). The assistants can be identical to the customary aids (c) or additives (f) used for preparing TPUs and therefore already be present in the TPU (A). The proportion of assistant tE) is in general from 0 to 10 ~
by weight, preferably from 0 to 5 ~ by weight, based on the total weight of formative components (A) to (C). Such assistants are for example: nucleating agents, anti-oxidants, stabilizers, lubricants, demolding agents and dyes.
The nucleating agent used can be for example talc, calcium fluoride, sodium phenylphosphinate, alumi-num oxide or finely-divided polytetrafluoroethylene in an amount of up to S ~ by weight, based on the weight of formative components (A) to (C).
Suitable antioxidants and heat stabilizers which may ~e added to the TPU/PES molding materials are for example halides of metals of group I of the periodic table, for example halides of ~odium, potassium or lithium, alone or combined with copper(I) halides, eg.
chlorides, bromides or iodides, sterically hindered phenols, hydroquinones and also substituted compounds of the3e groups and mixtures thereof, which are preferably used in concentrations of up to 1 % by weight, based on 202~3~3 - 17 - o.z. 0050/41134 the weight of formative components (A) to (C).
Examples of W ~tabilizers are various substitu-ted resorcinols, salicylates, benzotriazoles and benzo-phenones and also sterically hindered amines, which in general are used in amounts of up to 2.0 ~ by weight, based on the weight of formative components (A) to (C).
Lubricants and demolding agents which in general are likewise added in amounts of up to 1 % by weight based on the weight of formative component~ (A) to (C), are Cl2-C3~-fatty acids, for example stearic acid~, fatty alcohol~, eg. stearyl alcohol, fatty acid esters or amides, eg. stearic esters and stearamides, and also the fatty acid esters of pentaerythritol and montan ester waxes.
It is also possible to add organic dyes, eg.
nigrosine, and pigment~, eg. titanium dioxide, cadmium sulfide, cadmium sulfide selenide, phthalocyanines, ultramarine blue or carbon black, in amount~ of for example up to 5 % by weight, based on formative compo-nent~ (A) to (C).
The impact modified thermoplastic TPU/PES molding materials according to the present invention can be prepared by any desired method for forming an essentially homogeneous composition from the TPU (A), the PES (B) and the ethylene copolymer (C) and optionally the fillers (D) and assi~tants (E). For example, the formative components (A) to (C) and optionally (D) and/or (E) can be mixed at from 0 to 150C, preferably at from 15 to 30Co and then melted, or the cGmponents can be mixed directly in the melt, Alternatively, (A) can be mixed with (C) or (B) with (C) and the~e mixtures be incorporated into (B) or (A) respectively, in which case (D) and/or (E) may already be present in one of the formative components (A) to (C) or may be added sub~equently.
The TPU/PES molding materials according to the pre~ent invention are prepared at from l90 to 250C, preferably from 210 to 240C, in the cour~e of a - 18 - O.Z. 0050t41134 residence time of from 0.S to 10 minutes, preferably of from 0.5 to 3 minutes, in for example the fluent, softened or preferably molten state of formative components (A) to (C), for example by ~tirring, rolling, kneading or preferably extruding, u~ing for example customary plasticating apparatus, eg. Brabender or Banbury mills, kneaders and extruders, preferably a twin-screw extruder or a mixing extruder for tran~fer molding.
In the most convenient and therefore preferable method of preparation, the TPU (A), the PES (B) and the ethylene copolymer (C) are mixed with or without (D) and/or (E) and melted together at 190-250C, preferably in an extruder, the melt ha~ incorporated into it any component (D) and/or (E) not introduced earlier and is then cooled, and the resulting TPU/PES molding material is comminuted.
The TPU/PES molding material~ obtained according to the present invention are easy to proces~ into shaped articles possessing good surface properties and improved impact toughness combined with high stiffness, in par-ticular at low temperatures, without separation into components (A) or (B) or (C) occurring in the melt or in the molding.
EXAMPLES
Impact modified thermoplastic TPU/PES molding materials according to the present invention are prepared using the following components:
A) Thermopla~tic polyurethane elastomers Al: TPU having a Shore D hardness of 69 prepared by reaction of a mixture of 0.5 mol of 1,4-butanediol polyadipate of molecular weight 2000 and 5.86 mol of 1,4-butanediol with 4,4'-diphenylmethane diisocyan-ate in an NCOsOH group ratio of l at 80-170C by the belt technique.
A2s TPU having a Shore D hardne~s of 74 prepared in the same way as A1 except that the NCOsOH group ratio used was 1.04.
- 19 - O. Z . 0050/41134 A3: TPU having a Shore A hardness of 90 prepared in the same way as Al, except that 1.7 mol of 1,4-butane-diol were used.
The above-described TPUS Al to A3 each contain, based on the alkanediol polyadipate welght, 1 % by weight of diisopropylphenylcarbodiimide a~ hydroly~is stabilizer.
A4: TPU having a Shore D hardness of 64 prepared by reaction of a mixture of 1 mol of polytetramethylene glycol of molecular weight lO00 and 3.87 mol of 1,4-butanediol with 4,4'-diphenylmethane dii~ocyanate in an NCO:OH group ratio of 1 a~ 90-170C by the belt technique.
B) Thermoplastic polyesters Bl: Polyethylene terephthalate having a relative visco-sity of 1.38 (measured on a 0.5 % strength by weight solution in 1:1 w/w phenol/o-dichloroben~ene).
B2: Polybutylene terephthalate having a relative visco-sity of 1.4, measured in the same way as B1.
C) Ethylene copolymer Cl: Terpolymer of ethylene, n-butyl acrylate and acrylic acid in a weight ratio of 65:30:5, prepared by high pressure polymerization as described in EP-A-0 106 999. The terpolymer had an NFI of 10 g/10 min, measured at 190C under a load of 2.16 kg in accord-ance with German Standard Specification DIN 53 735.
C2: Terpolymer of ethylene, n-butyl acrylate and maleic anhydride in a weight ratio of 65:35:0.5, prepared in the same way as Cl.
The terpolymer had an MFI of 12 g/10 min, measured at 190C under a load of 2.16 kg.
C3s Terpolymer of ethylene, n-butyl acrylate and gly-cidyl methacrylate in a weight ratio of 67:30:3, prepared as described under C1.
The terpolymer had an MFI of 10 g/10 min, measured at 190C under a load of 2.16 kg.
D) Fillers 202~383 - 20 - o.Z. 0050/41134 E-glass fibers in the form of a roving or in the form of chopped fiber. The gla~s fiber diameter was 10 ~m.
Preparation of the impact modified thermoplastic TPU/PES
molding materials COMPAR~TIVE ExAr~LEs I TO IV
To prepare the TPU/PES molding materials, com-ponents (A), (B) and (C) are intensively mixed at 23 C, the mixture is introduced into a twin-screw extruder and melted at 230C, and the melt i8 homogenized for 2 min-utes and then extruded into a water bath.
If E-glass fibers were used, these were incor-porated into the homogenized melt in the form of chopped fibers or rovings.
Following granulation and drying, the TPU/PES
molding materials were in~ection molded at 230C into test specimens on which measurements were carried out, without further aftertreatment, of the notched impact strength according to German Standard Specification DIN
53 453, the breaking extension according to German Standard Specification DIN 53 455 and the modulu~ of elasticity according to German Standard Specification DIN
53 457.
The identity and quantity of the TPUs (A), PES ' s (B) and ethylene copolymers (C) used and of any reinfor-cing fillers (D) and the mechanical propertie~ measured on the test specimen~ are summarized below in Table~ I
and II.
.
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~ ~ 0 _ C~
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202~383 - 22 - O.Z. 0050/41134 s ~ ~* ~
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~ D O
The TPU-forming components (a) to (d) and option-ally (e) and/or (f) may be described in detail as follows:
a) Suitable organic diisocyanate~ (a) are for example aliphatic, cycloaliphatic and preferably aromatic diisocyanateR. Specific examples are: aliphatic diiso-cyanates such as 1,6-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylene dii~ocyanate, ~-ethyl-1,4-butylene diisocyanate and mixtures of at least two ofsaid aliphatic diisocyanates, cycloaliphatic diisocyan-ates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, l-methyl-2,4-cyclohexane diisocyanate and l-methyl-2,6-cyclohexane dii~ocyanate and the correspond-ing isomeric mixtures, 4,4'-, 2,4'- or 2,2~-dicyclohexyl-methane diisocyanate and the correQponding isomeric mixtures and preferably aromatic diisocyanates such a~
2,4-toluylene diisocyanate, mixtures of 2,4- and 2,6-toluylene diisocyanate, 4,4'-, 2,4'- and 2,2'-diphenyl-methane diisocyanate, mixtures of 2,4'- and 4,4~-di-phenylmethane diisocyanate, urethane-modified liquid 4,4~- and/or 2,4'-diphenylmethane diisocyanates, 4,4'-diisocyanato-1,2-diphenylethane, mixtures of 4,4'-, 2,4'-and 2,2~-diisocyanato-1,2-diphenylethane, preferably those having a 4,4'-diisocyanato-1,2-diphenylethane content of at least 95 % by weight, and 1,5-naphthylene diisocyanate. Preference is given to using diphenyl-methane diisocyanate i omer mixture~ having a 4,4'-diphenylmethane diisocyanate content of greater ~han 96 %
by weight and in particular essentially pure 4,4'-di-phenylmethane diisocyanate.
The organic diisocyanates may be replaced to a minor extent, for example in an amount of up to 3 mol %, preferably up to 1 mol %, based on the organic diisocyan-ate, by a trifunctional or more highly functional poly-isocyanate, the amount of which, however, must be limited in such a way a~ to produce a still thermoplastic poly-2026~3 O.Z. 0050/41134 urethane. A ma~or amount of such tri- or more highly functional isocyanates is advantageously balanced by the inclusion of less than difunctional compounds having reactive hydrogen atoms, in order that excessive chemical crosslinking of the polyurethane may be avoided. Example~
of more than difunctional isocyanates are mixtures of diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates, so-called crude MDI, and liquid 4,4~-and/or 2,4'-diphenylmethane diisocyanate modified with isocyanurate, urea, biuret, allophanate, urethane and/or carbodiimide groups.
Suitable monofunctional compounds having a reactive hydrogen atom which are also usable as molecular weight regulators are for example: monoamines such as butylamine, dibutylamine, octylamine, stearylamine, N-methylstearylamine, pyrrolidone, piperidine and cyclo-hexylamine and monoalcohols such as butanol, amyl alcohol, 1-ethylhexanol, octanol, dodecanol, cyclohexanol and ethylene glycol monoethyl ether.
b) Preferred polyhydroxy co~pounds (b) having molecular weights of from 500 to 8000 are polyetherols and in particular polyesterols. However, it is also possible to u~e other hydroxyl-containing polymers containing ether or ester group~ as bridge members, for example polyacetals, such as polyoxymethylenes and in particular water-insoluble formals, eg. polybutanediol formal and polyhexanediol formal, and polycarbonates, in particular those formed from diphenyl carbonate and 1,6-hexanediol, prepared by transesterification. The poly-hydroxy compound~ must be at least predominantly linear,ie. difunctional within ths meaning of the i~ocyanate reaction. The polyhydroxy compound~ mentioned may be used as individual components or in the form of mixtures.
Suitable polyetherols can be prepared from one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene moiety in a conventional manner, for example by anionic polymerization with alkali metal hydroxide~, 20263~3 - 6 - O.Z. OOSO/41134 such as sodium hydroxide or pota3sium hydroxide, or alkali metal alcoholates, ~uch as sodium methoxide, sodium ethoxide, potassium ethoxide or potassium isoprop-oxide, as catalysts and in the presence of at least one initiator molecule which contains 2 or 3, preferably 2 reactive hydrogen atoms, or ~y cationic polymerization with Lewi~ acids, such as antimony pentachloride, boron fluoride etherate, etc. or bleaching earth, as catalysts.
Preferred alkylene oxides are for example tetra-hydrofuran, 1,3-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and in particular ethylene oxide and 1,2-propylene oxide. The alkylene oxides may be used indi-vidually, alternately in succession or as mixtures.
Suitable initiator molecules are for example: water, organic dicarboxylic acids, such as succinic acid, adipic acid and/or glutaric acid, alkanolamines, such as ethan-olamine, N-alkylalkanolamines, N-alkyldialkanolamines, eg. N-methyl- and N-ethyl-diethanolamine, and preferably dihydric alcohols which may contain ether linkages, eg.
ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butane-diol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, 2-methyl-1,5-pentanediol and 2-ethyl-1,4-butanediol. The initiator molecules may be used individually or as mixtures.
Preference is given to using polyetherols from 1,2-propylene oxide and ethylene oxide in which more than 50 %, preferably from 60 to 80 ~, of the OH groups are primary hydroxyl groups and where at lea~t some of the ethylene oxide units are present a~ a terminal block.
Such polyethero}~ can be obtained by, for example, polymerizing onto the initiator molecule fir~t the 1,2-propylene oxide and then the ethylene oxide, or first the entire 1,2-propylene oxide mixed with ~ome of the ethyl-ene oxide and then the remainder of the ethylene oxide, or step by step first some of the ethylene oxide, then the entire 1,2-propylene oxide and then the remainder of tha ethylene oxide.
202~3~3 - 7 - O.Z. 0050/41134 Other preferred possibilitie~ are the hydroxyl-containing polymerization products of tetrahydrofuran.
The essentially linear polyetherols have mole-cular weights of from 500 to 8000, preferably from 600 to 6000, in particular from 800 to 3500, the polyoxytetra-methylene glycols preferably having molecular weights of from 500 to 2800. They can be used not only individually but also in the form of mixtures with one another.
Suitable polyesterols may be prepared for example from dicarboxylic acids of from 2 to 12, preferably from 4 to 6, carbon atoms and polyhydric alcohols. Suitable dicarboxylic acids are for example: aliphatic dicar-boxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and ~ebacic acid, and aromatic dicarboxylic acids, such a~ phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, for example in the form of a mixture of succinic acid, glutaric acid and adipic acid. To prepare the poly-esterols it may be advantageous to use instead of the dicarboxylic acids the corresponding dicarboxylic acid derivatives, such as dicarboxylic monoesters or diesters having from 1 to 4 carbon atoms in the alcohol moiety, dicarboxylic anhydrides or dicarbonyl dichlorides.
Examples of polyhydric alcohol~ are glycols of from 2 to 10, preferably from 2 to 6, carbon atoms, such as ethyl-ene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-di-methylpropane-1,3-diol, 1,3-propanediol and dipropylene glycol. Depending on the properties which are desired, the polyhydric alcohols may be used alone or optionally mixed with one another.
It i8 also possible to use esters of carbonic acid with the diols mentioned, in particular those having from 4 to 6 carbon atoms, such as 1,4-butanediol and/or 1,6-hexanediol, condensation products of ~-hydroxycar-boxylic acids, eg. w-hydroxycaproic acid, and preferably - 8 - o.z 0050/41134 polymer~zation produ~tY of lactones, for example ~ubsti-tuted or unsubstituted ~-caprolactone~.
Preferred polyesterols are ethanediol poly-adipates, 1,4-butanediol polyadipates, ethanediol/1,4-butanediol polyadipates, 1,6-hexanediol/neopentylglycol polyadipates, 1,6-hexanediol/1,4-butanediol polyadipates and polycaprolactones.
The polyesterols have molecular weights of from 500 to 6000, preferably from 800 to 3500.
c) Suitable chain extenders (c) having molecular weights of from 60 to 400, preferably from 60 to 300, are preferably aliphatic diols of from 2 to 12 carbon atoms, preferably of 2, 4 or 6 carbon atoms, eg. ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and in particular 1,4-butanediol. However, it is also pos-sible to use diesters of terephthalic acid with glycols of from 2 to ~ carbon atoms, eg. bisethylene glycol terephthalata, 1,4-butanediol terephthalate, and hydroxy-alkylene ethers of hydroquinone, eg. 1,4-di-(~-hydroxy-ethyl)-hydroquinone, and also polytetramethylene glycols having molecular weights of from 162 to 378.
To ~et the hardne3s and the melt flow index, the formative components can be varied within relatively wide molar ratios bearing in mind that the hardness and melt viscosity increase with an increasing level of chain extenders (c) while the melt flow index decrea3es.
To prepare relatively soft TPUs (A), for example those having a Shore A hardnes~ of less than 95, prefer-ably from 95 to 75, it is advantageous for exhmple to use the es~entially difunctional polyhydroxy compounds (b) and the diols (c) in a molar ratio of from 1:1 to 1:5, preferably from 1:1.5 to 1:4.5, 80 that the resulting mixture3 of (b) and (c) have a hydroxy equivalent weight of greater than 200, in particular from 230 to 450, while harder TPU8 (A), for example those having a Shore A
hardnes~ of greater than 98, preferably from 55 to 75 Shore D, are prepared u~ing molar ratios of (b):(c) _ g _ O.Z. 0050/41134 within the range from 1:5.5 to 1:15, preferably from 1:6 to 1:12, so that the re~ulting mixtures of (b) and (c) have a hydroxy equivalent weight of from 110 to 200, preferably from 120 to 180.
d) Suitable catalysts, in particular for the reac-tion between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the formative components (b) and (c), are the customary tertiary amines, such as triethyl-amine, dimethylcyclohexylamine, N-msthylmorpholine, N,N~-dimethylpiperazine, diazabicyclo[2.2.2]octane and the like, and in particular organic metal compounds such as titanic esters, iron compounds, tin compounds, eg. ~in diacetate, tin dioctanoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate and the like.
The catalysts are customarily u~ed in amounts of from 0.001 to 0.1 part by weight per 100 parts by weight of the mixture of polyhydroxy compounds (b) and diols (c).
In addition to catalysts, the formative compo-nents may also contain aids (e) and/or additives (f).
Examples are lubricants, inhibitors, stabili~ers against hydrolysis, light, heat or discoloration, flame retar-dants, dyes, pigments, inorganic and/or organic fillers and reinforcing agents.
The aids (e) and/or additives (f) may be intro-duced into the formative components or into the reaction mixture for preparing the ~PUs (A). Alternatively, the aids (e) and/or additives (f), which may be identical to the assistant (E), may be mixed with the TPU (A), the PES
(B) and/or the ethylene copolymer (C) and then melted, or they are incorporated directly into the melt of com-ponents (A), (B) and (C). The latter method is also adopted in particular for incorporating the fibrous and/or particulate fillers (D).
Whera, in what follows, no details are provided concerning the usable aids or additives, they can be gathered from the relevant technical literature, for - 10 - O.Z. 0050/41134 example J.H. Saunders and K.C. Frisch's monograph, High Polymers, volume XVI, Polyurethanes, parts 1 and 2 (Interscience Publishers 1962 and 1964 respectively), Kunststoff-Handbuch, volume 7, Polyurethane~, 1st and 2nd editions (Carl Hanser Verlag 1966 and 1983 respectively), or DE-A-2,901,774.
To prepare the TPUs (A), the formative components (a), (b) and (c) are made to react in the presence of a catalyst (d) and in the presence or absence of aids (e) and/or additives (f) in such amounts that the equivalence ratio of the diisocyanate NCO groups to the total number of hydroxyl groups of components (b) and (c) is from 0.95 to 1.10:1, preferably 0.98 to 1.08:1, in particular approximately 1.0 to 1.05:1.
The TPUs (A) which are usable according to the present invention and which customarily contain from 8 to 20 % by weight, preferably from 8 to 16 % by weight, based on the total weight, of urethane groups and have a melt flow index at 210C of from 500 to 1, preferably from 100 to 1, can be prepared by the extruder technique or preferably the belt technique by batchwi~e or con-tinuous mixing of formative components (a) to (d) and optionally (e) and/or (f~, fully reacting the mixture in an extruder or on a support belt at from 60 to 250C, preferably at from 70 to 150C, and then granulating the resulting TPUs (A). It may be advantageous to heat the resulting TPU (A) at from 80 to 120C, preferably at from 100 to 110C, for a period of from 1 to 24 hour3 before further processing into the TPU/PES molding materials according to the present invention.
The TPUs (A) are, as mentioned, preferably prepared by the belt technique. To this end, the forma-tive components (a) to (d) and optionally (e) and/or (f) are continuously mixed with the aid of a mixing head at above the melting point of formative components (a) to (c). The reaction mixture is discharged onto a support, preferably a conveyor belt, for example a metal belt, and 202~383 ~ O.Z. 0050/41134 i~ passed at 1-20 m/min, preferably 4-10 m~min, through a hot zone from 1 to 20 m, preferably from 3 to 10 m, in length. The temperature in the hot zone is 60-200C, preferably 80-180C. Depending on the diisocyanate content of the reaction mixture, the reacSion is con-trolled by cooling or heating in such a way that at least 90 %, preferably at least 98 %, of the isocyanate groups of the diisocyanates react and the reaction mixture solidifies at the chosen reaction temperature. Owing to the free isocyanate groups in the solidified reaction product, which based on the total weight are within the range from O.OS to 1 % by weight, preferably from 0.1 to 0.5 % by weight, the TPUs (A) obtained have a very low melt vi~cosity or a high melt flow index.
B) Formative component (B) of the TPU/PES molding materials according to the present invention comprises, as mentioned, an amount, based on 100 parts by weight of (A), (B) and (C), of from 5 to 65 parts by weight, preferably from 10 to 60 parts by weight, in particular 12 to 50 parts by weight, of one or more thermoplastic polye~ters. Polyesters ~uitable for this purpose are described in the literature. They contain in the ~olycon-den~ate main chain at least one aromatic ring derived from an aromatic dicarboxylic acid. The aromatic ring may also be sub~tituted, for example by halogen, eg. chlorine or bromine, or/and by linear or branched alkyl, prefer-ably of from l to 4 carbon atoms, in particular of 1 or 2 carbon atoms, eg. methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl or tert-butyl.
The polyesters can be prepared by polycondens-ation of aromatic dicarboxylic acids or mixture~ of aromatic and aliphatic and/or cycloaliphatic dicarboxylic acids and the corresponding ester-forming derivatives, for example dicarboxylic anhydrides, monoester~ and/or diester~ having advantageously not more than 4 carbon atoms in the alcohol moiety, with aliphatic dihydroxy compounds at elevated temperature~, for example at from 20263~3 - 12 - O.Z. 0050/41134 160 to 260C, in the presence or absence of e~terifica-tion catalysts.
The preferred aromatic dicarboxylic acids are the naphthalenedicarboxylic acids, i~ophthalic acid and in particular terephthalic acid or mixtures of these dicarb-oxylic acids. Ifmixtures of aromatic and (cyclo)aliphatic dicarboxylic acids are used, up to 10 mol ~ of the aromatic dicarboxylic acids may be replaced by aliphatic and/or cycloaliphatic dicarboxylic acids of advantage-ously 4-14 carbon atoms, eg. succinic, adipic, azelaic, sebacic or dodecanedioic acid and/or cyclohexanedicar-boxylic acid.
The preferred aliphatic dihydroxy compounds are alkanediols of from 2 to 6 carbon atoms and cycloalkane-diols of from 5 to 7 carbon atom~. Specific examples of preferred aliphatic dihydroxy compounds are 1,2-ethane-diol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol and 1,4-cyclohexanediol and mixtures of at least two of said diols.
Particularly suitable PES's (B) are specifically the polyalkylene terephthalates of alkanediols of from 2 to 6 carbon atom~, 80 that polye~hylene terephthalate and in particular polybutylene terephthalate are preferred.
The relative vi~cosity of the PES's (B) is in 2S general within the range from 1.2 to 1.8, measured in a 0.5 ~ strength by weight solution in 1:1 w/w phenol/o-dichlorobenzene at 25C.
C) The TPU/PES molding materials according to the present invention contain one or more ethylene copolymers (C) for improving the impect toughnes~, in particular at low temperatures, and increasing the fluidity as addi-tional formative component in an amount, based on 100 parts by weight of the molding materials consisting of (A), (B) and (C~, of from 5 to 30 parts by weight, especially from 8 to 30 parts by weight, in particular from 10 to 25 parts by weight.
Suitable ethylene copolymers (C) are 202~c~83 - 13 - O.Z. 0050/41134 advantageously ba~ed on Ca) ethylene, Cb) at least one alkyl (meth)acrylate having from 1 to 8 carbon atoms in a linear or branched alkyl moiety, but not tert-butyl (meth)acrylate, and Cc) at least one further monomer which contain~ a ~roup which is reactive towards the TPU (A) or PES (B).
Preference is given to using those ethylene copolymers (C) which based on the total weight contain in polymerized form:
Ca) ethylene units in an amount of from 50 to 98% by weight, preferably from 60 to 95% by weight, Cb) alkyl (meth)acrylate units in an amount of 1 to 45%
by weight, preferably from 10 to 35% by weight, and Cc) an amount of a further comonomer (Cc) having a group which is reactive toward TPU (A) or PES (B) ranging from 0.1 to 40~ by weight, preferably from l to 40%
by weight, in particular from 2 to 20% by weight.
Ca) Ethylene as monomer is sufficiently well known in polymer chemistry enough to make further remarks redundant.
Cb) The (meth)acrylic e~ters used as acrylates and/or methacrylate~ (Cb) having from 1 to 8 carbon atoms, preferably from 2 to 8 carbon atoms, in a linear or branched alkyl moiety are those where, in the ready-prepared ethylene copolymer (C), the ester groups of the polymerizable (meth)acrylate units react essen-tially not at all or only to a minor extent with the TPU (A) or PES (B) under the reaction conditions of formin~ TPU/PES molding material~. Specific examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl and n-octyl acrylates and methacrylates. The alkyl (meth)acrylates can be used indi~idually or in the form of mixtures. Preference is gi~en to using n-butyl and/or 2-ethylhexyl (meth)acrylate.
Cc) Suitable comonomerC (Cc) are olefinically 2026 38~`
- 14 - O.Z. 0050/41134 unsaturated monomers which are copolymerizable with ethylene and alkyl (meth)acrylates and contain a reactive group which, in the ready-prepared ethylene copolymer (C), reacts with the TPU (A) or PES (B) under the reaction conditions for forming TPU/PES
molding materials, the reaction taking place to such an extent that, after the reaction has ended, the degree o~ coupling to the TPU (A) and PES (B) i5 greater than 0.01, preferably within the range from 0.03 to 1, in particular from 0.05 to 0.8, the degree of coupling being defined here as the ratio of ethylene copolymer (C) not extractable with toluene from the TPU/PES molding material to the total amount of ethylene copolymer (C) used.
Examples of groups which are reactive with TPU (A) or PES (B) are sulfo, sulfonyl, oxazoline and epoxy groups, preferably carboxyl, tert~butyl carboxylate and carboxylic anhydride groups.
Suitable comonomers (Cc) for preparing the ethylene copolymers (C) are for example olefinically unsaturated monocarboxylic acids, eg. acrylic acid and methacrylic acid and the corresponding tert-butyl esters, eg. tert-butyl (meth)acrylate, olefinically unsaturated dicarboxylic acids, eg. fumaric acid and maleic acid, and the corresponding mono- and/or di-tert-butyl esters, eg.
mono- and di-tert-butyl fumarate and mono- or di-tert-butyl maleate, olefinically unsaturated dicarboxylic anhydride~, eg. maleic anhydride, sulfo- or sulfonyl-containing olefinically unsaturated monomers, eg. p-styrene~ulfonicacid,2-(meth)acrylamido-2-methylpropene-sulfonic acid or 2-sulfonyl (meth)acrylate, oxazolinyl-containing olefinically unsaturated monomers, eg. vinyl oxazolines and vinyl oxazoline derivatives, and olefini-cally unsaturated monomers which contain epoxy groups, eg. glycidyl (meth)acrylate or allyl glycidyl ether.
Particularly preferred comonomers (Cc) are acrylic acid, methacrylic acid, tert-butyl (meth)acrylate '~02~83 - 15 - O.Z. 0050/41134 and/or in particular maleic anhydride and also glycidyl methacrylate.
Said comonomers (Cc), like the alkyl (meth)acryl-ates, can be used individually or in the form of mixtures for preparing the ethylene copolymer (C).
The ethylene copolymers (C) can be prepared in a conventional manner, preferably by random copolymeriza-tion under high pressure, for example at from 200 to 4000 bar, and at elevated temperature, for example within the range from approximately 120 to 300C. Appropriate techniques are described in literature and patent publi-cation~.
~ he melt flow index of suitable ethylene copoly-mers (C) is advantageously within the range from 1 to 80 g/10 min, preferably from 2 to 25 g/10 min (measured at 190C under a load of 2.16 kg in accordance with German Standard Specification DIN 53 735).
The impact modified thermoplastic TPU/PES molding materials according to the present invention may in addition to the e ~ential components (A), (B) and (C) optionally also contain fibrous and/or particulate fillers (D) and/or assistant3 (E).
D) The proportion of filler (D) is customarily from 0 to 60 % by weight, preferably from 2 to 50 % by weight, in particular from 5 to 30 % by weight, based on the total weight of components (A) to (C).
Suitable particulate fillers are for example:
organic fillers, such a~ carbon black, chlorinated polyethylenes and melamine, and inorganic fillers such as wollastonite, calcium carbonate, magnesium carbonate, amorphous silica, calcium ~ilicate, calcium metasilicate, quartz powder, talc, kaolin, mica, feldspar, glass spheres, silicon nitride, boron nitride and mixtures thereof.
Particularly suitable reinforcing fillers which are therefore preferred are fiber~, for example carbon fibers and in particular gla~s fiber~, with or without an 202~38'~
- 16 - O.Z. 0050/41134 adhesion promoting or/and size finish. Suitable glas~
fibers, which are also for example in the form of glass weaves, mats, webs and/or preferably glass filament rovings or chopped glass filament formed from low-alkali E-glasses from 5 to 200 ~m, preferably from 6 to 15 ~m, in diameter, generally have a mean fiber length of from O.05 to 1 mm, preferably from 0.1 to 0.5 mm, after incorporation into the TPU/PES molding materials.
Of the aforementioned particulate or fibrous reinforcing fillers, glass fibers in particular are advantageous, in particular when a high heat resistance or very high stiffness is required.
E) As mentioned, the TPU/PES molding materials according to the present invention may also contain assistants (E). The assistants can be identical to the customary aids (c) or additives (f) used for preparing TPUs and therefore already be present in the TPU (A). The proportion of assistant tE) is in general from 0 to 10 ~
by weight, preferably from 0 to 5 ~ by weight, based on the total weight of formative components (A) to (C). Such assistants are for example: nucleating agents, anti-oxidants, stabilizers, lubricants, demolding agents and dyes.
The nucleating agent used can be for example talc, calcium fluoride, sodium phenylphosphinate, alumi-num oxide or finely-divided polytetrafluoroethylene in an amount of up to S ~ by weight, based on the weight of formative components (A) to (C).
Suitable antioxidants and heat stabilizers which may ~e added to the TPU/PES molding materials are for example halides of metals of group I of the periodic table, for example halides of ~odium, potassium or lithium, alone or combined with copper(I) halides, eg.
chlorides, bromides or iodides, sterically hindered phenols, hydroquinones and also substituted compounds of the3e groups and mixtures thereof, which are preferably used in concentrations of up to 1 % by weight, based on 202~3~3 - 17 - o.z. 0050/41134 the weight of formative components (A) to (C).
Examples of W ~tabilizers are various substitu-ted resorcinols, salicylates, benzotriazoles and benzo-phenones and also sterically hindered amines, which in general are used in amounts of up to 2.0 ~ by weight, based on the weight of formative components (A) to (C).
Lubricants and demolding agents which in general are likewise added in amounts of up to 1 % by weight based on the weight of formative component~ (A) to (C), are Cl2-C3~-fatty acids, for example stearic acid~, fatty alcohol~, eg. stearyl alcohol, fatty acid esters or amides, eg. stearic esters and stearamides, and also the fatty acid esters of pentaerythritol and montan ester waxes.
It is also possible to add organic dyes, eg.
nigrosine, and pigment~, eg. titanium dioxide, cadmium sulfide, cadmium sulfide selenide, phthalocyanines, ultramarine blue or carbon black, in amount~ of for example up to 5 % by weight, based on formative compo-nent~ (A) to (C).
The impact modified thermoplastic TPU/PES molding materials according to the present invention can be prepared by any desired method for forming an essentially homogeneous composition from the TPU (A), the PES (B) and the ethylene copolymer (C) and optionally the fillers (D) and assi~tants (E). For example, the formative components (A) to (C) and optionally (D) and/or (E) can be mixed at from 0 to 150C, preferably at from 15 to 30Co and then melted, or the cGmponents can be mixed directly in the melt, Alternatively, (A) can be mixed with (C) or (B) with (C) and the~e mixtures be incorporated into (B) or (A) respectively, in which case (D) and/or (E) may already be present in one of the formative components (A) to (C) or may be added sub~equently.
The TPU/PES molding materials according to the pre~ent invention are prepared at from l90 to 250C, preferably from 210 to 240C, in the cour~e of a - 18 - O.Z. 0050t41134 residence time of from 0.S to 10 minutes, preferably of from 0.5 to 3 minutes, in for example the fluent, softened or preferably molten state of formative components (A) to (C), for example by ~tirring, rolling, kneading or preferably extruding, u~ing for example customary plasticating apparatus, eg. Brabender or Banbury mills, kneaders and extruders, preferably a twin-screw extruder or a mixing extruder for tran~fer molding.
In the most convenient and therefore preferable method of preparation, the TPU (A), the PES (B) and the ethylene copolymer (C) are mixed with or without (D) and/or (E) and melted together at 190-250C, preferably in an extruder, the melt ha~ incorporated into it any component (D) and/or (E) not introduced earlier and is then cooled, and the resulting TPU/PES molding material is comminuted.
The TPU/PES molding material~ obtained according to the present invention are easy to proces~ into shaped articles possessing good surface properties and improved impact toughness combined with high stiffness, in par-ticular at low temperatures, without separation into components (A) or (B) or (C) occurring in the melt or in the molding.
EXAMPLES
Impact modified thermoplastic TPU/PES molding materials according to the present invention are prepared using the following components:
A) Thermopla~tic polyurethane elastomers Al: TPU having a Shore D hardness of 69 prepared by reaction of a mixture of 0.5 mol of 1,4-butanediol polyadipate of molecular weight 2000 and 5.86 mol of 1,4-butanediol with 4,4'-diphenylmethane diisocyan-ate in an NCOsOH group ratio of l at 80-170C by the belt technique.
A2s TPU having a Shore D hardne~s of 74 prepared in the same way as A1 except that the NCOsOH group ratio used was 1.04.
- 19 - O. Z . 0050/41134 A3: TPU having a Shore A hardness of 90 prepared in the same way as Al, except that 1.7 mol of 1,4-butane-diol were used.
The above-described TPUS Al to A3 each contain, based on the alkanediol polyadipate welght, 1 % by weight of diisopropylphenylcarbodiimide a~ hydroly~is stabilizer.
A4: TPU having a Shore D hardness of 64 prepared by reaction of a mixture of 1 mol of polytetramethylene glycol of molecular weight lO00 and 3.87 mol of 1,4-butanediol with 4,4'-diphenylmethane dii~ocyanate in an NCO:OH group ratio of 1 a~ 90-170C by the belt technique.
B) Thermoplastic polyesters Bl: Polyethylene terephthalate having a relative visco-sity of 1.38 (measured on a 0.5 % strength by weight solution in 1:1 w/w phenol/o-dichloroben~ene).
B2: Polybutylene terephthalate having a relative visco-sity of 1.4, measured in the same way as B1.
C) Ethylene copolymer Cl: Terpolymer of ethylene, n-butyl acrylate and acrylic acid in a weight ratio of 65:30:5, prepared by high pressure polymerization as described in EP-A-0 106 999. The terpolymer had an NFI of 10 g/10 min, measured at 190C under a load of 2.16 kg in accord-ance with German Standard Specification DIN 53 735.
C2: Terpolymer of ethylene, n-butyl acrylate and maleic anhydride in a weight ratio of 65:35:0.5, prepared in the same way as Cl.
The terpolymer had an MFI of 12 g/10 min, measured at 190C under a load of 2.16 kg.
C3s Terpolymer of ethylene, n-butyl acrylate and gly-cidyl methacrylate in a weight ratio of 67:30:3, prepared as described under C1.
The terpolymer had an MFI of 10 g/10 min, measured at 190C under a load of 2.16 kg.
D) Fillers 202~383 - 20 - o.Z. 0050/41134 E-glass fibers in the form of a roving or in the form of chopped fiber. The gla~s fiber diameter was 10 ~m.
Preparation of the impact modified thermoplastic TPU/PES
molding materials COMPAR~TIVE ExAr~LEs I TO IV
To prepare the TPU/PES molding materials, com-ponents (A), (B) and (C) are intensively mixed at 23 C, the mixture is introduced into a twin-screw extruder and melted at 230C, and the melt i8 homogenized for 2 min-utes and then extruded into a water bath.
If E-glass fibers were used, these were incor-porated into the homogenized melt in the form of chopped fibers or rovings.
Following granulation and drying, the TPU/PES
molding materials were in~ection molded at 230C into test specimens on which measurements were carried out, without further aftertreatment, of the notched impact strength according to German Standard Specification DIN
53 453, the breaking extension according to German Standard Specification DIN 53 455 and the modulu~ of elasticity according to German Standard Specification DIN
53 457.
The identity and quantity of the TPUs (A), PES ' s (B) and ethylene copolymers (C) used and of any reinfor-cing fillers (D) and the mechanical propertie~ measured on the test specimen~ are summarized below in Table~ I
and II.
.
20263~3 - 21 - O.Z. 0050/41134 .C,o ~
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L ~ ~ ~ D O ao ~ `t O ~ D _ ~ ~ '~
1 0 ~ t O ~
_ ~ C ~ u~ -J C ~ ~ t ~ D C
~) , _ ~ ~ n o o o u~ o u o o o Z ~ Z~o ~ ~ CO GO ~ U7 Cr~ ~ ~ Cl~ ~O ~ O
--IIII ooooooooooo _~L.~ ___________ ,~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
~ ~ ~ m ~ a~ c~ CD ~ ~ ~ ~ a~ ~ 0 ~, . -oooo ooooooooooo L'OI 1~ t t~ _t ~ ~ ~t ~ ~t ~ ~ ~t ~!~ 4 -- ~. ____ ____~__~
.c a~ C .t ~ c t e ~_ .,. oooo oo'ooC~oooooo E ~ ~I) J
~ ~ 0 _ C~
o-- X ~ o _ O
202~383 - 22 - O.Z. 0050/41134 s ~ ~* ~
o o~
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Claims (14)
1. An impact modified thermoplastic polyurethane-polyester molding material containing, based on 100 parts by weight of (A) to (C), A) from 30 to 90 parts by weight of at least one thermoplastic polyurethane elastomer (A), B) from 5 to 65 parts by weight of at least one thermo-plastic polyester (B) and C) from 5 to 30 parts by weight of at least one ethy-lene copolymer (C) and also, based on the total weight of (A) to (C), D) from 0 to 60 % by weight of at least one fibrous or particulate filler and E) from 0 to 10 % by weight of at least one assistant.
2. An impact modified thermoplastic polyurethane-polyester molding material consisting of A) from 30 to 90 parts by weight of at least one thermoplastic polyurethane elastomer (A), B) from 5 to 65 parts by weight of at least one thermo-plastic polyester (B) and C) from 5 to 30 parts by weight of at least one ethy-lene copolymer (C), the proportions by weight of (A) to (C) adding up to 100 parts by weight, and also, based on the total weight of (A) to (C), D) from 0 to 60 % by weight of at least one fibrous or particulate filler and E) from 0 to 10 % by weight of at least one assistant.
3. An impact modified thermoplastic polyurethane polyester molding material as claimed in claim 1, wherein the thermoplastic polyurethane elastomer (A) is prepared by reaction of a) an aromatic diisocyanate with b) a polyhydroxy compound having a molecular weight of from 500 to 8000 and c) a diol having a molecular weight of from 60 to 400 in an equivalence ratio of NCO groups of organic diiso-cyanate (a) to the total number of hydroxyl groups of - 24 - O.Z. 0050/41134 components (b) and (c) of from 0.95:1.0 to 1.1:1Ø
4. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1, wherein the thermoplastic polyurethane elastomer (A) is prepared by reaction of a) 4,4'-diphenylmethane diisocyanate with b) an essentially linear polyhydroxy compound, prefer-ably a polyalkylene glycol polyadipate, having from 2 to 6 carbon atoms in the alkylene moiety and a molecular weight of from 500 to 6000 or a hydroxyl-containing polytetrahydrofuran having a molecular weight of from 500 to 8000, and c) 1,4-butanediol.
5. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim l, wherein the thermoplastic polyurethane elastomer (A) has a hardness within the range from Shore A 75 to Shore D 75 and is prepared by the belt technique.
6. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1, wherein the thermoplastic polyester (B) has a relative viscosity within the range from 1.2 to 1.8, measured in a 0.5 %
strength by weight solution in 1:1 w/w phenol/o-dichloro-benzene at 25°C, and is prepared by polycondensation of an aromatic dicarboxylic acid with an alkanediol having 2 to 6 carbon atoms in the alkylene moiety.
strength by weight solution in 1:1 w/w phenol/o-dichloro-benzene at 25°C, and is prepared by polycondensation of an aromatic dicarboxylic acid with an alkanediol having 2 to 6 carbon atoms in the alkylene moiety.
7. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1, wherein the thermoplastic polyester (B) is polyethylene tereph-thalate or preferably polybutylene terephthalate.
8. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1, wherein the ethylene copolymer (C) is based on Ca) ethylene, Cb) at least one alkyl (meth)acrylate having from 1 to 8 carbon atoms in a linear or branched alkyl moiety, but not tert-butyl (meth)acrylate, and - 25 - O.Z. 0050/41134 Cc) at least one further monomer which contains a group which is reactive towards the thermoplastic polyure-thane elastomer (A) or the thermoplastic polyester (B).
9. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1, wherein the ethylene copolymer (C) is based on Ca) ethylene, Cb) at least one alkyl (meth)acrylate having from 1 to 8 carbon atoms in a linear or branched alkyl moiety, but not tert-butyl (meth)acrylate, and Cc) at least one further monomer selected from the group consisting of the olefinically unsaturated monocar-boxylic acids and the corresponding tert-butyl esters, olefinically unsaturated dicarboxylic acids and the corresponding tert-butyl esters, olefini-cally unsaturated dicarboxylic anhydrides, sulfo-and sulfonyl-containing olefinically unsaturated monomers, oxazolinyl-containing olefinically un-saturated monomers and olefinically unsaturated monomers having epoxy groups.
10. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1, wherein the ethylene copolymer (C) is based on Ca) ethylene, Cb) at least one alkyl (meth)acrylate having from 1 to 8 carbon atoms in a linear or branched alkyl moiety, but not tart-butyl (meth)acrylate, and Cc) at least one further monomer selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid and the tert-butyl esters of the aforementioned monocarboxylic and dicarboxylic acids and in particular maleic anhydride and also glycidyl methacrylate.
11. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1, wherein the ethylene copolymer (C) is based on - 26 - O.Z. 0050/41134 Ca) from 50 to 98% by weight of ethylene, Cb) from 1 to 45% by weight of at least one alkyl (meth)acrylate having from 1 to 8 carbon atoms in a linear or branched alkyl moiety, but not tert-butyl (meth)acrylate and Cc) from 0.1 to 40% by weight of at least one further monomer which contains a group which is reactive towards the thermoplastic polyurethane (A) or the thermoplastic polyester (B) and is selected from the group consisting of the olefinically unsaturated monocarboxylic acids and the corresponding tert-butyl esters, olefinically unsaturated dicarboxylic acids and the corresponding tert-butyl esters, olefinically unsaturated dicarboxylic anhydrides, sulfo- and sulfonyl-containing olefinically un-saturated monomers, oxazolinyl-containing olefini-cally unsaturated monomers and olefinically un-saturated monomers having epoxy groups, the weight percentages being based on the total weight of monomers (Ca), (Cb) and (Cc) and always adding up to 100%
by weight.
by weight.
12. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1, wherein the ethylene copolymer (C) is based on Ca) from 50 to 98% by weight of ethylene, Cb) from 1 to 45% by weight of n-butyl (meth)acrylate and/or 2-ethylhexyl (meth)acrylate and Cc) from 0.1 to 40% by weight of (meth)acrylic acid, maleic anhydride and/or tert-butyl (meth)acrylate, the weight percentages being based on the total weight of monomers (Ca), (Cb) and (Cc) and always adding up to 100%
by weight.
by weight.
13. A process for preparing an impact modified thermoplastic polyurethane polyester molding material, which comprises homogenizing, based on 100 parts by weight of (A) to (C), A) from 30 to 90 parts by weight of at least one - 27 - O.Z. 0050/41134 thermoplastic polyurethane elastomer (A), B) from 5 to 65 parts by weight of at least one thermo-plastic polyester (B) and C) from 5 to 30 parts by weight of at least one ethy-lene copolymer (C) and also, based on the total weight of (A) to (C), D) from 0 to 60 % by weight of at least one fibrous or particulate filler and E) from 0 to 10 % by weight of at least one assistant in a suitable mixing apparatus at 190-250°C for 0.5-10 minutes.
14. A process for preparing an impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 13, wherein components (A) to (C) and optionally (D) and/or (E) are homogenized in a twin-screw extruder at 190-250°C for 0.5-10 minutes.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19893932360 DE3932360A1 (en) | 1989-09-28 | 1989-09-28 | IMPACT MODIFIED THERMOPLASTIC POLYURETHANE-POLYESTER MOLDING MATERIALS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
DEP3932360.9 | 1989-09-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2026383A1 true CA2026383A1 (en) | 1991-03-29 |
Family
ID=6390368
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2026383 Abandoned CA2026383A1 (en) | 1989-09-28 | 1990-09-27 | Impact modified thermoplastic polyurethane-polyester molding materials and preparation thereof |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0420017A3 (en) |
JP (1) | JPH03166257A (en) |
CA (1) | CA2026383A1 (en) |
DE (1) | DE3932360A1 (en) |
FI (1) | FI904688A0 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2548856B2 (en) * | 1991-10-29 | 1996-10-30 | 株式会社ジャパンエナジー | Method for purifying alkylphosphine |
TW257781B (en) * | 1991-10-24 | 1995-09-21 | Du Pont | |
JPH09183200A (en) * | 1995-12-28 | 1997-07-15 | Kureha Chem Ind Co Ltd | Laminated film |
US6284839B1 (en) | 1995-12-29 | 2001-09-04 | The B.F. Goodrich Company | Blends of thermoplastic polymers, electrostatic dissipative polymers and electrostatic dissipative enhancers |
EP2810986B1 (en) * | 2013-06-05 | 2017-04-19 | Carl Freudenberg KG | Thermoplastic elastomer compound and its use |
EP3186310A4 (en) * | 2014-07-14 | 2018-04-18 | Vertellus Holdings LLC | Modification of engineering plastics using olefin-maleic anhydride copolymers |
WO2018210609A1 (en) * | 2017-05-17 | 2018-11-22 | Basf Se | Impact-resistance polymer mixture |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3562355A (en) * | 1968-03-20 | 1971-02-09 | Shell Oil Co | Block copolymer blends with certain polyurethanes or ethylene-unsaturated ester copolymers |
US4179479A (en) * | 1978-04-20 | 1979-12-18 | Mobay Chemical Corporation | Thermoplastic polyurethane blends containing a processing aid |
DE3810078A1 (en) * | 1988-03-25 | 1989-10-05 | Bayer Ag | THERMOPLASTIC POLYMER BLEND AND METHOD FOR THE PRODUCTION THEREOF |
-
1989
- 1989-09-28 DE DE19893932360 patent/DE3932360A1/en not_active Withdrawn
-
1990
- 1990-09-19 EP EP19900117975 patent/EP0420017A3/en not_active Withdrawn
- 1990-09-24 FI FI904688A patent/FI904688A0/en not_active IP Right Cessation
- 1990-09-26 JP JP25437090A patent/JPH03166257A/en active Pending
- 1990-09-27 CA CA 2026383 patent/CA2026383A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
FI904688A0 (en) | 1990-09-24 |
JPH03166257A (en) | 1991-07-18 |
EP0420017A3 (en) | 1991-05-15 |
DE3932360A1 (en) | 1991-04-11 |
EP0420017A2 (en) | 1991-04-03 |
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