US20020058716A1 - Composites consisting of polyurethane and a thermoplastic material containing an inorganic polar additive - Google Patents
Composites consisting of polyurethane and a thermoplastic material containing an inorganic polar additive Download PDFInfo
- Publication number
- US20020058716A1 US20020058716A1 US09/529,707 US52970700A US2002058716A1 US 20020058716 A1 US20020058716 A1 US 20020058716A1 US 52970700 A US52970700 A US 52970700A US 2002058716 A1 US2002058716 A1 US 2002058716A1
- Authority
- US
- United States
- Prior art keywords
- composite according
- thermoplastic
- polymers
- polar compound
- polyurethane
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 239000004814 polyurethane Substances 0.000 title claims abstract description 30
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 24
- 239000012815 thermoplastic material Substances 0.000 title claims description 13
- 239000000654 additive Substances 0.000 title claims description 7
- 230000000996 additive effect Effects 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229920003023 plastic Polymers 0.000 claims abstract description 7
- 239000004033 plastic Substances 0.000 claims abstract description 7
- 150000002739 metals Chemical class 0.000 claims abstract description 6
- 230000000737 periodic effect Effects 0.000 claims abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- 229920000728 polyester Polymers 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 21
- 229920000578 graft copolymer Polymers 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 15
- 229920000515 polycarbonate Polymers 0.000 claims description 15
- 239000004417 polycarbonate Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 9
- 239000010419 fine particle Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920002396 Polyurea Polymers 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- 239000011135 tin Substances 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- -1 for example Natural products 0.000 description 45
- 239000000178 monomer Substances 0.000 description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical class C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 13
- 125000003118 aryl group Chemical group 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 239000005056 polyisocyanate Substances 0.000 description 12
- 229920001228 polyisocyanate Polymers 0.000 description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 11
- 229920005862 polyol Polymers 0.000 description 11
- 150000003077 polyols Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 239000004970 Chain extender Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 8
- 229920002601 oligoester Polymers 0.000 description 8
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 8
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 7
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 150000003951 lactams Chemical class 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000012190 activator Substances 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 150000004760 silicates Chemical class 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000011496 polyurethane foam Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical class CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000006085 branching agent Substances 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
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- 125000004185 ester group Chemical group 0.000 description 1
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- 125000003916 ethylene diamine group Chemical group 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000006072 paste Substances 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
- 150000002989 phenols Chemical class 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- MOMGDEWWZBKDDR-UHFFFAOYSA-M sodium;3,4,5,6-tetrahydro-2h-azepin-7-olate Chemical compound [Na+].O=C1CCCCC[N-]1 MOMGDEWWZBKDDR-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000004448 titration Methods 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
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical class OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- B32—LAYERED PRODUCTS
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C7/00—Methods or apparatus for discharging liquefied, solidified, or compressed gases from pressure vessels, not covered by another subclass
- F17C7/02—Discharging liquefied gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0214—Materials belonging to B32B27/00
- B32B2266/0278—Polyurethane
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31562—Next to polyamide [nylon, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31609—Particulate metal or metal compound-containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31645—Next to addition polymer from unsaturated monomers
Definitions
- the invention relates to composites of at least 2 different plastics materials joined directly to one another, one material of which is composed of at least one thermoplastic polymer which contains polar compounds of metals of the 1st to the 5th main group or of the 1 st to the 8th subsidiary group of the Periodic System as an extremely fine particle inorganic powder, and the other material is made of polyurethane.
- the object according to the invention is achieved by composites which are composed of at least two different plastics materials joined directly to one another, of which
- A) is a thermoplastic polymer or a mixture of thermoplastic polymers which contain at least one polar compound of at least one of the metals of the 1st to the 5th main group or of the 1st to the 8th subsidiary group of the Periodic System as an extremely fine particle inorganic powder, and
- B) is polyurethane
- the composite materials may be prepared in a known way.
- the composite part is preferably produced beforehand from thermoplastic polymers and the polyurethane reaction system applied to it and reacted. Depending on the reactivity of the polyurethane reaction components, these may already be premixed or mixed in a known way during application. Application takes place preferably by spraying, knife coating or calendering. It is also possible, however, to prepare the composites according to the invention by coextrusion according to known methods.
- thermoplastic materials are all well known thermoplastics, preferably thermoplastic polyolefins, polycarbonates, polyester carbonates, polyesters, styrene copolymers, optionally rubber-containing graft (co)polymers such as ABS polymers, polyamides and/or thermoplastic mixtures thereof.
- thermoplastic material A is suitable as thermoplastic material A:
- Polyolefins according to the invention are polymers of aliphatic unsaturated hydrocarbons such as, for example, ethylene, propylene, butylene or isobutylene which are obtained by conventional processes, e.g. free radical polymerisation, and have average weight-average molecular weights ⁇ overscore (M) ⁇ w (measured by gel chromatography methods) of between 5,000 and 3,000,000. Both low density and high density polyolefin are suitable.
- the unsaturated hydrocarbons may also be copolymerised in a known way with other vinyl monomers such as, e.g. vinyl acetate, acrylic acid or acrylic acid ester, the proportion of vinyl monomers being a maximum of 30 wt. %, preferably up to 25 wt. %.
- thermoplastic polymers according to the invention are also thermoplastic aromatic polycarbonates, particularly those based on diphenols corresponding to formula (I)
- A means a single bond, C 1 -C 5 -alkylene, C 2 -C 5 -alkylidene, C 5 -C 6 -cycloalkylidene, —S—, —SO 2 —, —O—, —CO— or C 6 -C 12 -arylene, which may optionally be condensed with further aromatic rings containing heteroatoms,
- B independently of one another, means halogen, preferably chlorine, bromine, C 1 -C 8 -alkyl, C 6 -C 10 -aryl, preferably phenyl, C 7 -C 12 -aralkyl, preferably benzyl,
- x independently of one another, means 0, or 2 in each case, and
- R 1 and R 2 independently of one another, mean hydrogen, halogen, preferably chlorine or bromine, C 1 -C 8 -alkyl, C 5 -C 6 -cycloalkyl, C 6 -C 10 -aryl, preferably phenyl and C 7 -C 12 -aralkyl, preferably phenyl-C 1 -C 4 -alkyl, particularly benzyl,
- m is an integer from 4 to 7, preferably 4 or 5
- R 3 and R 4 which may be chosen individually for each Z, independently of one another, mean hydrogen or C 1 -C 6 -alkyl, preferably hydrogen, methyl or ethyl,
- Z means carbon, provided that on at least one atom Z R 3 and R 4 at the same time mean alkyl.
- Suitable diphenols having the formula (1) are e.g. hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)propane, 2,4-bis-(4-hydroxyphenyl) -2-methylbutane, 1,1 -bis-(4-hydroxyphenyl)cyclohexane, 2,2-bis-(3-chloro-4-hydroxyphenyl)propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)propane.
- hydroquinone resorcinol, 4,4′-dihydroxydiphenyl
- 2,2-bis-(4-hydroxyphenyl)propane 2,4-bis-(4-hydroxyphenyl) -2-methylbutane
- 1,1 -bis-(4-hydroxyphenyl)cyclohexane 2,2-bis-(3-chloro-4-hydroxyphenyl)propane
- Preferred diphenols having formula (I) are 2,2-bis-(4-hydroxyphenyl)propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)propane and 1,1-bis-(4-hydroxyphenyl) cyclohexane.
- the polycarbonates suitable according to the invention may be branched in a known way, preferably by the incorporation of 0.05 to 2.0 mole-%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, e.g. those with three or more than three phenolic groups, for example
- Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindol.
- Preferred polycarbonates apart from the bisphenol A-homopolycarbonate, are the copolycarbonates of bisphenol A with up to 15 mole-%, based on the mole sums of diphenols, of 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)propane.
- the aromatic polycarbonates used as component A may be partially exchanged by aromatic polyester carbonates.
- Aromatic polycarbonates and/or aromatic polyester carbonates according to component A are known from the literature or may be prepared according to processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, “Chemistry and Physics of Polycarbonates”, Interscience Publishers, 1964, and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; for the preparation of aromatic polyester carbonates, e.g. DE-OS 3 007 934).
- aromatic polycarbonates and/or aromatic polyester carbonates may take place, e.g. by reaction of diphenols with carbonic acid halides, preferably phosgene and/or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides, according to the interphase process, optionally using chain terminating agents and optionally using trifunctional or more than trifunctional branching agents.
- carbonic acid halides preferably phosgene and/or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides
- styrene (co)polymers of one or at least two ethylenically unsaturated monomers are suitable as thermoplastic material, such as, for example, styrene, ⁇ -methylstyrene, ring-substituted styrenes, acrylonitrile, methacrylonitrile, methylmethacrylate, maleic anhydride, N-substituted maleinimides and (meth)acrylic acid alkyl esters with 1 to 18 carbon atoms.
- the (co)polymers are resin-like, thermoplastic and rubber-free.
- Preferred styrene (co)polymers are those of at least one monomer from the series comprising styrene, ⁇ -methylstyrene and/or ring-substituted styrenes with at least one monomer from the series comprising acrylonitrile, methacrylonitrile, methylmethacrylate, maleic anhydride and/or N-substituted maleinimide.
- Particularly preferred weight ratios in the thermoplastic copolymer are 60 to 100 wt. % of the styrene monomers and 40 to 0 wt. % of the other vinyl monomers.
- Particularly preferred (co)polymers are those of styrene with acrylonitrile and optionally with methylmethacrylate, of ⁇ -methylstyrene with acrylonitrile and optionally with methylmethacrylate, or of styrene and ⁇ -methylstyrene with acrylonitrile and optionally with methylmethacrylate.
- the (co)polymers are well known and may be prepared by free radical polymerisation, particularly by emulsion, suspension, solution or bulk polymerisation.
- the (co)polymers preferably have molecular weights ⁇ overscore (M) ⁇ w (weight-average, determined by light scattering or sedimentation) of between 15,000 and 200,000.
- Particularly preferred (co)polymers are also random (co)polymers of styrene and maleic anhydride, which may be prepared preferably by a continuous bulk or solution polymerisation with incomplete conversions from the corresponding monomer.
- the proportions of both components of the random styrene-maleic anhydride copolymers suitable according to the invention may vary widely.
- the preferred maleic anhydride content is 5 to 25 wt. %.
- the polymers may also contain ring-substituted styrenes, such as p-methylstyrene, 2,4-dimethylstyrene and other substituted styrenes, such as ⁇ -methylstyrene.
- ring-substituted styrenes such as p-methylstyrene, 2,4-dimethylstyrene and other substituted styrenes, such as ⁇ -methylstyrene.
- the molecular weights (number-average ⁇ overscore (M) ⁇ n ) of styrene-maleic anhydride copolymers may vary widely. The range from 60,000 to 200,000 is preferred. A limiting viscosity number of 0.3 to 0.9 is preferred for these products (measured in dimethylformamide at 25° C.; see Hoffmann, Krömer, Kuhn, Polymeranalytik I, Stuttgart 1977, page 316 ff).
- thermoplastic composite materials are also graft (co)polymers. These include graft (co)polymers with rubber-elastic properties, which are obtainable essentially from at least 2 of the following monomers:
- Preferred graft (co)polymers include graft (co)polymers C of:
- polybutadienes grafted with acrylic or methacrylic acid alkyl esters, vinyl acetate, acrylonitrile, styrene and/or alkylstyrenes, butadiene/styrene or butadiene/acrylonitrile (co)polymers, polyisobutenes or polyisoprenes, of the kind described in e.g. DE-OS 2 348 377 ( U.S. Pat. No. 3,919,353).
- Particularly preferred graft (co)polymers are obtainable by a grafting reaction of
- ⁇ 10 to 70 preferably 15 to 50, particularly 20 to 40 wt. %, based on graft copolymer, of at least one (meth)acrylic acid ester or 10 to 70, preferably 15 to 50, particularly 20 to 40 wt. % of a mixture of 10 to 50, preferably 20 to 35 wt. %, based on mixture, of acrylonitrile or (meth)acrylic acid ester and 50 to 90, preferably 65 to 80 wt. %, based on mixture, of styrene as graft side chain C.1, onto
- ⁇ 30 to 90 preferably 50 to 85, particularly 60 to 80 wt. %, based on graft copolymer, of a butadiene polymer with at least 50 wt. %, based on ⁇ , of butadiene radicals as graft substrate C.2,
- the gel proportion of the graft substrate ⁇ is at least 70 wt. % (measured in toluene)
- the degree of grafting G is 0.15 to 0.55
- the average particle diameter d 50 of the graft polymer C.2 is 0.05 to 2 ⁇ m, preferably 0.1 to 0.6 ⁇ m.
- (Meth)acrylic acid esters ⁇ are esters of acrylic acid or methacrylic acid and monohydric alcohols with 1 to 18 carbon atoms. Methyl, ethyl and propyl esters of methacrylic acid, n-butylacrylate, t-butylacrylate and t-butylmethacrylate are particularly preferred.
- the graft substrate ⁇ may contain, in addition to butadiene radicals, up to 50 wt. %, based on ⁇ , of radicals of other ethylenically unsaturated monomers such as styrene, acrylonitrile, esters of acrylic or methacrylic acid with 1 to 4 carbon atoms in the alcohol component (such as methylacrylate, ethylacrylate, methylmethacrylate, ethylmethacrylate), vinyl esters and/or vinyl ethers.
- the preferred graft substrate ⁇ is composed of pure polybutadiene.
- graft (co)polymers according to the invention is also taken to mean those products that are obtained by polymerisation of graft monomers in the presence of the graft substrate.
- the degree of grafting G designates the weight ratio of grafted graft monomers to the graft substrate and is dimensionless.
- the average particle size d 50 is the diameter above and below which 50 wt. % of the particles lie in each case. It may be determined by an ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid Z. and Z. Polymere 250 (1972), 782-796).
- Particularly preferred polymers are. e.g. also graft polymers of
- the polyacrylate rubbers ⁇ of the graft polymers are preferably polymers of acrylic acid alkyl esters, optionally with up to 40 wt. %, based on ⁇ , of other polymerisable, ethylenically unsaturated monomers.
- the preferred polymerisable acrylic acid esters include C 1 -C 8 -alkyl esters, for example, methyl-, ethyl-, butyl-, n-octyl- and 2-ethylhexyl esters; halogen alkyl esters, preferably halogen-C 1 -C 8 -alkyl esters, such as chloroethylacrylate and mixtures of said monomers.
- crosslinking monomers with more than one polymerisable double bond may be copolymerised.
- Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated monohydric alcohols with 3 to 12 carbon atoms or saturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms, such as, e.g. ethylene glycol dimethacrylate, allylmethacrylate; polyunsaturated heterocyclic compounds such as, e.g. trivinyl and triallylcyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; and also triallylphosphate and diallylphthalate.
- Preferred crosslinking monomers are allylmethacrylate, ethylene glycol dimethacrylate, diallylphthalate and heterocyclic compounds having at least 3 ethylenically unsaturated groups.
- crosslinking monomers are the cyclic monomers triallylcyanurate, triallylisocyanurate, trivinylcyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.
- the amount of crosslinked monomers is preferably 0.02 to 5, particularly 0.05 to 2 wt. %, based on the graft substrate ⁇ .
- Preferred “other” polymerisable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, may optionally be used for the preparation of the graft substrate ⁇ , are e.g. acrylonitrile, styrene, ⁇ -methylstyrene, acrylamides, vinyl-C 1 -C 6 -alkylethers, methylmethacrylate, butadiene.
- Polyacrylate rubbers preferred as graft substrate ⁇ are emulsion polymers with a content of at least 60 wt. %.
- Suitable graft substrates according to C.2 are silicone rubbers with active grafting sites of the kind described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
- the gel content of the graft substrate C.2 is determined at 25° C. in dimethylformamide (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
- the graft copolymers may be prepared according to known processes such as bulk, suspension, emulsion or bulk-suspension processes.
- thermoplastic polyesters are suitable as thermoplastic material for the composites according to the invention.
- Polyesters that may be used are reaction products of aromatic dicarboxylic acids or their reactive derivatives e.g. dimethyl esters or anhydrides and aliphatic, cycloaliphatic or arylaliphatic diols and mixtures of such reaction products.
- Preferred polyalkylene terephthalates may be prepared according to known methods from terephthalic acids or their reactive derivatives and aliphatic and cycloaliphatic diols with 2 to 10 carbon atoms (Kunststoff-Handbuch, volume VIII, p. 695 ff, Carl Hanser Verlag, Kunststoff 1973).
- Preferred polyalkylene terephthalates contain 80 to 100, preferably 90 to 100 mole-%, based on the dicarboxylic acid component, of terephthalic acid radicals and 80 to 100, preferably 90 to 100 mole-%, based on the diol component, of ethylene glycol and/or butane-1,4-diol radicals.
- esters of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or aliphatic dicarboxylic acids with 4 to 12 carbon atoms are suitable, such as phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, succinic, adipic, sebacic, azelaic or cyclohexane diacetic acid or mixtures thereof.
- aliphatic diols with 3 to 12 carbon atoms are suitable such as pentane-1,5-diol, hexane-1,6-diol, cyclohexane dimethanol-1,4, 3-methylpentane-1,3- and 1,6-diol, 2-ethylhexane-1,3-diol, 2,2-diethylpropane-1,3-diol, hexane-2,5-diol, 1,4-(di( ⁇ -hydroxyethoxyphenyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis-(3 ⁇ -hydroxyethoxyphenyl) propane and 2,2-bis-(4-hydroxypropoxyphenyl) propane (DE-OS 2 407 647, 2 407 776, 2 715 932) or mixtures thereof.
- the polyesters may be branched by incorporation of relatively small quantities of tri- or tetrahydric alcohols or 3- or 4-basic carboxylic acid, of the kind described in DE-OS 1 900 270 and U.S. Pat. No. 3,692,744.
- preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane, and pentaerythritol. It is advisable to use not more than 1 mole-% of the branching agent, based on the acid component.
- Polyalkylene terephthalates prepared from terephthalic acid or reactive derivatives thereof e.g. their dialkyl esters and ethane diol and/or butane-1,4-diol (polyethylene terephthalate, polybutylene terephthalate), and mixtures thereof are particularly preferred.
- Preferred polyalkylene terephthalates are also copolyesters prepared from at least two of the above-mentioned diols; particularly preferred copolyesters are poly-(ethylene glycol/butane-1,4-diol) terephthalates.
- the various diol radicals may be in the form of blocks or randomly distributed in the copolyesters.
- the polyesters generally have a limiting viscosity number of 0.4 to 1.4 dl/g, preferably 0.5 to 1.3 dl/g, particularly 0.6 to 1.2 dl/g, measured in phenol/o-dichlorobenzene (1:1 parts by wt.) at 25° C. in each case.
- Polyamide 6 prepared by activated anionic polymerisation, or copolyamide with main constituent polycaprolactam prepared by activated anionic polymerisation is preferred.
- the activated anionic polymerisation of lactams to polyamides is carried out on an industrial scale in such a way that a solution of catalyst in lactam, optionally with impact strength modifier, is prepared on the one hand and a solution of activator in lactam on the other hand, both solutions usually having a composition such that a combined feed in the same ratio produces the desired overall formulation. This is not, however, necessary. It is also possible to choose other compositions, for example, to meter a concentrated activator and catalyst melt into a lactam melt. Further additives may be introduced into the activator, catalyst or optionally lactam melt, depending on compatibilities.
- Polymerisation takes place by mixing the individual solutions to obtain the overall formulation at 80° C. to 200° C., preferably 100° C. to 140° C.
- the catalyst is an alkali metal or alkaline earth metal lactamate, preferably as a solution in lactam, particularly preferably sodium caprolactamate in ⁇ -caprolactam.
- the activator within the context of the invention may be N-acyl lactams or acid chlorides or, preferably, aliphatic isocyanates, particularly preferably oligomers of hexamethylene diisocyanate. Both the pure substance and preferably a solution, for example, in N-methylpyrrolidone, may be used as activator.
- 0 to 50 preferably 1 to 50, particularly preferably 2 to 30, particularly preferably 8 to 25 parts by wt., of at least one of the styrene copolymers mentioned,
- thermoplastic material A [0106] are used in particular preference as thermoplastic material A.
- Extremely fine particle inorganic compounds are composed of compounds of one or more metals of the 1st to the 5th main group and the 1st to the 8th subsidiary group of the Mendeleev Periodic System, preferably the 2nd to the 5th main group or the 4th to the 8th subsidiary group, particularly preferably the 3rd to the 5th main group or the 4th to the 8th subsidiary group with at least one element selected from the group oxygen, sulfur, boron, phosphorus, carbon, nitrogen, hydrogen or silicon.
- Preferred compounds are, for example, oxides, hydroxides, water-containing oxides, sulfates, sulfites, sulfides, carbonates, carbides, nitrates, nitrites, nitrides, borates, silicates, phosphates, hydrides, phosphites or phosphonates.
- Preferred extremely fine particle inorganic compounds are, for example, TiN, TiO 2 , SnO 2 , WC, ZnO, Al 2 O 3 , AlO(OH), ZrO 2 , Sb 2 O 3 , SiO 2 , iron oxides, NaSO 4 , BaSO 4 , vanadium oxides, zinc borate, silicates such as Al silicates, Mg silicates, uni-, two- and three-dimensional silicates. Mixtures and doped compounds may also be used. Moreover, these nano-scale particles may be surface-modified with organic molecules in order to obtain better compatibility with the matrix. In this way, hydrophobic or hydrophilic organic surfaces may be obtained.
- the average particle diameters are smaller than 200 nm, preferably less than 150 nm, particularly 1 to 100 nm, more particularly preferably 1 to 70 nm.
- Particle size and particle diameter always means the average particle diameter d 50 determined by ultracentrifuge measurements according to W. Scholtan et at., Kolloid-Z. and Z. Polymere 250 (1972), pp 782 to 796.
- the inorganic compounds may take the form of powders, pastes, sols, dispersions or suspensions. Powders may be obtained from dispersions, sols or suspensions by precipitation.
- the powders may be incorporated in the thermoplastic materials according to conventional processes, for example, by direct kneading or extrusion of the constituents of the molding compound and the extremely fine particle inorganic powders.
- Preferred processes are the preparation of a masterbatch, e.g. in additives, monomers, solvents or in thermoplastic A, the co-precipitation of dispersions of component A with dispersion, suspensions, pastes or sols of the extremely fine particle inorganic materials.
- the molding compounds according to the invention may contain at least one of the conventional additives, such as lubricants and mold release agents, nucleating agents, antistatic agents, stabilisers and coloring agents and pigments.
- the inorganic powder is incorporated in the thermoplastic material in quantities of 0.5 to 50, preferably 1 to 25, particularly preferably 3 to 15 wt. %, based on the thermoplastic material A.
- thermoplastic, foamed or solid polyurethane materials or preferably molded parts may be prepared in a sandwich construction.
- polyurethanes or polyurethane ureas or polyureas used according to the invention are obtained by reaction of polyisocyanates with H-active polyfunctional compounds, preferably polyols.
- Suitable polyisocyanates are preferably those that are known from polyurethane chemistry and are conventionally used in that context. These are, in particular, polyisocyanates on an aromatic basis, e.g. 2,4-diisocyanatotoluene, the industrial mixtures thereof with 2,6-diisocyanatotoluene, 4,4′-diisocyanatodiphenylmethane, the mixtures thereof with the corresponding 2,4′- and 2,2′- isomers, polyisocyanate mixtures of the diphenylmethane series, of the kind that may be obtained in an inherently known way by phosgenation of aniline/formaldehyde condensates, the modification products of said industrial polyisocyanates having biuret or isocyanate groups, and in particular, NCO prepolymers of the kind mentioned based on said industrial polyisocyanates on the one hand, and the simple polyols and/or polyether polyols and/or
- Relatively high molecular weight modified polyisocyanates of particular interest include the prepolymers known from polyurethane chemistry with terminal isocyanate groups in the molecular weight range of 400 to 10,000, preferably 600 to 8,000 and particularly 800 to 5,000. These compounds are prepared in an inherently known way by reaction of excess quantities of simple polyisocyanates of the kind mentioned by way of example with organic compounds with at least two groups that are reactive towards isocyanate groups, particularly organic polyhydroxyl compounds.
- Suitable polyhydroxyl compounds of this kind are both simple polyhydric alcohols in the molecular weight range from 82 to 599, preferably 62 to 200, such as, e.g. ethylene glycol, trimethylol propane, propane-1,2-diol or butane-1,4-diol, or butane-2,3-diol, but in particular relatively high molecular weight polyether polyols and/or polyester polyols of the kind inherently known from polyurethane chemistry with molecular weights from 600 to 8,000, preferably 800 to 4,000, which have at least two, usually 2 to 8, but preferably 2 to 4 primary and/or secondary hydroxyl groups.
- NCO prepolymers which were obtained, for example, from low molecular weight polyisocyanates of the kind mentioned by way of example and less preferred compounds with groups that are reactive towards isocyanate groups, such as, e.g. polythioether polyols, hydroxyl group-containing polyacetals, polyhydroxy-polycarbonates, hydroxyl group-containing polyester amides or hydroxyl group-containing copolymers of olefinically unsaturated compounds.
- groups that are reactive towards isocyanate groups such as, e.g. polythioether polyols, hydroxyl group-containing polyacetals, polyhydroxy-polycarbonates, hydroxyl group-containing polyester amides or hydroxyl group-containing copolymers of olefinically unsaturated compounds.
- NCO prepolymers Compounds with groups that are reactive towards isocyanate groups, particularly hydroxyl groups, suitable for the preparation of NCO prepolymers, are, for example, the compounds disclosed by way of example in U.S. Pat. No. 4,218,543, column 7, line 29 to column 9, line 25.
- these compounds with groups that are reactive towards isocyanate groups are caused to react with simple polyisocyanates of the kind mentioned above by way of example whilst maintaining an NCO excess.
- the NCO prepolymers generally have an NCO content of 10 to 25, preferably 15 to 22 wt. %.
- NCO prepolymers and “prepolymers with terminal isocyanate groups” means both the reaction products as such and their mixtures with excess quantities of unreacted starting polyisocyanates which are often also called “semiprepolymers”.
- Polyester polyols of the kind which can be obtained in an inherently known way by reaction of low molecular weight alcohols with polyvalent carboxylic acids such as adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, or the anhydrides of these acids are also suitable, provided that the viscosity of the H-active component does not become too high.
- a preferred polyol having ester groups is castor oil.
- preparations with castor oil of the kind that may be obtained by dissolution of resins e.g. of aldehyde ketone resins, and modifications of castor oil and polyols based on other natural oils are also suitable.
- Relatively high molecular weight polyhydroxy polyethers in which high molecular weight polyadducts and polycondensates or polymers are present in the fine particle, dissolved or grafted form are also suitable.
- Such modified polyhydroxyl compounds are obtained, e.g., if polyaddition reactions (e.g. reactions between polyisocyanates and amino-functional compounds) or polycondensation reactions (e.g. between formaldehyde and phenols and/or amines) are allowed to take place in situ in the compounds containing hydroxyl groups.
- Polyhydroxyl compounds modified by vinyl polymers of the kind obtained e.g. by polymerisation of styrene and acrylonitrile in the presence of polyethers (U.S. Pat. Nos. 3,383,351, 3,304,273, 3,523,093, 3,110,695; DE-A-1 152 5369) or polycarbonate polyols (DE-PS 1 769 795; U.S. Pat. No. 3,637,909) are also suitable for the preparation of polyurethanes.
- polyethers U.S. Pat. Nos. 3,383,351, 3,304,273, 3,523,093, 3,110,695; DE-A-1 152 5369
- DE-PS 1 769 795 U.S. Pat. No. 3,637,909
- polyether polyols which were modified according to DE-A-2 442 101, 2 844 922 and 2 646 141 by graft polymerisation with vinyl phosphonic acid esters and optionally (meth)acrylonitrile, (meth)acrylamide or OH-functional (meth)acrylic acid esters are used, plastics with particular flame resistance are obtained.
- H-active compounds Representatives of the above-mentioned compounds to be used as H-active compounds are described, e.g., in High Polymers, Vol. XVI, “Polyurethanes Chemistry and Technology”, edited by Saunders-Frisch, Interscience Publishers, New York, London, Volume 1, 1982, pages 32 to 42 and pages 44 to 54 and Volume II, 1984, pages 5 to 6 and 198 to 199, and in Kunststoff-Handbuch, Volume VII, Carl Hanser Verlag, Kunststoff, 1983, e.g. on pages 45 to 61.
- auxiliaries and additives such as, e.g. release agents, blowing agents, fillers, catalysts and flame retardants may be used.
- the reaction mixture may be introduced into a mold in an inherently known way.
- the expandable reaction mixture foams in the mold and forms the molded part.
- Form molding may be carried out in such a way that the molded part has a cellular structure on its surface. It may also, however, be carried out in such a way that the molded part has a compact skin and a cellular core (integral foams).
- Polyurethane foams may also be prepared as slabstock foam.
- the preparation of polyurethane composite parts in a sandwich construction is also preferred.
- the process may be designed both as a sandwich or envelope process. Both the sandwich construction and the envelope construction are inherently known.
- sandwich process filled structure
- two half-shells e.g. outer layers of plastics
- the envelope construction a core of PUR foam is placed in a mold and then enveloped with a suitable envelope material, e.g. with one of the above-mentioned thermoplastics.
- the envelope construction is preferred for the preparation of sandwich composite parts.
- Thermoplastic polyurethanes according to the present invention are reaction products of diisocyanates, wholly or predominantly aliphatic oligo- and/or polyesters and/or -ethers, and one or more chain extenders. These thermoplastic polyurethanes are essentially linear and have thermoplastic processing characteristics.
- thermoplastic polyurethanes are either well known or may be prepared by known processes (see, for example, U.S. Pat. No. 3,214,411, J. H. Saunders and K. C. Frisch, “Polyurethanes, Chemistry and Technology”, vol. II, pages 299 to 451, Interscience Publishers, New York, 1964 and Mobay Chemical Corporation, “A Processing Handbook for Texin Urethane Elastoplastic Materials”, Pittsburgh, Pa.).
- Starting materials for the preparation of oligoesters and polyesters are, for example, adipic acid, succinic acid, suberic acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid and isophthalic acid.
- Adipic acid is preferred in this case.
- Suitable glycols for the preparation of oligoesters and polyesters are, for example, ethylene glycol, 1,2- and 1,3-propylene glycol, butane-1,2-, 1,3-, 1,4-, 2,3-, 2,4-diol, hexane diol, bishydroxymethylcyclohexane, diethylene glycol and 2,2-dimethylpropylene glycol.
- small quantities of up to 1 mole-% of trifunctional or higher functionality alcohols e.g. trimethylol propane, glycerol, hexane triol etc. may be used together with the glycols.
- the resulting hydroxyl oligoesters or polyesters have a molecular weight of at least 600, a hydroxyl number of about 25 to 190, preferably about 40 to 150, an acid value of about 0.5 to 2 and a water content of about 0.01 to 0.2%.
- Oligoesters and polyesters are also oligomeric or polymeric lactones, such as, for example, oligocaprolactone or polycaprolactone, and aliphatic polycarbonates such as, for example, polybutane diol-(1,4-)-carbonate or polyhexane diol-(1,6)-carbonate.
- a particularly suitable oligoradical which may be used as a starting material for the thermoplastic polyurethanes is prepared from adipic acid and a glycol which has at least one primary hydroxyl group. Condensation is ended when an acid value of 10, preferably about 0.5 to 2 is reached. The water produced during the reaction is thus separated at the same time or afterwards so that the water content at the end lies in the region of approximately 0.01 to 0.05%, preferably 0.01 to 0.02.
- Oligoethers and polyethers for the preparation of the thermoplastic polyurethanes according to component B are, for example, those based on tetramethylene glycol, propylene glycol and ethylene glycol.
- Polyacetals are also to be understood as polyethers and may be used as such.
- the oligoethers and polyethers should have an average molecular weight n (number-average, determined by way of the OH number of the products) of 600 to 2,000, preferably 1,000 to 2,000.
- the organic diisocyanate used for the preparation of the polyurethanes according to component B is preferably 4,4′-diphenylmethane diisocyanate. It should contain less than 5% of 2,4′-diphenylmethane diisocyanate and less than 2% of the dimer of diphenylmethane diisocyanate. It is also desirable that the acidity, calculated as HCl, be in the region of about 0.005 to 0.2%.
- the acidity calculated as HCl, is determined by extraction of chloride from the isocyanate in hot, aqueous methanol solution or by liberation of the chloride on hydrolysis with water and titration of the extract with standard silver nitrate solution in order to obtain the chloride ion concentration present therein.
- diisocyanates may also be used for the preparation of the thermoplastic polyurethanes according to component B, for example, the diisocyanates of ethylene, ethylidene, propylene, butylene, cyclopentylene-1,3, cyclohexylene-1,4,cyclohexylene-1,2, 2,4-toluene, 2,6-toluene, p-phenylene, n-phenylene, xylene, 1,4-naphthylene, 1,5-naphthylene, 4,4′-diphenylene, 2,2-diphenylpropane-4,4′-diisocyanate, azobenzene-4,4′-diisocyanate, diphenylsulfone-4,4′-diisocyanate, dichlorohexane methylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1-chlorobenz
- Chain extenders that may be used are organic difunctional compounds containing active hydrogen that is reactive with isocyanates, e.g. diols, hydroxycarboxylic acids, dicarboxylic acids, diamines and alkanolamines and water.
- Such compounds include, for example, ethylene-, propylene-, butylene glycol, butane-1,4-diol, butane diol, butyne diol, xylylene glycol, amylene glycol, 1,4-phenylene-bis- ⁇ -hydroxyethylether, 1,3-phenylene-bis- ⁇ -hydroxyethylether, bis-(hydroxymethyl cyclohexane), hexane diol, adipic acid, hydroxycaproic acid, thiodiglycol, ethylene diamine-, propylene-, butylene-, hexamethylene-, cyclohexylene-, phenylene-, toluene-, xylylene diamine, diaminodicyclohexylmethane, isophorone diamine, 3,3′-dichlorobenzidine, 3,3′-dinitrobenzidine, ethanolamine, aminopropyl alcohol, 2,2-dimethylpropan
- trifunctional or more than trifunctional chain extenders may also be used in minor quantities up to about 5 mole-%, based on moles of difunctional chain extenders used.
- Such trifunctional or more than trifunctional chain extenders are, for example, glycerol, trimethylol propane, hexane triol, pentaerythritol, and triethanolamine.
- thermoplastic polyurethanes may also be used for the preparation of the thermoplastic polyurethanes according to component B.
- thermoplastic polyurethanes are either known from the literature or may be obtained according to processes known from the literature.
- the oligoesters and polyesters, the organic diisocyanates and the chain extenders may be heated by themselves, preferably to a temperature of about 50 to 220° C. and then mixed.
- the oligoesters and polyesters are preferably heated individually first, then mixed with the chain extenders and the mixture obtained mixed with the preheated isocyanate.
- the mixing of the starting components for the preparation of the polyurethanes may be carried out with any mechanical stirrer that permits intensive mixing within a short period. If the viscosity of the mixture during stirring should prematurely rise too rapidly, the temperature may either be lowered or a small quantity (0.001 to 0.05 wt. %, based on ester) of citric acid or similar may be added in order to reduce the rate of the reaction. Suitable catalysts such as, e.g. tertiary amines, which are mentioned in U.S. Pat. No. 2,729,618, may be used to increase the rate of reaction.
- Graft polymer of 40 parts by wt. of a copolymer of styrene and acrylonitrile in a ratio of 73:27 on 60 parts by wt. of a particulate crosslinked polybutadiene rubber (average particle size d 50 0.3 ⁇ m), prepared by emulsion polymerisation.
- AlO (OH) as polar compound (Plural 200 from Condea, Hamburg);
- PETS penentaerythritol tetrastearate
- polyurethane foam system Bayfill 51 IF 02 P from Bayer AG, Leverkusen, Germany.
Abstract
Description
- The invention relates to composites of at least 2 different plastics materials joined directly to one another, one material of which is composed of at least one thermoplastic polymer which contains polar compounds of metals of the 1st to the 5th main group or of the 1 st to the 8th subsidiary group of the Periodic System as an extremely fine particle inorganic powder, and the other material is made of polyurethane.
- It is known that composites of a thermoplastic material and a polyurethane, particularly a polyurethane foam material, do not have sufficient bond adhesion. As there is an increasing desire in the motor vehicle industry to use composite materials whose bond adhesion is capable of withstanding even extreme temperature variations, yet the fewest possible different materials should be used on account of recycling requirements, the object of the present invention was to improve sufficiently the bond adhesion of thermoplastic materials joined directly to one another with polyurethane.
- The object according to the invention is achieved by composites which are composed of at least two different plastics materials joined directly to one another, of which
- A) is a thermoplastic polymer or a mixture of thermoplastic polymers which contain at least one polar compound of at least one of the metals of the 1st to the 5th main group or of the 1st to the 8th subsidiary group of the Periodic System as an extremely fine particle inorganic powder, and
- B) is polyurethane.
- The composite materials may be prepared in a known way. The composite part is preferably produced beforehand from thermoplastic polymers and the polyurethane reaction system applied to it and reacted. Depending on the reactivity of the polyurethane reaction components, these may already be premixed or mixed in a known way during application. Application takes place preferably by spraying, knife coating or calendering. It is also possible, however, to prepare the composites according to the invention by coextrusion according to known methods.
- Suitable thermoplastic materials are all well known thermoplastics, preferably thermoplastic polyolefins, polycarbonates, polyester carbonates, polyesters, styrene copolymers, optionally rubber-containing graft (co)polymers such as ABS polymers, polyamides and/or thermoplastic mixtures thereof.
- In preference, the following polymers are suitable as thermoplastic material A:
- Polyolefins according to the invention are polymers of aliphatic unsaturated hydrocarbons such as, for example, ethylene, propylene, butylene or isobutylene which are obtained by conventional processes, e.g. free radical polymerisation, and have average weight-average molecular weights {overscore (M)}w (measured by gel chromatography methods) of between 5,000 and 3,000,000. Both low density and high density polyolefin are suitable. The unsaturated hydrocarbons may also be copolymerised in a known way with other vinyl monomers such as, e.g. vinyl acetate, acrylic acid or acrylic acid ester, the proportion of vinyl monomers being a maximum of 30 wt. %, preferably up to 25 wt. %.
- Polyethylene and polypropylene are preferred.
-
- wherein
- A means a single bond, C1-C5-alkylene, C2-C5-alkylidene, C5-C6-cycloalkylidene, —S—, —SO2—, —O—, —CO— or C6-C12-arylene, which may optionally be condensed with further aromatic rings containing heteroatoms,
- B independently of one another, means halogen, preferably chlorine, bromine, C1-C8-alkyl, C6-C10-aryl, preferably phenyl, C7-C12-aralkyl, preferably benzyl,
- x independently of one another, means 0, or 2 in each case, and
- p means 1 or 0,
-
- wherein
- R1 and R2, independently of one another, mean hydrogen, halogen, preferably chlorine or bromine, C1-C8-alkyl, C5-C6-cycloalkyl, C6-C10-aryl, preferably phenyl and C7-C12-aralkyl, preferably phenyl-C1-C4-alkyl, particularly benzyl,
- m is an integer from 4 to 7, preferably 4 or 5,
- R3 and R4, which may be chosen individually for each Z, independently of one another, mean hydrogen or C1-C6-alkyl, preferably hydrogen, methyl or ethyl,
- and
- Z means carbon, provided that on at least one atom Z R3 and R4 at the same time mean alkyl.
- Suitable diphenols having the formula (1) are e.g. hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)propane, 2,4-bis-(4-hydroxyphenyl) -2-methylbutane, 1,1 -bis-(4-hydroxyphenyl)cyclohexane, 2,2-bis-(3-chloro-4-hydroxyphenyl)propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)propane.
- Preferred diphenols having formula (I) are 2,2-bis-(4-hydroxyphenyl)propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)propane and 1,1-bis-(4-hydroxyphenyl) cyclohexane.
-
- 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (formula (IIa) being particularly preferred.
- The polycarbonates suitable according to the invention may be branched in a known way, preferably by the incorporation of 0.05 to 2.0 mole-%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, e.g. those with three or more than three phenolic groups, for example
- phloroglucinol,
- 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)heptene-2,
-
- 1,3,5-tri-(4-hydroxyphenyl)benzene,
- 1,1,1,-tri-(4-hydroxyphenyl)ethane,
- tri-(4-hydroxyphenyl)phenylmethane,
- 2,2-bis-(4,4-bis-(4-hydroxyphenyl)-cyclohexyl)propane,
- 2,4-bis-(4-hydroxyphenyl)-isopropyl)phenol,
- 2,6-bis-(2-hydroxy-5′-methylbenzyl)-4-methylphenol,
- 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane,
- hexa-(4-(4-hydroxyphenylisopropyl)-phenyl)-orthoterephthalate,
- tetra-(4-hydroxyphenyl)methane,
- tetra-(4-(4-hydroxyphenylisopropyl)-phenoxy)methane, and
- 1,4-bis-((4′,4″-dihydroxytriphenyl)-methyl)benzene.
- Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindol.
- Preferred polycarbonates, apart from the bisphenol A-homopolycarbonate, are the copolycarbonates of bisphenol A with up to 15 mole-%, based on the mole sums of diphenols, of 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)propane.
- The aromatic polycarbonates used as component A may be partially exchanged by aromatic polyester carbonates.
- Aromatic polycarbonates and/or aromatic polyester carbonates according to component A are known from the literature or may be prepared according to processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, “Chemistry and Physics of Polycarbonates”, Interscience Publishers, 1964, and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; for the preparation of aromatic polyester carbonates, e.g. DE-OS 3 007 934).
- The preparation of aromatic polycarbonates and/or aromatic polyester carbonates may take place, e.g. by reaction of diphenols with carbonic acid halides, preferably phosgene and/or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides, according to the interphase process, optionally using chain terminating agents and optionally using trifunctional or more than trifunctional branching agents.
- Moreover, styrene (co)polymers of one or at least two ethylenically unsaturated monomers (vinyl monomers) are suitable as thermoplastic material, such as, for example, styrene, α-methylstyrene, ring-substituted styrenes, acrylonitrile, methacrylonitrile, methylmethacrylate, maleic anhydride, N-substituted maleinimides and (meth)acrylic acid alkyl esters with 1 to 18 carbon atoms.
- The (co)polymers are resin-like, thermoplastic and rubber-free.
- Preferred styrene (co)polymers are those of at least one monomer from the series comprising styrene, α-methylstyrene and/or ring-substituted styrenes with at least one monomer from the series comprising acrylonitrile, methacrylonitrile, methylmethacrylate, maleic anhydride and/or N-substituted maleinimide.
- Particularly preferred weight ratios in the thermoplastic copolymer are 60 to 100 wt. % of the styrene monomers and 40 to 0 wt. % of the other vinyl monomers. Particularly preferred (co)polymers are those of styrene with acrylonitrile and optionally with methylmethacrylate, of α-methylstyrene with acrylonitrile and optionally with methylmethacrylate, or of styrene and α-methylstyrene with acrylonitrile and optionally with methylmethacrylate.
- The (co)polymers are well known and may be prepared by free radical polymerisation, particularly by emulsion, suspension, solution or bulk polymerisation. The (co)polymers preferably have molecular weights {overscore (M)}w (weight-average, determined by light scattering or sedimentation) of between 15,000 and 200,000.
- Particularly preferred (co)polymers are also random (co)polymers of styrene and maleic anhydride, which may be prepared preferably by a continuous bulk or solution polymerisation with incomplete conversions from the corresponding monomer.
- The proportions of both components of the random styrene-maleic anhydride copolymers suitable according to the invention may vary widely. The preferred maleic anhydride content is 5 to 25 wt. %.
- Instead of styrene, the polymers may also contain ring-substituted styrenes, such as p-methylstyrene, 2,4-dimethylstyrene and other substituted styrenes, such as α-methylstyrene.
- The molecular weights (number-average {overscore (M)}n) of styrene-maleic anhydride copolymers may vary widely. The range from 60,000 to 200,000 is preferred. A limiting viscosity number of 0.3 to 0.9 is preferred for these products (measured in dimethylformamide at 25° C.; see Hoffmann, Krömer, Kuhn, Polymeranalytik I, Stuttgart 1977, page 316 ff).
- Suitable thermoplastic composite materials are also graft (co)polymers. These include graft (co)polymers with rubber-elastic properties, which are obtainable essentially from at least 2 of the following monomers:
- Chloroprene, butadiene-1,3, isopropene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and (meth)acrylic acid ester with 1 to 18 carbon atoms in the alcohol component; that is, polymers such as those described, e.g. in “Methoden der Organischen Chemie” (Houben-Weyl), vol. 14/1, Georg Thieme-Verlag, Stuttgart 1961, pp. 393-406 and in C. B. Bucknall, “Toughened Plastics”, Appl. Science Publishers, London 1977. Preferred graft polymers are partially crosslinked and have gel contents of more than 20 wt. %, preferably over 40 wt. % and particularly over 60 wt. %.
- Preferred graft (co)polymers include graft (co)polymers C of:
- C.1 5 to 95, preferably 30 to 80 parts by wt. of a mixture of
- C.1.1 50 to 99 parts by wt. of styrene, α-methylstyrene, halogen or methyl ring-substituted styrenes, methylmethacrylate or mixtures of said compounds, and
- C.1.2 1 to 50 parts by wt. of acrylonitrile, methacrylonitrile, methylmethacrylate, maleic anhydride, C1-C4-alkyl or phenyl-N-substituted maleinimides or mixtures of said compounds,
- C.2 5 to 95, preferably 20 to 70 parts by wt. of polymer based on diene and/or alkyl acrylate with a glass transition temperature of <10° C., preferably <−10° C.
- Preferred graft (co)polymers are substrates C.2. grafted e.g. with styrene and/or acrylonitrile and/or (meth)acrylic acid alkyl esters such as polybutadienes, butadiene/styrene copolymer and acrylate rubbers; i.e. (co)polymers of the kind described in DE-OS 1 694 173 (=U.S. Pat. No. 3,564,077); polybutadienes grafted with acrylic or methacrylic acid alkyl esters, vinyl acetate, acrylonitrile, styrene and/or alkylstyrenes, butadiene/styrene or butadiene/acrylonitrile (co)polymers, polyisobutenes or polyisoprenes, of the kind described in e.g. DE-OS 2 348 377 (=U.S. Pat. No. 3,919,353).
- Particularly preferred polymers are e.g. ABS polymers of the kind described e.g. in DE-OS 2 035 390 (=U.S. Pat. No. 3,644,574) or in DE-OS 2 248 242 (=GB PS 1 409 275).
- Particularly preferred graft (co)polymers are obtainable by a grafting reaction of
- α 10 to 70, preferably 15 to 50, particularly 20 to 40 wt. %, based on graft copolymer, of at least one (meth)acrylic acid ester or 10 to 70, preferably 15 to 50, particularly 20 to 40 wt. % of a mixture of 10 to 50, preferably 20 to 35 wt. %, based on mixture, of acrylonitrile or (meth)acrylic acid ester and 50 to 90, preferably 65 to 80 wt. %, based on mixture, of styrene as graft side chain C.1, onto
- β 30 to 90, preferably 50 to 85, particularly 60 to 80 wt. %, based on graft copolymer, of a butadiene polymer with at least 50 wt. %, based on β, of butadiene radicals as graft substrate C.2,
- where preferably the gel proportion of the graft substrate β is at least 70 wt. % (measured in toluene), the degree of grafting G is 0.15 to 0.55 and the average particle diameter d50 of the graft polymer C.2 is 0.05 to 2 μm, preferably 0.1 to 0.6 μm.
- (Meth)acrylic acid esters α are esters of acrylic acid or methacrylic acid and monohydric alcohols with 1 to 18 carbon atoms. Methyl, ethyl and propyl esters of methacrylic acid, n-butylacrylate, t-butylacrylate and t-butylmethacrylate are particularly preferred.
- The graft substrate β may contain, in addition to butadiene radicals, up to 50 wt. %, based on β, of radicals of other ethylenically unsaturated monomers such as styrene, acrylonitrile, esters of acrylic or methacrylic acid with 1 to 4 carbon atoms in the alcohol component (such as methylacrylate, ethylacrylate, methylmethacrylate, ethylmethacrylate), vinyl esters and/or vinyl ethers. The preferred graft substrate β is composed of pure polybutadiene.
- As it is well known that the graft monomers are not necessarily fully grafted onto the graft substrate during the grafting reaction, the term graft (co)polymers according to the invention is also taken to mean those products that are obtained by polymerisation of graft monomers in the presence of the graft substrate.
- The degree of grafting G designates the weight ratio of grafted graft monomers to the graft substrate and is dimensionless.
- The average particle size d50 is the diameter above and below which 50 wt. % of the particles lie in each case. It may be determined by an ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid Z. and Z. Polymere 250 (1972), 782-796).
- Particularly preferred polymers are. e.g. also graft polymers of
- τ 20 to 90 wt. %, based on the graft polymer, of acrylate rubber with a glass transition temperature of <−20° C. as graft substrate C.2 and
- δ 10 to 80 wt. %, based on the graft polymer, of at least one polymerisable, ethylenically unsaturated monomer.
- The polyacrylate rubbers τ of the graft polymers are preferably polymers of acrylic acid alkyl esters, optionally with up to 40 wt. %, based on τ, of other polymerisable, ethylenically unsaturated monomers. The preferred polymerisable acrylic acid esters include C1-C8-alkyl esters, for example, methyl-, ethyl-, butyl-, n-octyl- and 2-ethylhexyl esters; halogen alkyl esters, preferably halogen-C1-C8-alkyl esters, such as chloroethylacrylate and mixtures of said monomers.
- For the purpose of crosslinking, monomers with more than one polymerisable double bond may be copolymerised. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated monohydric alcohols with 3 to 12 carbon atoms or saturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms, such as, e.g. ethylene glycol dimethacrylate, allylmethacrylate; polyunsaturated heterocyclic compounds such as, e.g. trivinyl and triallylcyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; and also triallylphosphate and diallylphthalate.
- Preferred crosslinking monomers are allylmethacrylate, ethylene glycol dimethacrylate, diallylphthalate and heterocyclic compounds having at least 3 ethylenically unsaturated groups.
- Particularly preferred crosslinking monomers are the cyclic monomers triallylcyanurate, triallylisocyanurate, trivinylcyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.
- The amount of crosslinked monomers is preferably 0.02 to 5, particularly 0.05 to 2 wt. %, based on the graft substrate τ.
- In the case of cyclic crosslinking monomers with at least 3 ethylenically unsaturated groups, it is advantageous to limit the quantity to less than 1 wt. % of the graft substrate τ.
- Preferred “other” polymerisable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, may optionally be used for the preparation of the graft substrate τ, are e.g. acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl-C1-C6-alkylethers, methylmethacrylate, butadiene. Polyacrylate rubbers preferred as graft substrate τ are emulsion polymers with a content of at least 60 wt. %.
- Further suitable graft substrates according to C.2 are silicone rubbers with active grafting sites of the kind described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
- The gel content of the graft substrate C.2 is determined at 25° C. in dimethylformamide (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
- The graft copolymers may be prepared according to known processes such as bulk, suspension, emulsion or bulk-suspension processes.
- Moreover, thermoplastic polyesters are suitable as thermoplastic material for the composites according to the invention.
- Polyesters that may be used are reaction products of aromatic dicarboxylic acids or their reactive derivatives e.g. dimethyl esters or anhydrides and aliphatic, cycloaliphatic or arylaliphatic diols and mixtures of such reaction products.
- Preferred polyalkylene terephthalates may be prepared according to known methods from terephthalic acids or their reactive derivatives and aliphatic and cycloaliphatic diols with 2 to 10 carbon atoms (Kunststoff-Handbuch, volume VIII, p. 695 ff, Carl Hanser Verlag, Munich 1973).
- Preferred polyalkylene terephthalates contain 80 to 100, preferably 90 to 100 mole-%, based on the dicarboxylic acid component, of terephthalic acid radicals and 80 to 100, preferably 90 to 100 mole-%, based on the diol component, of ethylene glycol and/or butane-1,4-diol radicals. In addition to terephthalic acid esters, esters of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or aliphatic dicarboxylic acids with 4 to 12 carbon atoms are suitable, such as phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, succinic, adipic, sebacic, azelaic or cyclohexane diacetic acid or mixtures thereof. In addition to ethylene glycol and/or butane-1,4-diol, other aliphatic diols with 3 to 12 carbon atoms are suitable such as pentane-1,5-diol, hexane-1,6-diol, cyclohexane dimethanol-1,4, 3-methylpentane-1,3- and 1,6-diol, 2-ethylhexane-1,3-diol, 2,2-diethylpropane-1,3-diol, hexane-2,5-diol, 1,4-(di(β-hydroxyethoxyphenyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis-(3β-hydroxyethoxyphenyl) propane and 2,2-bis-(4-hydroxypropoxyphenyl) propane (DE-OS 2 407 647, 2 407 776, 2 715 932) or mixtures thereof.
- The polyesters, particularly polyalkylene terephthalates, may be branched by incorporation of relatively small quantities of tri- or tetrahydric alcohols or 3- or 4-basic carboxylic acid, of the kind described in DE-OS 1 900 270 and U.S. Pat. No. 3,692,744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane, and pentaerythritol. It is advisable to use not more than 1 mole-% of the branching agent, based on the acid component.
- Polyalkylene terephthalates prepared from terephthalic acid or reactive derivatives thereof e.g. their dialkyl esters and ethane diol and/or butane-1,4-diol (polyethylene terephthalate, polybutylene terephthalate), and mixtures thereof are particularly preferred.
- Preferred polyalkylene terephthalates are also copolyesters prepared from at least two of the above-mentioned diols; particularly preferred copolyesters are poly-(ethylene glycol/butane-1,4-diol) terephthalates. The various diol radicals may be in the form of blocks or randomly distributed in the copolyesters.
- The polyesters generally have a limiting viscosity number of 0.4 to 1.4 dl/g, preferably 0.5 to 1.3 dl/g, particularly 0.6 to 1.2 dl/g, measured in phenol/o-dichlorobenzene (1:1 parts by wt.) at 25° C. in each case.
- The thermoplastic polyamides that may be used for the composites according to the invention are polyamide 66 (polyhexamethylene adipinamide) or polyamides of cyclic lactams with 6 to 12 carbon atoms, preferably of laurinlactam and particularly preferably ε-caprolactam=polyamide 6 (polycaprolactam) or copolyamides with main constituents 6 or 66 or compounds with main constituent of the polyamides mentioned. Polyamide 6 prepared by activated anionic polymerisation, or copolyamide with main constituent polycaprolactam prepared by activated anionic polymerisation is preferred.
- The activated anionic polymerisation of lactams to polyamides is carried out on an industrial scale in such a way that a solution of catalyst in lactam, optionally with impact strength modifier, is prepared on the one hand and a solution of activator in lactam on the other hand, both solutions usually having a composition such that a combined feed in the same ratio produces the desired overall formulation. This is not, however, necessary. It is also possible to choose other compositions, for example, to meter a concentrated activator and catalyst melt into a lactam melt. Further additives may be introduced into the activator, catalyst or optionally lactam melt, depending on compatibilities.
- Polymerisation takes place by mixing the individual solutions to obtain the overall formulation at 80° C. to 200° C., preferably 100° C. to 140° C.
- The catalyst is an alkali metal or alkaline earth metal lactamate, preferably as a solution in lactam, particularly preferably sodium caprolactamate in ε-caprolactam.
- The activator within the context of the invention may be N-acyl lactams or acid chlorides or, preferably, aliphatic isocyanates, particularly preferably oligomers of hexamethylene diisocyanate. Both the pure substance and preferably a solution, for example, in N-methylpyrrolidone, may be used as activator.
- Mixtures of at least
- 1 to 99, preferably 10 to 90, particularly preferably 20 to 80 parts by wt., of at least one of the polycarbonates mentioned,
- 0 to 50, preferably 1 to 50, particularly preferably 2 to 30, particularly preferably 8 to 25 parts by wt., of at least one of the styrene copolymers mentioned,
- and
- 1 to 99, preferably 7 to 80, particularly preferably 10 to 70 parts by wt., of one or more of the graft polymers mentioned
- are used in particular preference as thermoplastic material A.
- Extremely fine particle inorganic compounds (powders) are composed of compounds of one or more metals of the 1st to the 5th main group and the 1st to the 8th subsidiary group of the Mendeleev Periodic System, preferably the 2nd to the 5th main group or the 4th to the 8th subsidiary group, particularly preferably the 3rd to the 5th main group or the 4th to the 8th subsidiary group with at least one element selected from the group oxygen, sulfur, boron, phosphorus, carbon, nitrogen, hydrogen or silicon.
- Preferred compounds are, for example, oxides, hydroxides, water-containing oxides, sulfates, sulfites, sulfides, carbonates, carbides, nitrates, nitrites, nitrides, borates, silicates, phosphates, hydrides, phosphites or phosphonates.
- Preferred extremely fine particle inorganic compounds are, for example, TiN, TiO2, SnO2, WC, ZnO, Al2O3, AlO(OH), ZrO2, Sb2O3, SiO2, iron oxides, NaSO4, BaSO4, vanadium oxides, zinc borate, silicates such as Al silicates, Mg silicates, uni-, two- and three-dimensional silicates. Mixtures and doped compounds may also be used. Moreover, these nano-scale particles may be surface-modified with organic molecules in order to obtain better compatibility with the matrix. In this way, hydrophobic or hydrophilic organic surfaces may be obtained.
- The average particle diameters are smaller than 200 nm, preferably less than 150 nm, particularly 1 to 100 nm, more particularly preferably 1 to 70 nm.
- Particle size and particle diameter always means the average particle diameter d50 determined by ultracentrifuge measurements according to W. Scholtan et at., Kolloid-Z. and Z. Polymere 250 (1972), pp 782 to 796.
- The inorganic compounds may take the form of powders, pastes, sols, dispersions or suspensions. Powders may be obtained from dispersions, sols or suspensions by precipitation.
- The powders may be incorporated in the thermoplastic materials according to conventional processes, for example, by direct kneading or extrusion of the constituents of the molding compound and the extremely fine particle inorganic powders. Preferred processes are the preparation of a masterbatch, e.g. in additives, monomers, solvents or in thermoplastic A, the co-precipitation of dispersions of component A with dispersion, suspensions, pastes or sols of the extremely fine particle inorganic materials.
- The molding compounds according to the invention may contain at least one of the conventional additives, such as lubricants and mold release agents, nucleating agents, antistatic agents, stabilisers and coloring agents and pigments.
- The inorganic powder is incorporated in the thermoplastic material in quantities of 0.5 to 50, preferably 1 to 25, particularly preferably 3 to 15 wt. %, based on the thermoplastic material A.
- According to the invention, thermoplastic, foamed or solid polyurethane materials or preferably molded parts may be prepared in a sandwich construction.
- The polyurethanes or polyurethane ureas or polyureas used according to the invention are obtained by reaction of polyisocyanates with H-active polyfunctional compounds, preferably polyols.
- Suitable polyisocyanates are preferably those that are known from polyurethane chemistry and are conventionally used in that context. These are, in particular, polyisocyanates on an aromatic basis, e.g. 2,4-diisocyanatotoluene, the industrial mixtures thereof with 2,6-diisocyanatotoluene, 4,4′-diisocyanatodiphenylmethane, the mixtures thereof with the corresponding 2,4′- and 2,2′- isomers, polyisocyanate mixtures of the diphenylmethane series, of the kind that may be obtained in an inherently known way by phosgenation of aniline/formaldehyde condensates, the modification products of said industrial polyisocyanates having biuret or isocyanate groups, and in particular, NCO prepolymers of the kind mentioned based on said industrial polyisocyanates on the one hand, and the simple polyols and/or polyether polyols and/or polyester polyols mentioned by way of example in the case of component B described below on the other hand, and also any mixtures of such isocyanates, provided they are sufficiently stable in storage.
- Relatively high molecular weight modified polyisocyanates of particular interest include the prepolymers known from polyurethane chemistry with terminal isocyanate groups in the molecular weight range of 400 to 10,000, preferably 600 to 8,000 and particularly 800 to 5,000. These compounds are prepared in an inherently known way by reaction of excess quantities of simple polyisocyanates of the kind mentioned by way of example with organic compounds with at least two groups that are reactive towards isocyanate groups, particularly organic polyhydroxyl compounds.
- Suitable polyhydroxyl compounds of this kind are both simple polyhydric alcohols in the molecular weight range from 82 to 599, preferably 62 to 200, such as, e.g. ethylene glycol, trimethylol propane, propane-1,2-diol or butane-1,4-diol, or butane-2,3-diol, but in particular relatively high molecular weight polyether polyols and/or polyester polyols of the kind inherently known from polyurethane chemistry with molecular weights from 600 to 8,000, preferably 800 to 4,000, which have at least two, usually 2 to 8, but preferably 2 to 4 primary and/or secondary hydroxyl groups. Naturally, it is also possible to use NCO prepolymers which were obtained, for example, from low molecular weight polyisocyanates of the kind mentioned by way of example and less preferred compounds with groups that are reactive towards isocyanate groups, such as, e.g. polythioether polyols, hydroxyl group-containing polyacetals, polyhydroxy-polycarbonates, hydroxyl group-containing polyester amides or hydroxyl group-containing copolymers of olefinically unsaturated compounds.
- Compounds with groups that are reactive towards isocyanate groups, particularly hydroxyl groups, suitable for the preparation of NCO prepolymers, are, for example, the compounds disclosed by way of example in U.S. Pat. No. 4,218,543, column 7, line 29 to column 9, line 25. During the preparation of NCO prepolymers, these compounds with groups that are reactive towards isocyanate groups are caused to react with simple polyisocyanates of the kind mentioned above by way of example whilst maintaining an NCO excess. The NCO prepolymers generally have an NCO content of 10 to 25, preferably 15 to 22 wt. %. It follows from this that, within the scope of the present invention, the term “NCO prepolymers” and “prepolymers with terminal isocyanate groups” means both the reaction products as such and their mixtures with excess quantities of unreacted starting polyisocyanates which are often also called “semiprepolymers”.
- Polyester polyols of the kind which can be obtained in an inherently known way by reaction of low molecular weight alcohols with polyvalent carboxylic acids such as adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, or the anhydrides of these acids are also suitable, provided that the viscosity of the H-active component does not become too high. A preferred polyol having ester groups is castor oil. In addition, preparations with castor oil, of the kind that may be obtained by dissolution of resins e.g. of aldehyde ketone resins, and modifications of castor oil and polyols based on other natural oils are also suitable.
- Relatively high molecular weight polyhydroxy polyethers in which high molecular weight polyadducts and polycondensates or polymers are present in the fine particle, dissolved or grafted form are also suitable. Such modified polyhydroxyl compounds are obtained, e.g., if polyaddition reactions (e.g. reactions between polyisocyanates and amino-functional compounds) or polycondensation reactions (e.g. between formaldehyde and phenols and/or amines) are allowed to take place in situ in the compounds containing hydroxyl groups. Such processes are described, for example, in DE-AS 1 168 075 and 1 280 142 and DE-A 2 324 134, 2 423 984, 2 512 385, 2 513 815, 2 550 796, 2 550 797, 2 550 833, 2 550 882, 2 633 293 and 2 639 254. According to U.S. Pat. No. 3,869,413 and DE-A-2 550 860, it is also possible, however, to mix a finished aqueous polymer dispersion with a polyhydroxyl compound and then to remove the water from the mixture.
- Polyhydroxyl compounds modified by vinyl polymers, of the kind obtained e.g. by polymerisation of styrene and acrylonitrile in the presence of polyethers (U.S. Pat. Nos. 3,383,351, 3,304,273, 3,523,093, 3,110,695; DE-A-1 152 5369) or polycarbonate polyols (DE-PS 1 769 795; U.S. Pat. No. 3,637,909) are also suitable for the preparation of polyurethanes. If polyether polyols which were modified according to DE-A-2 442 101, 2 844 922 and 2 646 141 by graft polymerisation with vinyl phosphonic acid esters and optionally (meth)acrylonitrile, (meth)acrylamide or OH-functional (meth)acrylic acid esters are used, plastics with particular flame resistance are obtained.
- Representatives of the above-mentioned compounds to be used as H-active compounds are described, e.g., in High Polymers, Vol. XVI, “Polyurethanes Chemistry and Technology”, edited by Saunders-Frisch, Interscience Publishers, New York, London, Volume 1, 1982, pages 32 to 42 and pages 44 to 54 and Volume II, 1984, pages 5 to 6 and 198 to 199, and in Kunststoff-Handbuch, Volume VII, Carl Hanser Verlag, Munich, 1983, e.g. on pages 45 to 61.
- Of course, mixtures of the compounds listed may also be used.
- The limit of the average OH number and average functionality of the H-active component is established in particular by the increasing embrittlement of the resulting polyurethane. In principle, however, the expert is familiar with the potential influences on the physical polymer properties of the polyurethane, so NCO component, aliphatic diol and polyol may be matched to one another in a favourable manner.
- All inherently known auxiliaries and additives such as, e.g. release agents, blowing agents, fillers, catalysts and flame retardants may be used.
- In the event that foamed materials are to be prepared, the reaction mixture may be introduced into a mold in an inherently known way. The expandable reaction mixture foams in the mold and forms the molded part. Form molding may be carried out in such a way that the molded part has a cellular structure on its surface. It may also, however, be carried out in such a way that the molded part has a compact skin and a cellular core (integral foams). Polyurethane foams may also be prepared as slabstock foam.
- The preparation of polyurethane composite parts in a sandwich construction is also preferred. The process may be designed both as a sandwich or envelope process. Both the sandwich construction and the envelope construction are inherently known. In the sandwich process (filled structure), two half-shells (e.g. outer layers of plastics) are prepared beforehand, placed in a mold and the cavity between the shells is foamed with the PUR foam. In the envelope construction, a core of PUR foam is placed in a mold and then enveloped with a suitable envelope material, e.g. with one of the above-mentioned thermoplastics. The envelope construction is preferred for the preparation of sandwich composite parts.
- Thermoplastic polyurethanes according to the present invention are reaction products of diisocyanates, wholly or predominantly aliphatic oligo- and/or polyesters and/or -ethers, and one or more chain extenders. These thermoplastic polyurethanes are essentially linear and have thermoplastic processing characteristics.
- The thermoplastic polyurethanes are either well known or may be prepared by known processes (see, for example, U.S. Pat. No. 3,214,411, J. H. Saunders and K. C. Frisch, “Polyurethanes, Chemistry and Technology”, vol. II, pages 299 to 451, Interscience Publishers, New York, 1964 and Mobay Chemical Corporation, “A Processing Handbook for Texin Urethane Elastoplastic Materials”, Pittsburgh, Pa.).
- Starting materials for the preparation of oligoesters and polyesters are, for example, adipic acid, succinic acid, suberic acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid and isophthalic acid.
- Adipic acid is preferred in this case.
- Suitable glycols for the preparation of oligoesters and polyesters are, for example, ethylene glycol, 1,2- and 1,3-propylene glycol, butane-1,2-, 1,3-, 1,4-, 2,3-, 2,4-diol, hexane diol, bishydroxymethylcyclohexane, diethylene glycol and 2,2-dimethylpropylene glycol. Moreover, small quantities of up to 1 mole-% of trifunctional or higher functionality alcohols e.g. trimethylol propane, glycerol, hexane triol etc. may be used together with the glycols.
- The resulting hydroxyl oligoesters or polyesters have a molecular weight of at least 600, a hydroxyl number of about 25 to 190, preferably about 40 to 150, an acid value of about 0.5 to 2 and a water content of about 0.01 to 0.2%.
- Oligoesters and polyesters are also oligomeric or polymeric lactones, such as, for example, oligocaprolactone or polycaprolactone, and aliphatic polycarbonates such as, for example, polybutane diol-(1,4-)-carbonate or polyhexane diol-(1,6)-carbonate.
- A particularly suitable oligoradical which may be used as a starting material for the thermoplastic polyurethanes is prepared from adipic acid and a glycol which has at least one primary hydroxyl group. Condensation is ended when an acid value of 10, preferably about 0.5 to 2 is reached. The water produced during the reaction is thus separated at the same time or afterwards so that the water content at the end lies in the region of approximately 0.01 to 0.05%, preferably 0.01 to 0.02.
- Oligoethers and polyethers for the preparation of the thermoplastic polyurethanes according to component B are, for example, those based on tetramethylene glycol, propylene glycol and ethylene glycol.
- Polyacetals are also to be understood as polyethers and may be used as such.
- The oligoethers and polyethers should have an average molecular weight n (number-average, determined by way of the OH number of the products) of 600 to 2,000, preferably 1,000 to 2,000.
- The organic diisocyanate used for the preparation of the polyurethanes according to component B is preferably 4,4′-diphenylmethane diisocyanate. It should contain less than 5% of 2,4′-diphenylmethane diisocyanate and less than 2% of the dimer of diphenylmethane diisocyanate. It is also desirable that the acidity, calculated as HCl, be in the region of about 0.005 to 0.2%. The acidity, calculated as HCl, is determined by extraction of chloride from the isocyanate in hot, aqueous methanol solution or by liberation of the chloride on hydrolysis with water and titration of the extract with standard silver nitrate solution in order to obtain the chloride ion concentration present therein.
- Other diisocyanates may also be used for the preparation of the thermoplastic polyurethanes according to component B, for example, the diisocyanates of ethylene, ethylidene, propylene, butylene, cyclopentylene-1,3, cyclohexylene-1,4,cyclohexylene-1,2, 2,4-toluene, 2,6-toluene, p-phenylene, n-phenylene, xylene, 1,4-naphthylene, 1,5-naphthylene, 4,4′-diphenylene, 2,2-diphenylpropane-4,4′-diisocyanate, azobenzene-4,4′-diisocyanate, diphenylsulfone-4,4′-diisocyanate, dichlorohexane methylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1-chlorobenzene-2,4-diisocyanate, furfuryl diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and bis(-isocyanatophenyl) ethers of ethylene glycol, butane diol, etc.
- Chain extenders that may be used are organic difunctional compounds containing active hydrogen that is reactive with isocyanates, e.g. diols, hydroxycarboxylic acids, dicarboxylic acids, diamines and alkanolamines and water. Such compounds, include, for example, ethylene-, propylene-, butylene glycol, butane-1,4-diol, butane diol, butyne diol, xylylene glycol, amylene glycol, 1,4-phenylene-bis-β-hydroxyethylether, 1,3-phenylene-bis-β-hydroxyethylether, bis-(hydroxymethyl cyclohexane), hexane diol, adipic acid, hydroxycaproic acid, thiodiglycol, ethylene diamine-, propylene-, butylene-, hexamethylene-, cyclohexylene-, phenylene-, toluene-, xylylene diamine, diaminodicyclohexylmethane, isophorone diamine, 3,3′-dichlorobenzidine, 3,3′-dinitrobenzidine, ethanolamine, aminopropyl alcohol, 2,2-dimethylpropanolamine, 3-aminocyclohexyl alcohol and p-aminobenzyl alcohol. The molar ratio of oligoester or polyesters to difunctional chain extenders is from 1:1 to 1:50, preferably 1:2 to 1:30.
- Apart from difunctional chain extenders, trifunctional or more than trifunctional chain extenders may also be used in minor quantities up to about 5 mole-%, based on moles of difunctional chain extenders used.
- Such trifunctional or more than trifunctional chain extenders are, for example, glycerol, trimethylol propane, hexane triol, pentaerythritol, and triethanolamine.
- Monofunctional components, for example, butanol, may also be used for the preparation of the thermoplastic polyurethanes according to component B.
- The diisocyanates, oligoesters, polyesters, polyethers, chain extenders and monofunctional components mentioned as building blocks for the thermoplastic polyurethanes are either known from the literature or may be obtained according to processes known from the literature.
- The well known preparation of polyurethanes may be carried out, for example, as follows:
- For example, the oligoesters and polyesters, the organic diisocyanates and the chain extenders may be heated by themselves, preferably to a temperature of about 50 to 220° C. and then mixed. The oligoesters and polyesters are preferably heated individually first, then mixed with the chain extenders and the mixture obtained mixed with the preheated isocyanate.
- The mixing of the starting components for the preparation of the polyurethanes may be carried out with any mechanical stirrer that permits intensive mixing within a short period. If the viscosity of the mixture during stirring should prematurely rise too rapidly, the temperature may either be lowered or a small quantity (0.001 to 0.05 wt. %, based on ester) of citric acid or similar may be added in order to reduce the rate of the reaction. Suitable catalysts such as, e.g. tertiary amines, which are mentioned in U.S. Pat. No. 2,729,618, may be used to increase the rate of reaction.
- A1
- Linear polycarbonate based on bisphenol A with a relative solution viscosity of 1.252 measured in CH2Cl2 as solvent at 25° C. and in a concentration of 0.5 g/100 ml.
- A2
- Styrene-acrylonitrile copolymer with a styrene-acrylonitrile ratio of 72:28 and a MFR (melt flow ratio) of 12.5 g/10 min, measured at 23.0° C. and a weight of 3.8 kg.
- A3
- Graft polymer of 40 parts by wt. of a copolymer of styrene and acrylonitrile in a ratio of 73:27 on 60 parts by wt. of a particulate crosslinked polybutadiene rubber (average particle size d50=0.3 μm), prepared by emulsion polymerisation.
- AlO (OH) as polar compound, (Plural 200 from Condea, Hamburg);
- PETS (pentaerythritol tetrastearate) as mold release agent;
- polyurethane foam system: Bayfill 51 IF 02 P from Bayer AG, Leverkusen, Germany.
- The mixing of components A1, A2, A3, PETS and optionally AlO (OH) takes place in a 3 1 internal mixer at temperatures of 220 to 240° C. On an injection molding machine of the Arburg 270 E type, molded parts (sheets) with the dimensions 150×105×3.2 mm are prepared from this mixture at a mass temperature of 260° C., which are then coated in a known way with a conventional commercial polyurethane foam system of the Bayfill 51IF02P type. After the foaming reaction has ended, the test under changing climatic conditions described below is carried out with the composite sheets.
- In order to assess the bond adhesion, a test under changing climatic conditions is carried out in which the composites are exposed to temperatures of −40° C. to +80° C. at a rate of temperature change of 1 K/min. A 4 hour continuous period at the limiting temperatures mentioned in each case and a relative humidity of 80% at T=+80° C. is maintained. After 12 temperature cycles, the bond adhesion between the thermoplastic material and the PU material is measured by applying a force until such time as the bond ruptures. If the bond ruptures in the PU material, the bond adhesion is rated (+). If the composite materials separate before the PU material ruptures, the bond adhesion is rated (−).
TABLE 1 Example A 1 2 Thermoplastic mixture [parts by wt.] (Comparison) A1 58 55.2 52.7 A2 24 22.9 21.8 A3 18 17.1 16.4 A1O (OH) — 4.8 9.1 PETS 0.75 0.75 0.75 PU foam system 51IF02P x x x Thickness of PU foam (mm) 5 5 5 Bond adhesion in test under changing (−) (+) (+) climatic conditions - As the tests according to Table 1 show, the composites according to the invention exhibit excellent bond adhesion.
Claims (11)
Applications Claiming Priority (4)
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DE19746265.0 | 1997-10-20 | ||
DE19746265A DE19746265A1 (en) | 1997-10-20 | 1997-10-20 | Directly bonded composite of different plastic materials, used e.g. in motor industry |
DE19746265 | 1997-10-20 | ||
PCT/EP1998/006373 WO1999020464A1 (en) | 1997-10-20 | 1998-10-07 | Composites consisting of polyurethane and a thermoplastic material containing an inorganic polar additive |
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US20020058716A1 true US20020058716A1 (en) | 2002-05-16 |
US6461732B1 US6461732B1 (en) | 2002-10-08 |
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US09/529,707 Expired - Fee Related US6461732B1 (en) | 1997-10-20 | 1998-10-07 | Composites consisting of polyurethane and a thermoplastic material containing an inorganic polar additive |
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US (1) | US6461732B1 (en) |
EP (1) | EP1024955B1 (en) |
JP (1) | JP4458663B2 (en) |
KR (1) | KR100558231B1 (en) |
CN (1) | CN1138630C (en) |
AU (1) | AU1151399A (en) |
BR (1) | BR9812957A (en) |
CA (1) | CA2307629C (en) |
DE (1) | DE19746265A1 (en) |
RU (1) | RU2205756C2 (en) |
TW (1) | TW530074B (en) |
WO (1) | WO1999020464A1 (en) |
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US5726001A (en) * | 1996-06-12 | 1998-03-10 | Eastman Kodak Company | Composite support for imaging elements comprising an electrically-conductive layer and polyurethane adhesion promoting layer on an energetic surface-treated polymeric film |
-
1997
- 1997-10-20 DE DE19746265A patent/DE19746265A1/en not_active Withdrawn
-
1998
- 1998-10-01 TW TW087116317A patent/TW530074B/en not_active IP Right Cessation
- 1998-10-07 KR KR1020007004165A patent/KR100558231B1/en not_active IP Right Cessation
- 1998-10-07 CN CNB988103494A patent/CN1138630C/en not_active Expired - Fee Related
- 1998-10-07 AU AU11513/99A patent/AU1151399A/en not_active Abandoned
- 1998-10-07 EP EP98954367.3A patent/EP1024955B1/en not_active Expired - Lifetime
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- 1998-10-07 CA CA002307629A patent/CA2307629C/en not_active Expired - Fee Related
- 1998-10-07 WO PCT/EP1998/006373 patent/WO1999020464A1/en active IP Right Grant
- 1998-10-07 RU RU2000112639/04A patent/RU2205756C2/en not_active IP Right Cessation
- 1998-10-07 US US09/529,707 patent/US6461732B1/en not_active Expired - Fee Related
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US20070056451A1 (en) * | 2005-09-15 | 2007-03-15 | Klann Kenneth J | Composite printing die |
US20070144383A1 (en) * | 2005-12-21 | 2007-06-28 | Klann Kenneth J | Composite pad printing plate |
US10138370B2 (en) | 2013-10-18 | 2018-11-27 | Covestro Deutschland Ag | Polycarbonate compositions having improved adhesion to polyurethane layers |
US20170158801A1 (en) * | 2015-12-07 | 2017-06-08 | Covestro Llc | Rigid polyurethane foams suitable for wall insulation |
WO2018046698A1 (en) | 2016-09-09 | 2018-03-15 | Trinseo Europe Gmbh | Multi-layer composite article including a cover layer and a pc/abs layer and methods thereof |
CN116875041A (en) * | 2023-08-24 | 2023-10-13 | 江阴久盛科技有限公司 | Polyurethane composite material and preparation method and application thereof |
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JP2001520136A (en) | 2001-10-30 |
CN1138630C (en) | 2004-02-18 |
KR100558231B1 (en) | 2006-03-10 |
CA2307629A1 (en) | 1999-04-29 |
BR9812957A (en) | 2000-08-08 |
RU2205756C2 (en) | 2003-06-10 |
DE19746265A1 (en) | 1999-04-22 |
AU1151399A (en) | 1999-05-10 |
CA2307629C (en) | 2009-12-15 |
CN1276757A (en) | 2000-12-13 |
US6461732B1 (en) | 2002-10-08 |
EP1024955A1 (en) | 2000-08-09 |
JP4458663B2 (en) | 2010-04-28 |
TW530074B (en) | 2003-05-01 |
KR20010031213A (en) | 2001-04-16 |
WO1999020464A1 (en) | 1999-04-29 |
EP1024955B1 (en) | 2013-08-14 |
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