CA2134244A1 - Fiber-reinforced thermoplastic molding compositions using a modified thermoplastic polyurethane - Google Patents
Fiber-reinforced thermoplastic molding compositions using a modified thermoplastic polyurethaneInfo
- Publication number
- CA2134244A1 CA2134244A1 CA 2134244 CA2134244A CA2134244A1 CA 2134244 A1 CA2134244 A1 CA 2134244A1 CA 2134244 CA2134244 CA 2134244 CA 2134244 A CA2134244 A CA 2134244A CA 2134244 A1 CA2134244 A1 CA 2134244A1
- Authority
- CA
- Canada
- Prior art keywords
- thermoplastic
- percent
- fibers
- copolyester
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 116
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 65
- 238000009757 thermoplastic moulding Methods 0.000 title claims abstract description 27
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 19
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 106
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 95
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 82
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 82
- 239000000835 fiber Substances 0.000 claims abstract description 71
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 46
- 229920002635 polyurethane Polymers 0.000 claims abstract description 36
- 239000004814 polyurethane Substances 0.000 claims abstract description 36
- 125000003118 aryl group Chemical group 0.000 claims abstract description 30
- 239000003365 glass fiber Substances 0.000 claims abstract description 28
- 238000000465 moulding Methods 0.000 claims abstract description 28
- 229920001634 Copolyester Polymers 0.000 claims abstract description 26
- 230000000704 physical effect Effects 0.000 claims abstract description 22
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 133
- 229920000642 polymer Polymers 0.000 claims description 79
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 44
- 238000012545 processing Methods 0.000 claims description 41
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 27
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 25
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 24
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 229920000570 polyether Polymers 0.000 claims description 24
- 229920000728 polyester Polymers 0.000 claims description 22
- 229920006344 thermoplastic copolyester Polymers 0.000 claims description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229920002614 Polyether block amide Polymers 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000002344 surface layer Substances 0.000 claims description 9
- 229920006249 styrenic copolymer Polymers 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 abstract description 10
- 239000000306 component Substances 0.000 description 99
- 239000011521 glass Substances 0.000 description 47
- 238000013329 compounding Methods 0.000 description 39
- 239000004417 polycarbonate Substances 0.000 description 39
- 229920000515 polycarbonate Polymers 0.000 description 37
- 125000004432 carbon atom Chemical group C* 0.000 description 27
- 229920001577 copolymer Polymers 0.000 description 25
- 229920002554 vinyl polymer Polymers 0.000 description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 17
- 150000002334 glycols Chemical class 0.000 description 16
- 239000000543 intermediate Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 16
- 239000002131 composite material Substances 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- 239000007795 chemical reaction product Substances 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 14
- 238000001746 injection moulding Methods 0.000 description 14
- 239000008188 pellet Substances 0.000 description 14
- 150000001991 dicarboxylic acids Chemical class 0.000 description 13
- 239000000155 melt Substances 0.000 description 13
- 229920006324 polyoxymethylene Polymers 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- 125000001931 aliphatic group Chemical group 0.000 description 12
- 229920005862 polyol Polymers 0.000 description 12
- 150000003077 polyols Chemical class 0.000 description 12
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 10
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 10
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 10
- 239000004800 polyvinyl chloride Substances 0.000 description 10
- 229930182556 Polyacetal Natural products 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 229920000915 polyvinyl chloride Polymers 0.000 description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 229940043375 1,5-pentanediol Drugs 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 239000004760 aramid Substances 0.000 description 6
- 229920003235 aromatic polyamide Polymers 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 229920002492 poly(sulfone) Polymers 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 150000002596 lactones Chemical class 0.000 description 5
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 5
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 229940035437 1,3-propanediol Drugs 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 4
- 239000004801 Chlorinated PVC Substances 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000004606 Fillers/Extenders Substances 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 4
- 229940090044 injection Drugs 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 229920001748 polybutylene Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 description 4
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920006385 Geon Polymers 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001610 polycaprolactone Polymers 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 229960004063 propylene glycol Drugs 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- WTKWFNIIIXNTDO-UHFFFAOYSA-N 3-isocyanato-5-methyl-2-(trifluoromethyl)furan Chemical compound CC1=CC(N=C=O)=C(C(F)(F)F)O1 WTKWFNIIIXNTDO-UHFFFAOYSA-N 0.000 description 2
- IFWXLHDSWZWYAE-UHFFFAOYSA-N 3-octylhexane-1,6-diol Chemical compound CCCCCCCCC(CCO)CCCO IFWXLHDSWZWYAE-UHFFFAOYSA-N 0.000 description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WXBLLCUINBKULX-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 WXBLLCUINBKULX-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Thermoplastic molding compositions and articles comprise immiscible thermoplastic polymer components and reinforcing fibers. The immiscible thermoplastic polymer components and the fibers are blended together under high shear conditions. The molding composition generally contains at least two phases and has an extremely smooth and fiber-free surface. Generally, other very good physical properties are obtained such as high heat distortion temperatures, high tensile modulus, high flex modulus, and the like are also very good. A desired blend of thermoplastic components is thermoplastic polyurethane and modified polyethylene terephthalate with glass fibers. The molded polyethylene terephthalate copolyester blended with an immiscible thermoplastic polymer, preferably modified polyurethane, and glass fibers produces thermoplastic molding compositions and articles having surprisingly superior impact strength. In addition, if the thermoplastic polyurethane is modified by an aromatic polyester polyol, and blended with a modified polyethylene terephthalate, no fibers are necessary to produce compositions having greatly improved processability.
Description
~3~24~
- "
FIBER-REINFORCED THERMOPLASTIC
MOLDING COMPOSITIONS USING A
MODIFIED THERMOPLASTIC POLYURETHANE
PRIOR HISTORY
FIELD OF THE INVENTION
The present invention relates to thermoplastic molding compositions and more particularly to a blend of generally immiscible thermoplastic matrix polymers includ-ing a copolyester, which can be readily combined with rein-forcing fibers under moderate to high shear to provide a molding composition useful for molding parts substantially free from shrinkage and having very smooth substantially fiber free surfaces and markedly improved impact strength.
BACKGROUND
Thermoplastic polymers combined with glass rein-forcing fibers have been used in the past to produce mold-ing compositions capable of being molded under heat and pressure to form plastic molded parts. Blends of thermo-plastic polymers were often utilized in an effort to over come deficiencies in physical properties of one or both -thermoplastic polymers. The blends related to compatible or miscible polymers wherein the polymers were mutually soluble or one polymer was soluble in the other. If the two desired polymers were not miscible, then a third solu-bilizing polymer was added to provide solubilizing charac-teristics to the two desired polymers and impart compati-bility to the overall polymeric mixture.
In the past, in order to obtain a smooth surface -on molded plastic parts, a two-component injection molding process has been utilized wherein a second polymeric compo-sition was injected and molded over a first fiber rein-~orced polymer to achieve a smooth surface lamina. The two-component molding process, however, is di~ficult to control and operate in that the two separate molding compo-sitions require controlled extruded ratios of the respec-tive polymers, and the like.
- "
FIBER-REINFORCED THERMOPLASTIC
MOLDING COMPOSITIONS USING A
MODIFIED THERMOPLASTIC POLYURETHANE
PRIOR HISTORY
FIELD OF THE INVENTION
The present invention relates to thermoplastic molding compositions and more particularly to a blend of generally immiscible thermoplastic matrix polymers includ-ing a copolyester, which can be readily combined with rein-forcing fibers under moderate to high shear to provide a molding composition useful for molding parts substantially free from shrinkage and having very smooth substantially fiber free surfaces and markedly improved impact strength.
BACKGROUND
Thermoplastic polymers combined with glass rein-forcing fibers have been used in the past to produce mold-ing compositions capable of being molded under heat and pressure to form plastic molded parts. Blends of thermo-plastic polymers were often utilized in an effort to over come deficiencies in physical properties of one or both -thermoplastic polymers. The blends related to compatible or miscible polymers wherein the polymers were mutually soluble or one polymer was soluble in the other. If the two desired polymers were not miscible, then a third solu-bilizing polymer was added to provide solubilizing charac-teristics to the two desired polymers and impart compati-bility to the overall polymeric mixture.
In the past, in order to obtain a smooth surface -on molded plastic parts, a two-component injection molding process has been utilized wherein a second polymeric compo-sition was injected and molded over a first fiber rein-~orced polymer to achieve a smooth surface lamina. The two-component molding process, however, is di~ficult to control and operate in that the two separate molding compo-sitions require controlled extruded ratios of the respec-tive polymers, and the like.
2 ~ ~
U.S. Patent 4,179,479 to Russell P. Carter, Jr.
relates to novel thermoplastic polyurethane materials containing a processing aid. More partiularly, the patent relates to a thermoplastic polyurethane composition com-prising: (A) from ~0 to 100 percent by weight of a thermo-plastic polyurethane, (B~ from 0 to 60 percent by weight of a thermoplastic polymer selected from the group consisting of thermoplastic polycarbonates, thermoplastic polyoxymethylenes, thermoplastic acrylonitrile/butadiene/
styrene graft copolymers, thermoplastic polybutylene terephthalates, thermoplastic polyethylene terephthalates, and mixtures thereof and (C) from o. 5 to 10 percent by weight based on the amount of (A) and (B), of a processing aid which is an acrylic polymer having a number average molecular weight of from 500,000 to 1,500,000.
U.S. Patent No. 4,277,577 to Burg, et al., pro-vides a molding composition of a mixture of an o~ymethylene polymer, an elastomer having a softening temperature of below the crystallite melting point of the oxymethylene polymer and a second order transition temperature of from - ;
120 to +30C., and a segmented thermoplastic copolyester.
U.S. Patent 4,369,~85 to Sanderson, et al., re-lates to reinforced thermoplastic molding compositions comprising polyamides and from 0.1 to 10 percent by weight polyurethanes.
U.S. Patent 4,141,879 to Glenn G. McCarroll re-lates to a thermoplastic material for use under conditions demanding high strength at elevated temperatures, e.g., for under-the-hood automotive or truck components. The materi-al is essentially a three-component alloy of a homopolymer polyamide, a copolymer polyamide, and polyurethane rein-~orced with a relatively small amount of glass ~ibers and containing normal amounts of heat sta~ilizers, ultraviolet screen materials, etc.
IJ.S. Patent No. 4,350,799 to Hans G. Schmelzer, et al., relates to a molding composition comprising an inti-
U.S. Patent 4,179,479 to Russell P. Carter, Jr.
relates to novel thermoplastic polyurethane materials containing a processing aid. More partiularly, the patent relates to a thermoplastic polyurethane composition com-prising: (A) from ~0 to 100 percent by weight of a thermo-plastic polyurethane, (B~ from 0 to 60 percent by weight of a thermoplastic polymer selected from the group consisting of thermoplastic polycarbonates, thermoplastic polyoxymethylenes, thermoplastic acrylonitrile/butadiene/
styrene graft copolymers, thermoplastic polybutylene terephthalates, thermoplastic polyethylene terephthalates, and mixtures thereof and (C) from o. 5 to 10 percent by weight based on the amount of (A) and (B), of a processing aid which is an acrylic polymer having a number average molecular weight of from 500,000 to 1,500,000.
U.S. Patent No. 4,277,577 to Burg, et al., pro-vides a molding composition of a mixture of an o~ymethylene polymer, an elastomer having a softening temperature of below the crystallite melting point of the oxymethylene polymer and a second order transition temperature of from - ;
120 to +30C., and a segmented thermoplastic copolyester.
U.S. Patent 4,369,~85 to Sanderson, et al., re-lates to reinforced thermoplastic molding compositions comprising polyamides and from 0.1 to 10 percent by weight polyurethanes.
U.S. Patent 4,141,879 to Glenn G. McCarroll re-lates to a thermoplastic material for use under conditions demanding high strength at elevated temperatures, e.g., for under-the-hood automotive or truck components. The materi-al is essentially a three-component alloy of a homopolymer polyamide, a copolymer polyamide, and polyurethane rein-~orced with a relatively small amount of glass ~ibers and containing normal amounts of heat sta~ilizers, ultraviolet screen materials, etc.
IJ.S. Patent No. 4,350,799 to Hans G. Schmelzer, et al., relates to a molding composition comprising an inti-
3~24~
mate, well dispersed blend of thermoplastic polyurethane, thermoplastic polyphosphonate and thermoplastic polycarbonate which composition is characterized by an improved level of flame resistance.
Japanese Publication 61149330, dated July 8, 1986, relates to an injection-molded product having a smooth surface which is prepared from a blend containing 10 parts by weight of polypropylene and 90 parts by weight of inor-ganic filled polypropylene. There is little, if any, significant change in physical properties.
Additionally it has been surprisingly discovered that when a modified polyethylene terephthalate (PET), as described hereinbelow, is used instead of unmodi~ied PET, it is possible to use a lower processing temperature so as to essentially eliminate degradation of the other thermo-plastic polymer during compounding or molding. Even more surprising is the unexpectedly superior improvement in the impact strength of the polymers such that the notched and unnotched Izod impact values are two times or greater for formulations incorporating modified PET (M-PET) over formulations with unmodified PET.
SUMMARY OF THE IN~VENTION
Molding compositions of the present invention generally relate to two relatively immiscible thermoplastic polymer components. One such component generally has a relatively high viscosity, and the other component a rela-tively low viscosity at a suitable or desirable processing temperature. At the processing temperature, desirably only minimal degradation, if any, o~ either component occurs.
During processing under usually moderate to high shear conditions, efPective amounts of fibers are added to yield generally a two-phase composition having good adhesion between the components as well as good physical properties such as high heat distortion temperatures, high impact resistance, high tensile modulus, high flexural modulus, and the like, as well as very little shrinkage during
mate, well dispersed blend of thermoplastic polyurethane, thermoplastic polyphosphonate and thermoplastic polycarbonate which composition is characterized by an improved level of flame resistance.
Japanese Publication 61149330, dated July 8, 1986, relates to an injection-molded product having a smooth surface which is prepared from a blend containing 10 parts by weight of polypropylene and 90 parts by weight of inor-ganic filled polypropylene. There is little, if any, significant change in physical properties.
Additionally it has been surprisingly discovered that when a modified polyethylene terephthalate (PET), as described hereinbelow, is used instead of unmodi~ied PET, it is possible to use a lower processing temperature so as to essentially eliminate degradation of the other thermo-plastic polymer during compounding or molding. Even more surprising is the unexpectedly superior improvement in the impact strength of the polymers such that the notched and unnotched Izod impact values are two times or greater for formulations incorporating modified PET (M-PET) over formulations with unmodified PET.
SUMMARY OF THE IN~VENTION
Molding compositions of the present invention generally relate to two relatively immiscible thermoplastic polymer components. One such component generally has a relatively high viscosity, and the other component a rela-tively low viscosity at a suitable or desirable processing temperature. At the processing temperature, desirably only minimal degradation, if any, o~ either component occurs.
During processing under usually moderate to high shear conditions, efPective amounts of fibers are added to yield generally a two-phase composition having good adhesion between the components as well as good physical properties such as high heat distortion temperatures, high impact resistance, high tensile modulus, high flexural modulus, and the like, as well as very little shrinkage during
4 ~ 4 ~
, .
molding. Although the composition contains fibers therein, the surface of the molded article is generally fiber-free and is extremely smooth. When using modified PET as the relatively high viscosity component, both c~mpounders and end users, such as injection moldèrs, obtain the benefit of widening the processing temperature window. Vnexpectedly, the impact strength of the inventive polymers incorporating modified PET is substantially improved over polymers containing unmodified PET. Additionally, it has been surprisingly discovered when using TPU modified with an aromatic polyester polyol along with modi~ied PET, the processability of the composition increases. Moreover, no delamination occurs.
DETAILED DESCRIPTION OF THE INVENTION ~;~
According to the present invention, it has been ~ound that thermoplastic molding compositions having good flow at the processing temperature and typically excellent end-product physical properties can be produced by select-ing relatively immiscible thermoplastic polymers and blend-ing or compounding the same under at least moderate shear conditions with reinforcing fibers, and substantially molding the same under high shear conditions such as in injection molding. Although more than two thermoplastic components can be utilized, with the third or additional component being either immiscible or miscible with either of the ~irst two components but compatible with each of said two components, generally only two such components are required. The remaining portion of the specification shall thus o~ten be limited to a discussion of a two-component immiscible system although it is to be understood that additional components can be utilized. By the term "immis--cible," it i5 meant that there are at least two polymer phases as detected by thermal analysis, thermal mechanical analysis, mi.croscopy, or the like.
The shear required in initially blending the thermoplastic polymer components together during or at the r~l 1 3 ~ 2 4 ~
compounding stage generally i~ at least moderate. That is, only enough shear is required to disperse the fibers and the various immiscible polymers to produce generally a two-phase blend. The compounding shear is carried out at a temperature which is similar or the same as the subsequent processing temperature. By the term "two-phase blend," it is meant that one of the thermoplastic polymer components is generally dispersed within the other compon~nt such that two separate phases exist, or when a third or ~dditional thermoplastic polymer component is utilized possibly three or more separate phases exist. The amount of shear uti-lized in the compounding stage is generally at least 5 reciprocal seconds to about 1,000 reciprocal seconds, desirably at least 50 reciprocal seconds to about 700 or 800 reciprocal seconds, and preferably from about 50 recip-rocal seconds to about 500 reciprocal seconds, or at any suitable shear rate provided that the ~ibers are not unduly broken or reduced in size. The compounded molded composi-tion is generally preformed into any conventional shape such as strands, cubes, particles, pellets and the like so that it can subsequently be utilized in a high shear mold-ing apparatus or operation to yield an end product or article. In the forming of the end product or article, a high shear apparakus i5 utilized such that the shear rate is generally at least lOo reciprocal seconds, desirably at least 500 reciprocal seconds, more desirably at least 800 reciprocal seconds, preferably at least 1,000 reciprocal seconds, up to a value of a~out 3,000 reciprocal seconds.
Another general requirement of the present inven-tion is that the immlscible thermoplastic polymer component desirably has a relatively dissimil~r viscosity at a spe-ci~ic or suitable processing temperature. That is, whenev-Pr the two, or more, relatively immiscible thermoplastic polyn\er cQmponents are blended with each other and fibers, ~5 one component has a relatively low viscosity in somparison with the other, or more, thermoplastic polymer components which have a generally higher viscosity at the processing 3~2~4 or blending temperature. Often the low viscosity thermo-plastic polymer component forms a continuous phase, and the high viscosity thermoplastic polymer component forms a discontinuous phase. The difference between viscosities of the high viscosity component, or at least one of the higher viscosity components when two or more such components exist, to the low viscosity component, is generally a ratio o~ at least 1.5 or 2.0, desirably at least 3.0, and more desirably at least 5.0, and preferably at least 8.0 or 10.0, or even at least 50, at a given processing temper~
ature under generally high shear processing conditions.
Althouyh an upper limit is not always necessary, the upper ratio can be 1,000, or less, particularly when the system uses M-PET and M TPU, for which the upper limit is about 200. Thus, suitable viscosity ranges include any of the above values. Such effective viscosity differences at the processing temperature, along with high shear, contribute to the incorporation of the fibers within the thermoplastic molding compositions and result in a molded article having exceptionally smooth surfaces substantially or essentially and usually completely free of fibers, i.e., at least 95 percent, desirably at least 99 percent, and preferably at least 99.5 percent fiber-free by weight, and usually completely fiber-free.
The end product or article typically ha~ a surface layer which is generally rich in, enriched of, if not en-tirely composed of, the low viscosity component. The surface layer of the thermoplastic molded article, as noted above, .is generally substantially free of fibers with the incorporated fibers thus being located within the interior portlon, i.e., below the surface layer, of the molded article. The thickness of the fiber-free surface layer will depend upon the molding conditions, but generally can vary from ahout 0.5 mils up to about 8--10 mils, ~r even greater, and usually from about 1.0, 2.0 or 3.0 mils to about 5.0 or 7.0 mils. The mechanism by which the fibers are incorporated within the immiscible components is not 3 ~ ~ L' fully understood. Nor is it ~ully understood if a majority of the fibers is incorporated in the relatively high vis-cosity component(s), the low viscosity component, or both, but it is generally thought that the fibers are located in all of the thermoplastic components. In any event, the int~rior portion of the thermoplastic molded article is generally a two-phase portion containing the two immiscible thermoplastic polymer components and khe fibers, although it may contain three or more phases if three or more ther-moplastic polymeric components are utilized with the fi~
bers.
It has been unexpectedly found that when articles or end products of the immiscible thermoplastic polymer components desirably having different viscosities at the processing temperature when blended under high shear condi-tions have fibers incorporated within the interior portion of the article, blend, etc. such that the surface layer is exceptionally smooth. While not fully understood, the utilization of moderate and preferably high shear, desir-ably coupled with relative viscosity differences of the immiscible thermoplastic polymer components at the process-ing temperature to form a thermoplastic molded article, product, etc., unexpectedly yields an article or product having a very smooth surface. The surface smoothness can be measured by a Surtronic Roughness Meter, Model 10, manufactured by Taylor-Hobson. The compositions or blends of the present invention have surface smoothness values of generally 1.0 or 0.9 microns or less, 0.7 microns or less, desirably 0.5 microns or less, preferably 0.4 microns or less, and most preferably 0.3 or 0.02 microns or less are readily obtained. Another advantage of the moldin~ compo-sitions o~ the present invention is that certain molds which have irregular shapes, cavities, nooks, and the like, are readily ~illed, often because the low viscosity compo-nent tends to promote flow.
A requirement of the immiscible thermoplastic com-ponents is that they have minimal, and ~esirably, no degra-~8--dation at the suitable or mean processing temperature.
Stated difEerently, the suitable or typical processing temper~ture is generally below the degradation temperature of all of the polymeric components forming the molding composition. In a TPU/PET system, howeve~, the processing temperature is actually above the degradation temperature of the TPU. It has additionally been discovered that a modified PET having a lower melting temperature, that is, lower than unmodified PET, permits the processing system temperature to be lowered so as to essentially completely avoid degradation of the TPU or other similar relatively higher viscosity polymer with a degradation temperature similar to TPU.
Moreover, it has additionally been discovered that a modified TPU permits greater ease in processability. That is a much lower injection molding pressure is needed when modiPied TPU is used. For example, when modi~ied PET is processed using a Battenfeld 120 ton injection molding machine, the pressure necessary to process the material is 800 psi. In contradistinction, only approximately 400 psi pressure is necessary to process modified TPU. It is believed that the lower processing pressure is due to the increased compatability between the components when modified TPU is used.
Another important requirement is that the various immiscible thermoplastic components, when blended and espe-cially when molded, are mechanically compatible with each other in that they have yood adhesion with respect to one another and to the fibers incorporated therein. Good adhesion is obtained when good physical properties, such as high stiffness and high heat deflection, are achieved.
In yeneral, the molding compositions of the pres-ent invention have very good overall physical properties such as high impact resistance, high tensile modulus, high Elexural modulus, excellent smoothness, very little, i~
any, shrinkage upon molding, arid the like. Unexpectedly it has been discovered that a superior improvement in khe 3~2~
g impact strength of polymers is obtained when the higher viscosity polymer is modified PET. Additionally, it has been discovered that increased compatibility between the immiscible components occurs if the lower viscosity polymer is modi~ied by an aromatic polyester polyol.
The polymers utilized in the present invention which typically meet the above requisites are generally true polymers, that is a large molecule built up by the repetition of small, simple chemical units. In other words, the various polymers utilized can be conventional thermoplastic polymers having conventional molecular weights known to the art as well to the literature. A
preferred class o~ one of the immiscible thermoplastic polymer components are the various thermoplastic polyur-ethanes described hereinbelow with the second immisciblepolymer component being polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polycarbonate, polyacetal, and acrylonitrile-butadiene-styrene type copol-ymers encompassed by the term "ABS". From an overall standpoint, numerous blends of generally two, or more, thermoplastic polymer components can be utilized such as thermoplastic polyurethane, polyethylene terephthalate (PET), polyethylene terephthalateglycol (PETG), polyacetal, polycarbonate, polyvinyl chloride (PVC), copolymers o~
acrylonitrile-butadiene-styrene (ABS), copolymers of esters and ethers, copolymers of styrene and acrylonitrile (SAN), various polyacrylates, poly(phenylene ether), e.g. (PPO), polysul~ones, polybutylene, polyethylene, polypropylene, polystyrene, and the like. Generally, any of at least two of the above-noted types of polymers can be utilized to pro~ide fiber-rein~orced thermoplastic molding compositions of the present invention as long as the two, or more, dif~erent thermoplastic polymers generally have a dissimi-lar viscosity at the processing temperature, are molded under high shear conditions, yield at least a two-phase composition, are not subject to degradation, and have yood adhesion with respect to one another. A more detailed 3~2~
description of the above thermoplastic polymers is now set forth.
Thermoplastic polyurethanes form a desired and often a pre~erred class of polymers. Suitable polyurethanes are prepared by reacting a polyisocyanatP and one or more chain extenders with an intermediate such as a hydroxyl terminated polyester, a hydroxyl terminated polyether, a hydroxyl terminated polycaprolactone, a hy-droxyrl terminated polycarbonate (i.e., a polycarbonate polyol), or mixtures thereof, or amine terminated polyes-ters, polyethers, or polycarbonates, or mixtures thereof.
A preferred class of hydroxyl terminated polyester intermediates is generally a linear polyester having a molecular weight of from about 500 to about 10,000, desir-ably from about 700 to about 5,000, and preferably from about 700 to about 4,200, and an acid number generally less than 0.8 and preferably less than 0.5. The molecular weight is determined by assay of the hydroxyl gr~ups. The polyester intermediates are produced by (1) an esterifi-cation reaction of one or more glycols with one or more dicarboxylic acids or anhydrides, or (2) by transester-ification reaction, i.e., the reaction of one or more glycols with esters of dicarboxylic acids. Mole ratios generally in excess of more than one mole of glycol to acid are preferred so as to obtain linear chains having a pre-ponderance of terminal hydroxyl groups.
The dicarboxylic acids can be aliphatic, cycloaliphatic, aromatic, or combinations thereof. Suit-able dicarboxylic acids which may be used alone or in mixtures usually have a total of from ~ to 15 carbon atoms and include: succinic, glutaric, adipic, pimelic, suberic, aæelaic, sebacic, dodecanoic, isophthalic, terephthalic cyclohaxane dicarboxylic, and the like. Anhydrides of the above dicarboxylic acids, such as phthalic anhydride, tetrahydrophthalic anhydride, or the lilce, can also be utilized, with adipic acid being preferred.
2:~3~
The es~er-forming glycols can be aliphatic, aro-matic, or combinations thereof; have a total of from 2 to 12 carbon atoms; and include: ethylene glycol, propylene-1,2-glycol, 1,3-propanediol, butylene-1,3-glycol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-propane-1,3-diol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and the like, with 1,4-butanediol being a preferred glycol.
In addition to the above polyester intermediates, numerous other types of polyester intermediates known to the art and to the literatures can be utilized including those having diffërent molecular weights and/or contain branch polyesters therein. For example poly caprolactone diols can be u~ed. These are known polyester reaction products o~ lactones and bifunctional compounds having two reactive sites capable of opening the lactone r.ing. These bi~unctional materials may be represented by the formula HX-R-XH wherein R is an organic radical which can be aliphatic, cycloaliphatic, aromatic or heterocyclic and X
is 0, NH and NR where R is a hydrocarbon radical which can be alkyl, aryl, aralkyl and cycloalkyl. Such materials include diols, diamines and aminoalcohols preferablyO
Useful diols include alkylene ylycols wherein the alkylene group contains 2 to lO carbon atoms for example, ethylene glycol, 1,2-propane diol, butanediol-1,4, hexamethylene diol-1,6 and the like~ Ethylene glycol provides excellent polyesters.
The lactones preferred for preparing the polyesters are epsilon-caprolactones having the general formula R R R R R
H c - C - C ~ C - C - C = O
I R R R R
wherQin at least 6 of the R's are hydrogen and the r~mainder are hydrogen or alkyl groups containing 1 to 10 carbon atoms, preferably methyl. Mixtures o~ lactones may 3~24~
be employed to form the polyesters as epsilon-caprolactone and trimethyl-epsilon-caprolactone, 'IT" methyl-epsilon-caprolactone, "~" -methyl-epsilon-caprolactone, dimethyl-epsilon-caprolactone and the like. The lactones are polymerized readily by heating with the bifunctional reactant to a temperature of about 100 to about 200C.
Such polycaprolactone polyols are described in U.S. Patent No. 3,660,357 which is hereby fully incorporated by reference.
It is noted ~hat suitable polycarbonate polyols can also be utilized as an intermediate, and the same, as well as methods of preparation thereof, are disclosed in U.S. Patent No. 4,643,949, which is hereby fully incorporated by reference. Other low molecular weight polycarbonate polyol intermediates can also be made from diols such as those set forth hereinabove, including 1,6-hexanediol, and the like, and phosgene; or by transesterification with low molecular weight carbonates such as diethyl or diphenyl carbonate.
The hydroxyl terminated polyethers can be polyether polyols derived from a diol or polyol having a total of from 2 to 15 carbon atoms, preferably an alkyl diol or glycol which is reacted with an ether comprising an alkylene oxide having from 2 to 6 carbon atoms, typically ethylene oxide or propylene oxide, or mixtures thereof.
For example, hydroxyl functional polyether can be produced by first reacting propylene glycol with propylene oxide followed by subsequent reaction with ethylene oxide.
Primary hydroxyl yroups resulting ~rom ethylene oxide are more reactive than secondary hydroxyl groups and thus are preferred. Useful commercial polyether polyols include poly(ethylene glycol), poly(propylene glycol), poly-(propylene-ethylene glycol), poly (tetramethylene ether glycol) (PTMEG), copolyethers produced from tetrahydrofuran (THF) and ethylene oxide or THF and propylene oxide, glycerol adduct comprising glycerol reacted with propylene oxide, trimethylolpropane adduct comprising trimethylolpro-~ ~4~
-13~
pane reacted with propylene oxide, pentaerythritol adduct comprising pentaerythritol reacted with propylene oxide, and similar hydroxyl functional polyethers. Polyether polyols further include polyamide adducts of an alkylene oxide and can include, for example, ethylenediamine adduct comprising the reaction product of ethylenediamine and propylene oxide, diethylenetriamine adduct comprising the reaction product of diethylenetriamine with propylene oxide, and similar polyamide type polyether polyols. The various polyether interme~iates generally have an average molecular weight, as determined by assay of the terminal functional groups, of from about 500 to about 10,000, desirably from about 500 to about 6,000, more desirably from about 500 to about 4,000, and preferably from about 700 to about 3,000.
In addition to the above polyether type intermedi-ates, other intermediates can be utilized known to those skilled in the art as well as to the literature such as those having different molecular weights, made from differ-ent reactants, and the like.
The above-mentioned polyols can be used alone or in any sombinationO
The intermediate, such as a hydroxyl terminated polyester, a polyether, etc., is further reacted with one or more polyisocyanates and preferably a diisocyanate along with an extender glycol, desirably in a "one-shot" process, that is, a simultaneous coreaction of the intermediate, diisocyanate, and extender glycol, to produce a moderate molecular weight linear polyurethane having a melt index of from about 0 to about 150 and preferably from about 0 to about 75 at 230C at 2,160 grams. The equivalent amount of diisocyanates to the total amount of hydroxyl and/or amine-containing components, that is, the hydroxyl or amine terminated polyester, polyether, etc., and chain extender glycol, is from about 0.95 to about 1.12 or even 1.20, and de3irably from about 0.98 to about 1.06. Alternatively, the urethane can be made in a conventional two-step process t~ .~L 3 ~ ~ t~ t~
wherein initially a prepolymer is made from the polyisocya-nate and the intermediate, with the prepolymt_r subsequently being reacted with the chain extender glycol. The equiva-lent ratio of the one or more diisocyanates to the hydroxyl
, .
molding. Although the composition contains fibers therein, the surface of the molded article is generally fiber-free and is extremely smooth. When using modified PET as the relatively high viscosity component, both c~mpounders and end users, such as injection moldèrs, obtain the benefit of widening the processing temperature window. Vnexpectedly, the impact strength of the inventive polymers incorporating modified PET is substantially improved over polymers containing unmodified PET. Additionally, it has been surprisingly discovered when using TPU modified with an aromatic polyester polyol along with modi~ied PET, the processability of the composition increases. Moreover, no delamination occurs.
DETAILED DESCRIPTION OF THE INVENTION ~;~
According to the present invention, it has been ~ound that thermoplastic molding compositions having good flow at the processing temperature and typically excellent end-product physical properties can be produced by select-ing relatively immiscible thermoplastic polymers and blend-ing or compounding the same under at least moderate shear conditions with reinforcing fibers, and substantially molding the same under high shear conditions such as in injection molding. Although more than two thermoplastic components can be utilized, with the third or additional component being either immiscible or miscible with either of the ~irst two components but compatible with each of said two components, generally only two such components are required. The remaining portion of the specification shall thus o~ten be limited to a discussion of a two-component immiscible system although it is to be understood that additional components can be utilized. By the term "immis--cible," it i5 meant that there are at least two polymer phases as detected by thermal analysis, thermal mechanical analysis, mi.croscopy, or the like.
The shear required in initially blending the thermoplastic polymer components together during or at the r~l 1 3 ~ 2 4 ~
compounding stage generally i~ at least moderate. That is, only enough shear is required to disperse the fibers and the various immiscible polymers to produce generally a two-phase blend. The compounding shear is carried out at a temperature which is similar or the same as the subsequent processing temperature. By the term "two-phase blend," it is meant that one of the thermoplastic polymer components is generally dispersed within the other compon~nt such that two separate phases exist, or when a third or ~dditional thermoplastic polymer component is utilized possibly three or more separate phases exist. The amount of shear uti-lized in the compounding stage is generally at least 5 reciprocal seconds to about 1,000 reciprocal seconds, desirably at least 50 reciprocal seconds to about 700 or 800 reciprocal seconds, and preferably from about 50 recip-rocal seconds to about 500 reciprocal seconds, or at any suitable shear rate provided that the ~ibers are not unduly broken or reduced in size. The compounded molded composi-tion is generally preformed into any conventional shape such as strands, cubes, particles, pellets and the like so that it can subsequently be utilized in a high shear mold-ing apparatus or operation to yield an end product or article. In the forming of the end product or article, a high shear apparakus i5 utilized such that the shear rate is generally at least lOo reciprocal seconds, desirably at least 500 reciprocal seconds, more desirably at least 800 reciprocal seconds, preferably at least 1,000 reciprocal seconds, up to a value of a~out 3,000 reciprocal seconds.
Another general requirement of the present inven-tion is that the immlscible thermoplastic polymer component desirably has a relatively dissimil~r viscosity at a spe-ci~ic or suitable processing temperature. That is, whenev-Pr the two, or more, relatively immiscible thermoplastic polyn\er cQmponents are blended with each other and fibers, ~5 one component has a relatively low viscosity in somparison with the other, or more, thermoplastic polymer components which have a generally higher viscosity at the processing 3~2~4 or blending temperature. Often the low viscosity thermo-plastic polymer component forms a continuous phase, and the high viscosity thermoplastic polymer component forms a discontinuous phase. The difference between viscosities of the high viscosity component, or at least one of the higher viscosity components when two or more such components exist, to the low viscosity component, is generally a ratio o~ at least 1.5 or 2.0, desirably at least 3.0, and more desirably at least 5.0, and preferably at least 8.0 or 10.0, or even at least 50, at a given processing temper~
ature under generally high shear processing conditions.
Althouyh an upper limit is not always necessary, the upper ratio can be 1,000, or less, particularly when the system uses M-PET and M TPU, for which the upper limit is about 200. Thus, suitable viscosity ranges include any of the above values. Such effective viscosity differences at the processing temperature, along with high shear, contribute to the incorporation of the fibers within the thermoplastic molding compositions and result in a molded article having exceptionally smooth surfaces substantially or essentially and usually completely free of fibers, i.e., at least 95 percent, desirably at least 99 percent, and preferably at least 99.5 percent fiber-free by weight, and usually completely fiber-free.
The end product or article typically ha~ a surface layer which is generally rich in, enriched of, if not en-tirely composed of, the low viscosity component. The surface layer of the thermoplastic molded article, as noted above, .is generally substantially free of fibers with the incorporated fibers thus being located within the interior portlon, i.e., below the surface layer, of the molded article. The thickness of the fiber-free surface layer will depend upon the molding conditions, but generally can vary from ahout 0.5 mils up to about 8--10 mils, ~r even greater, and usually from about 1.0, 2.0 or 3.0 mils to about 5.0 or 7.0 mils. The mechanism by which the fibers are incorporated within the immiscible components is not 3 ~ ~ L' fully understood. Nor is it ~ully understood if a majority of the fibers is incorporated in the relatively high vis-cosity component(s), the low viscosity component, or both, but it is generally thought that the fibers are located in all of the thermoplastic components. In any event, the int~rior portion of the thermoplastic molded article is generally a two-phase portion containing the two immiscible thermoplastic polymer components and khe fibers, although it may contain three or more phases if three or more ther-moplastic polymeric components are utilized with the fi~
bers.
It has been unexpectedly found that when articles or end products of the immiscible thermoplastic polymer components desirably having different viscosities at the processing temperature when blended under high shear condi-tions have fibers incorporated within the interior portion of the article, blend, etc. such that the surface layer is exceptionally smooth. While not fully understood, the utilization of moderate and preferably high shear, desir-ably coupled with relative viscosity differences of the immiscible thermoplastic polymer components at the process-ing temperature to form a thermoplastic molded article, product, etc., unexpectedly yields an article or product having a very smooth surface. The surface smoothness can be measured by a Surtronic Roughness Meter, Model 10, manufactured by Taylor-Hobson. The compositions or blends of the present invention have surface smoothness values of generally 1.0 or 0.9 microns or less, 0.7 microns or less, desirably 0.5 microns or less, preferably 0.4 microns or less, and most preferably 0.3 or 0.02 microns or less are readily obtained. Another advantage of the moldin~ compo-sitions o~ the present invention is that certain molds which have irregular shapes, cavities, nooks, and the like, are readily ~illed, often because the low viscosity compo-nent tends to promote flow.
A requirement of the immiscible thermoplastic com-ponents is that they have minimal, and ~esirably, no degra-~8--dation at the suitable or mean processing temperature.
Stated difEerently, the suitable or typical processing temper~ture is generally below the degradation temperature of all of the polymeric components forming the molding composition. In a TPU/PET system, howeve~, the processing temperature is actually above the degradation temperature of the TPU. It has additionally been discovered that a modified PET having a lower melting temperature, that is, lower than unmodified PET, permits the processing system temperature to be lowered so as to essentially completely avoid degradation of the TPU or other similar relatively higher viscosity polymer with a degradation temperature similar to TPU.
Moreover, it has additionally been discovered that a modified TPU permits greater ease in processability. That is a much lower injection molding pressure is needed when modiPied TPU is used. For example, when modi~ied PET is processed using a Battenfeld 120 ton injection molding machine, the pressure necessary to process the material is 800 psi. In contradistinction, only approximately 400 psi pressure is necessary to process modified TPU. It is believed that the lower processing pressure is due to the increased compatability between the components when modified TPU is used.
Another important requirement is that the various immiscible thermoplastic components, when blended and espe-cially when molded, are mechanically compatible with each other in that they have yood adhesion with respect to one another and to the fibers incorporated therein. Good adhesion is obtained when good physical properties, such as high stiffness and high heat deflection, are achieved.
In yeneral, the molding compositions of the pres-ent invention have very good overall physical properties such as high impact resistance, high tensile modulus, high Elexural modulus, excellent smoothness, very little, i~
any, shrinkage upon molding, arid the like. Unexpectedly it has been discovered that a superior improvement in khe 3~2~
g impact strength of polymers is obtained when the higher viscosity polymer is modified PET. Additionally, it has been discovered that increased compatibility between the immiscible components occurs if the lower viscosity polymer is modi~ied by an aromatic polyester polyol.
The polymers utilized in the present invention which typically meet the above requisites are generally true polymers, that is a large molecule built up by the repetition of small, simple chemical units. In other words, the various polymers utilized can be conventional thermoplastic polymers having conventional molecular weights known to the art as well to the literature. A
preferred class o~ one of the immiscible thermoplastic polymer components are the various thermoplastic polyur-ethanes described hereinbelow with the second immisciblepolymer component being polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polycarbonate, polyacetal, and acrylonitrile-butadiene-styrene type copol-ymers encompassed by the term "ABS". From an overall standpoint, numerous blends of generally two, or more, thermoplastic polymer components can be utilized such as thermoplastic polyurethane, polyethylene terephthalate (PET), polyethylene terephthalateglycol (PETG), polyacetal, polycarbonate, polyvinyl chloride (PVC), copolymers o~
acrylonitrile-butadiene-styrene (ABS), copolymers of esters and ethers, copolymers of styrene and acrylonitrile (SAN), various polyacrylates, poly(phenylene ether), e.g. (PPO), polysul~ones, polybutylene, polyethylene, polypropylene, polystyrene, and the like. Generally, any of at least two of the above-noted types of polymers can be utilized to pro~ide fiber-rein~orced thermoplastic molding compositions of the present invention as long as the two, or more, dif~erent thermoplastic polymers generally have a dissimi-lar viscosity at the processing temperature, are molded under high shear conditions, yield at least a two-phase composition, are not subject to degradation, and have yood adhesion with respect to one another. A more detailed 3~2~
description of the above thermoplastic polymers is now set forth.
Thermoplastic polyurethanes form a desired and often a pre~erred class of polymers. Suitable polyurethanes are prepared by reacting a polyisocyanatP and one or more chain extenders with an intermediate such as a hydroxyl terminated polyester, a hydroxyl terminated polyether, a hydroxyl terminated polycaprolactone, a hy-droxyrl terminated polycarbonate (i.e., a polycarbonate polyol), or mixtures thereof, or amine terminated polyes-ters, polyethers, or polycarbonates, or mixtures thereof.
A preferred class of hydroxyl terminated polyester intermediates is generally a linear polyester having a molecular weight of from about 500 to about 10,000, desir-ably from about 700 to about 5,000, and preferably from about 700 to about 4,200, and an acid number generally less than 0.8 and preferably less than 0.5. The molecular weight is determined by assay of the hydroxyl gr~ups. The polyester intermediates are produced by (1) an esterifi-cation reaction of one or more glycols with one or more dicarboxylic acids or anhydrides, or (2) by transester-ification reaction, i.e., the reaction of one or more glycols with esters of dicarboxylic acids. Mole ratios generally in excess of more than one mole of glycol to acid are preferred so as to obtain linear chains having a pre-ponderance of terminal hydroxyl groups.
The dicarboxylic acids can be aliphatic, cycloaliphatic, aromatic, or combinations thereof. Suit-able dicarboxylic acids which may be used alone or in mixtures usually have a total of from ~ to 15 carbon atoms and include: succinic, glutaric, adipic, pimelic, suberic, aæelaic, sebacic, dodecanoic, isophthalic, terephthalic cyclohaxane dicarboxylic, and the like. Anhydrides of the above dicarboxylic acids, such as phthalic anhydride, tetrahydrophthalic anhydride, or the lilce, can also be utilized, with adipic acid being preferred.
2:~3~
The es~er-forming glycols can be aliphatic, aro-matic, or combinations thereof; have a total of from 2 to 12 carbon atoms; and include: ethylene glycol, propylene-1,2-glycol, 1,3-propanediol, butylene-1,3-glycol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-propane-1,3-diol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and the like, with 1,4-butanediol being a preferred glycol.
In addition to the above polyester intermediates, numerous other types of polyester intermediates known to the art and to the literatures can be utilized including those having diffërent molecular weights and/or contain branch polyesters therein. For example poly caprolactone diols can be u~ed. These are known polyester reaction products o~ lactones and bifunctional compounds having two reactive sites capable of opening the lactone r.ing. These bi~unctional materials may be represented by the formula HX-R-XH wherein R is an organic radical which can be aliphatic, cycloaliphatic, aromatic or heterocyclic and X
is 0, NH and NR where R is a hydrocarbon radical which can be alkyl, aryl, aralkyl and cycloalkyl. Such materials include diols, diamines and aminoalcohols preferablyO
Useful diols include alkylene ylycols wherein the alkylene group contains 2 to lO carbon atoms for example, ethylene glycol, 1,2-propane diol, butanediol-1,4, hexamethylene diol-1,6 and the like~ Ethylene glycol provides excellent polyesters.
The lactones preferred for preparing the polyesters are epsilon-caprolactones having the general formula R R R R R
H c - C - C ~ C - C - C = O
I R R R R
wherQin at least 6 of the R's are hydrogen and the r~mainder are hydrogen or alkyl groups containing 1 to 10 carbon atoms, preferably methyl. Mixtures o~ lactones may 3~24~
be employed to form the polyesters as epsilon-caprolactone and trimethyl-epsilon-caprolactone, 'IT" methyl-epsilon-caprolactone, "~" -methyl-epsilon-caprolactone, dimethyl-epsilon-caprolactone and the like. The lactones are polymerized readily by heating with the bifunctional reactant to a temperature of about 100 to about 200C.
Such polycaprolactone polyols are described in U.S. Patent No. 3,660,357 which is hereby fully incorporated by reference.
It is noted ~hat suitable polycarbonate polyols can also be utilized as an intermediate, and the same, as well as methods of preparation thereof, are disclosed in U.S. Patent No. 4,643,949, which is hereby fully incorporated by reference. Other low molecular weight polycarbonate polyol intermediates can also be made from diols such as those set forth hereinabove, including 1,6-hexanediol, and the like, and phosgene; or by transesterification with low molecular weight carbonates such as diethyl or diphenyl carbonate.
The hydroxyl terminated polyethers can be polyether polyols derived from a diol or polyol having a total of from 2 to 15 carbon atoms, preferably an alkyl diol or glycol which is reacted with an ether comprising an alkylene oxide having from 2 to 6 carbon atoms, typically ethylene oxide or propylene oxide, or mixtures thereof.
For example, hydroxyl functional polyether can be produced by first reacting propylene glycol with propylene oxide followed by subsequent reaction with ethylene oxide.
Primary hydroxyl yroups resulting ~rom ethylene oxide are more reactive than secondary hydroxyl groups and thus are preferred. Useful commercial polyether polyols include poly(ethylene glycol), poly(propylene glycol), poly-(propylene-ethylene glycol), poly (tetramethylene ether glycol) (PTMEG), copolyethers produced from tetrahydrofuran (THF) and ethylene oxide or THF and propylene oxide, glycerol adduct comprising glycerol reacted with propylene oxide, trimethylolpropane adduct comprising trimethylolpro-~ ~4~
-13~
pane reacted with propylene oxide, pentaerythritol adduct comprising pentaerythritol reacted with propylene oxide, and similar hydroxyl functional polyethers. Polyether polyols further include polyamide adducts of an alkylene oxide and can include, for example, ethylenediamine adduct comprising the reaction product of ethylenediamine and propylene oxide, diethylenetriamine adduct comprising the reaction product of diethylenetriamine with propylene oxide, and similar polyamide type polyether polyols. The various polyether interme~iates generally have an average molecular weight, as determined by assay of the terminal functional groups, of from about 500 to about 10,000, desirably from about 500 to about 6,000, more desirably from about 500 to about 4,000, and preferably from about 700 to about 3,000.
In addition to the above polyether type intermedi-ates, other intermediates can be utilized known to those skilled in the art as well as to the literature such as those having different molecular weights, made from differ-ent reactants, and the like.
The above-mentioned polyols can be used alone or in any sombinationO
The intermediate, such as a hydroxyl terminated polyester, a polyether, etc., is further reacted with one or more polyisocyanates and preferably a diisocyanate along with an extender glycol, desirably in a "one-shot" process, that is, a simultaneous coreaction of the intermediate, diisocyanate, and extender glycol, to produce a moderate molecular weight linear polyurethane having a melt index of from about 0 to about 150 and preferably from about 0 to about 75 at 230C at 2,160 grams. The equivalent amount of diisocyanates to the total amount of hydroxyl and/or amine-containing components, that is, the hydroxyl or amine terminated polyester, polyether, etc., and chain extender glycol, is from about 0.95 to about 1.12 or even 1.20, and de3irably from about 0.98 to about 1.06. Alternatively, the urethane can be made in a conventional two-step process t~ .~L 3 ~ ~ t~ t~
wherein initially a prepolymer is made from the polyisocya-nate and the intermediate, with the prepolymt_r subsequently being reacted with the chain extender glycol. The equiva-lent ratio of the one or more diisocyanates to the hydroxyl
5 or amine terminated intermediate is generally a sufficient amount such that upon subsequent chain extension with a suitable glycol, the overall equivalent ratio of the hy-droxyl or amine terminated compounds to the one or more polyisocyanates is approximately 0.95 to about 1.06, and the like. Often it can be an excess such as up to about 1.20 or less, or 1.15 or less. Suitable diisocyanates include non-hindered aromatic diisocyanates such as: 4,4'-methylenebis-(phenyl isocyanate) (MDI~; isophorone diiso-cyanate (IPDI), m-xylylene diisocyanate (XDI), as well as non-hindered cyclic aliphatic diisocyanates such as 1,4-cyclohexyl diisocyanate (CHDI), decane-1,10-diisocyanate, phenylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, diphenylmethane-3,3'-dimethoxy-4,4'-diisocyanate, dicyclo-hexylmethane-4,4'-diisocyanate, and cyclohexyl-1,4-diisoc-yanate, as well as combinations thereof. The. most pre-ferred non-hindered diisocyanate is 4,4'-methylenebis-(phenyl isocyanate) i.e., MDI.
Suitable extender glycols (i.e., chain extenders) are saturated low molecular weight glycols, preferably aliphatic, and in particular, alkylene glycols containing ~rom 2 to about 1~ carbon atoms. These normally have molecular weights not over about 300. Representative glycols include ethylene glycol, diethylene glycol, propyl-ene glycol, dipropylene glycol, 1,4- butanediol, 1,6-hexanediol, 1,3-butanediol, 1,5-pentanediol, l,qt-cyclohex-ane-dimethanol, hydroquinone di(hydroxyethyl)ether, dieth-ylene glycol, neopentyl glycol and 3-methyl-1,5-pentane-diol, as well as cycloaliphatic and aromatic glycols, and combinations thereof, with 1,4-butanediol btsing preferred.
In the one-shot polymerization process, a simulta-neous reaction occurs between three componPnts: one or more polyol prepolymers, polyisocyanate, and extender glycol.
~3~2~4 The reaction is generally initiated at temperatures above 100C and desirably above 120C. Inasmuch as the reaction is exothermic, the reaction temperature generally increases to about 200c to 280c. Similar reaction temperatures are utilized when the polyurethane is made in a two-step pro-cess.
Examples of the above, as well as other suitablè
thermoplastio polyurethanes which can be utilized, are set ~orth in Vol. 13 of the EncycloPedia of Polvmer Science and Enqinee~n~, John Wiley & Sons, Inc., New York, New York, 1988, pages 243-303, which is hereby fully incorporated by reference.
~ dditionally, it has been discovered that surprising improved processing results and increased compatibility can be obtained when a modified TPU is used.
The modi~ied TPU is any thermoplastic TPU as described above containing an aromatic polyester polyol. The number average molecular weight of the aromatic polyester polyol is about 2,000 to about 20,000. Examples of aromatic polyester polyols include terephthalate based aromatic polyester polyol such as polyethy]ene terephthalate. Other copolyester can be formed from suitable glycols and dicarboxylic acids. Any glycol or diacid which is reactive to form a copolyester can be used. Suitable glycols include aliphatic, cycloaliphatic and aromatic glycols.
Aliphatic glycols include straight or branched chain alkane and alkene diols, including 1,3-propanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 3-methyl-1,5-pentanediol; 2,2-dimethyl-1,3-propanediol; 2-methyl~1,3-propanediol; 3-octyl-1,6-hexanediol; and cyclohexane dimethanol. Aromatics include benzene glycol and ethoxylated bis-phenol A. Polyether glycols such as diethylene g].ycol may also be used. Although less desirable, triols may be u~ed. The preferred glycols are 1,5-pentanediol and 1,6-hexanediol.
Suitable dicarboxylic acids include aliphatic, straight and branched chain diacids, and aromatics. Exem-~` 1 3~L2~
,",..~
-16- .
plary aliphatic diacids include C4 - Cl2 diacids, which c~rbons include the carboxyl groups, such as adipic acid, glutaric acid, sebacic acid, aæelaic acid, succinic acid, and 1,12-dodecanedioic acid. The preferred diacids are glutaric or azaleic acid.
Typically, the aromatic dicarboxylic acids have a molecular weight less than about 500 and are aromatic dicarboxylic acids including isophthalic acid (m-phthalic acid), phthalic acid (o-phthalic acid), t-butyl isophthalic :
acid, 4,4'-dibenzoic acid, 4,4'-substituted dicarboxy :.
compounds with two benzene nuclei such as bis(p-carboxyphenyl)methane, p-oxy(p-carboxyphenyl)benzoic acid, ethylene-bis(p-oxybenzoic acid), 1~5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-sul~onyl dibenzoic acid, and symmetrically substituted derivatives thereof, with substituents such as Cl - C4 alkyl, halo and alkoxy groups. The preferred aromatic dicarboxylic acid is isophthalic acid.
A preferred aromatic polyester polyol is one comprised of polyethylene terephthalate. An example of such a preferred aromatic polyester polyol will have an intrinsic viscosity of about .37, a molecular weight (Mn) of 9200, and a melting point of 255C.
The modified TPU can be made in the one step polymerization process as described above for the polyurethanes. In addition, the two step process may be used to form the modi~ied TPU. The polyurethane can be modified with about 2 to about 20 mole % of the aromatic polyester polyol. Most preferably, the amount of polyol used is from about 5 to about 15 mole %.
Another specific thermoplastic component which can be utiliæed is polyethylene terephthalate (PET), known to the art and to the literature, and yenerally made from the reaction product oP ethylene glycol and dimethyl terephtha-late or by direct esterification between ethylene glycoland terephthalic acid under heat and a high vacuum. More-over, PETG polymers can also be utilized, as known to the r ~ 1 3 ~L 2 ~
art and to the literature, and generally are the reaction products of ethylene glycol, a short-chain glycol other than ethylene glycol, and dimethyl terephthalate or tere- ~i.
phthalic acid. Examples of other polyesters which can be utilized are set forth in Encyclopedia of Pol~r Science and Enqineerina, Vol. 12, John Wiley ~ Sons, Inc., New York, New York, 1988, pages 217-256, which is hereby fully incorporated by reference.
Another use~ul class of thermoplastic polymers are polyacetals, i.e., polyoxymethylene, including homopolymers or copolymers thereof which are known to the art and to the literature. Inasmuch as the homopolymer, which is usually made from formaldehyde, must generally be processed at temperatures below about 185F, copolymers are generally utilized because they have better processing character-istics. Acetal copolymers are made by a reaction between trioxane, a trimer of formaldehyde, and another monomer such as formaldehyde. An example of a commercially avail-able polyacetal copolymer is Celcon, made by Celanese Chemical Company. These and examples of other polyacetals which can be utilized are set forth in the nc~clopedia of PolYmer Science and Engineerinq, Vol. 11, John Wiley &
sons, Inc., New York, New York, 1988, page 286, which is hereby ~ully incorporated by reference, as well as in U.S.
Patent Nos. 3,850,373 and ~,017,558, which are also fully incorporated by reference.
Another thermoplastic component is the various polycarbonates, including those which are known to the art and to the literature. Polycarbonates are generally esters derived from a diol, or preferably a dihydric or polyhydric phenol such as bisphenol A, and carhonic acid, phosgene, and the like~ Polycarbonates generally have a repeating carbonate group, i.e., o O C--O--and generally always have a - ~ radical attached r J 1 3 41 2 ~L ~
to the carbonate group. Polycarbonates are well known and described in many patents and other technical references.
Desirably, the polycarbonate can be characterized by the formula (R1)n (R2)n ~ rt\
_ 0 ~ O~ ~ Z ~(\O~
wherein Z is a single bond, an alkylene or alkylidene radical with 1 to 7 carbon atoms, a cycloalkylene or cyclo-alkylidene radical with 5 to 12 carbon atoms,-O-, -CO-, -SO or SO2-, preferably methylene or isopro-pylidene; R1 and R2 are hydrogen, halogen or an alkylene or alkylidene radical having 1 to 7 carbon atoms; and n equals 0 to 4. Most preferahly, the aromatic polycarbonates useful in the practice of the invention have a melt flow rate range of about 1 to 60 gms/10 min. at 300C, as measured by ASTM D 1238. The most important aromatic polycarbonate which is commercially available from many different sources is the polycarbonate of bis(4 hydroxy-phenyl) 2,2-p~opane, known as bisphenol-A polycarbonate.
These and examples of other polycarbonates which can be utilized are set forth in the EncvcloPedia af Pol~mer Science and_ Engineerin~, Vol. 11, John Wiley & Sons, Inc., New York, New York, 1988, pages 648-718, which is hereby fully incorporated by reference.
Other thermoplastic polymers suitable for use in the present invention are the various ABS type copolymers which are known in the art and to the literature. Such polymers are generally graft copolymers of acrylonitrile, conjugated dienes having from 4 to 8 carbon atoms with butadiene being highly preferred, and a vinyl substituted aromatic having from 8 to about 12 carbon atoms, with styrene being preferred, often referred to as an acrylonitrile-butadiene~styrene copolymer. The amount of the acrylonitrile is generally from about 10 to about 40 percent by weight; the amount of styrene is generally from IL3~2~
--19-- ..
about 20 to about 70 percent by weight; and the amount of butadiene is generally from about 20 to about 60 percent by weight based upon the total weight of the three-component mixture. Although ABS copolymers are generally a mixture of a styrene-acrylon.itrile copolymer and a styrene-acrylo-nitrile grafted polybutadiene rubber, a terpolymer made from acrylonitrile, butadiene, and styrene monomers can also be used. In lieu of butadiene, other conjugated dienes such as isoprene, pentadiene, dimethylbutadiene, di-methyl pentadiene, and the like can also be utilized. Simi-larly, in lieu of styrene, vinyl toluene, alpha methyl vinyl toluene, alpha methyl styrene, and the like can be utilized. Although acrylonitrile is normally always uti-lized, other vinyl cyanides can be utilized such as methac-rylonitrile, ethacrylonitrile, and the like. These andexamples of other ABS type polymers which can be utilized are set ~orth in the Encyclopedia of_Polymer science and Enqineerinq, Vol. 1, John Wiley ~ Sons, Inc., New York, New York, 1985, pages 388-426, which is hereby fully incorpo-rated by reference.
Another thermoplastic polymer component which canbe utilized in the present invention is polyvinyl chloride and the various copolymers thereof which are known to the art and to the literature. Polyvinyl chloride copolymers are generally made from a majority of vinyl chloride mono-mers and a vinyl component monomer. By the term "vinyl component," it is meant a vinyl-type monomer other than vinyl chlor.ide. Such monomers are well known to the art and to the literature and include esters of acrylic acicl wherein the ester portion has from l to 12 carbon atoms, for example, methyl acrylate, ethyl acrylate, butyl acry-late, octyl acrylate, cyanoethyl acrylate, and the like;
vinyl acetate; esters of methacrylic acid wherein the ester /;~
portion has erom l to 12 carbon atoms, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like; styrene and styrene derivatives having a total of from 8 to 15 carbon atoms such as alpha methyl styrene, ~3~124~
~20-vinyl toluene, chlorostyrene; vinyl; naphthalene; diolefins having a total of from 4 to 8 carbon atoms such as butadiene, isoprene, and including halogenated diole~ins such as chloroprene; monoolefins having ~rom 2 to 10 carbon atoms and preferably 2 to 4 carbon atoms; and the like, and mixtures thereof. An amount of vinyl chloride monomer is utilized to produce a copolymer containing at least aboùt 70 percent by weiyht, and preferably from about 80 to about 93 percent by weight of vinyl chloride repeating units therein. The remainder of the copolymer is made up of the one or more above-noted vinyl component monomers, for example, vinyl acetate. Thus, an amount of vinyl component monomer, when utilized to produce a copolymer, is from up to about 30 percent and preferably from about 7 to about 20 percent by weight of vinyl component repeating units there-in. Also included within the definition of the polyvinyl chloride type polymers and copolymers as set forth above are chlorinated polyvinyl chloride polymers (CPVC) and copolymers having a total chlorine content of from about 57 to about 72 percent by weight. These and examples of other polyvinyl chloride type polymers and copolymers which can be utilized are set forth in the Encyclopedia of Polymer Science and Enqineerinq, Vol. 17, John Wiley & Sons, Inc., New York, New York, 1989, pages 295~376, which is hereby fully incorporated by reference.
Another thermoplastic polymer component which can be utilized in the present invention is a polyester-ether polymer which in reality is a copolyetherester block copol-ymer generally comprising one or more riny containing polyester blocks as well as one or more acyclic polyether block~. The polyester block is generally made ~rom an aromatic containing dicarboxylic acid or diester such as terephthalic acid, dimethyl terephthalate, and the like, with a diol generally containing from about 2 to about 10 carbon atoms. The acyclic polyether is generally made ~rom polyalkylene oxide glycols having a total of from about 3 to about 12 atoms including up to about 3 or ~ oxygen atoms ~ L 3 ~
with remaining atoms being hydrocarbon atoms. The polyes-ter-ether polymers can be represented by the following formula:
-(ring containing polyester-b-acyclic polyether) n.
Such polyester-ether copolymers are commercially available such as Hytrel, manufactured by DuPont, and the like, w~th polybutyleneterephthalate-b-poly(oxytetramethylen~) block copolymer being preferred. These and other examples of other polyester-ether copolymers which can be utilized are set forth in the EncYclopedia of Pol~mer ~cience and Enqi-neering, Vol. 12, John Wiley & Sons, Inc., NY, NY, ~98~, pages 49 52, which is hereby fully incorporated by refer-ence as well as U.S. Patent Nos. 2,623,031; 3,651,014;
3,763,109; and 3,896,078.
Another thermoplastic polymer component which can be utilized in the present invention is copolymers of generally styrene and acrylonitrile, typically known as SAN, that is, styrene-acrylonitrile copolymers. Such copolymers can generally be produced by either emulsion, suspension, or continuous mass polymerization, and usually are made from a majority, by weight, of styrene monomers.
Comonomers other than styrene which can be utilized include vinvl acetate, methyl acrylate, and vinyl chloride. These and a further detailed description of SAN type polymers in general are set forth in the Encyclopnedia_of Polymer sci-ence and Enqineering, Vol. 1, John Wiley & Sons, Inc., New York, New York, 1985, pages 452-470, which is hereby fully incorporated by reference.
Another thermoplastic polymer component which can be utilized in the present invention are the various esters of acrylic or methacrylic acid where the ester portion is typically an alkyl containing from 1 to about 16 carbon atoms, a secondary branched-chain alkyl ester containing from 3 to about 10 carbon atoms, an ester of an olefinic alcohol containing from 3 to about 8 carbon atoms, an aminoalkyl ester containing from about 3 to about 10 carbon 2134~
atoms, an ester of ether alcohols containing from about 2 to about 10 carbon atoms, a cycloalkyl ester containing from about 4 to about 12 carbon atoms, or a glycol diacryl-ate containing from about 2 to about lo carbon atoms, and the like. very often, copolymers of various acrylates and blends thereof can be utilized. Examples of common, com-mercially available, acrylates include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylat~, 2-ethylhexyl acrylate, and the like. Examples of the various methacrylates include methyl methacrylate, ethyl methacry~
late, n-butyl methacrylate, isodecyl methacrylate, stearyl methacrylate, and the like. These and examples of other acrylate or methacrylate esters which can be utilized are set forth in the Encyclopedia of Polvmer scien~e and Enqineerin~, Vol. 1, John Wiley & Sons, Inc., New York, New York, 1985, pages 234-325, which is hereby fully incorpo-rated by reference.
Another thermoplastic which can be utilized in the present invention is poly(phenylene ether). The most important polymer which can be utilized is poly(2,6-dimeth-yl-1,4-phenylene ether). Other polymers include poly(2,6-diphenyl-1,4-phenylene ether), poly(2-methyl-6-phenylphen-ol), as well as copolymers of 2,6-dimethylphenol and 2,6-diphenylphenol. Blends of polystyrene with poly(phenylene ether) can also be utilized. These and examples of other -poly(phenylene ether) compounds which can be utilized are set forth in the Encyclopedia of Polymer Science and En~i-neering, Vol. 13, John Wiley & Sons, Inc., NY~ NY, 1988, pages 1 through 30, which is hereby fully incorporated by reference.
The polysulfones constitute yet another class of thermoplastic polymer components which can be utilized in the present invention. Polysulfones are generally classi-fied as high molecular weight polymers containing sulfone groups and aromatic nuclei in the main polymer chain. The term "polysulfone" also denotes a class of polymers pre-pared by radical-induced copolymerization of olefins and ~ " ~ A
~ :~ 3 ~ 4 sulfur dioxide. Polysulfones are generally clear, rigid, tough thermoplastics with generally high glass transition temperatures, i.e., 180C to about 250C, with a chain rigidity generally being derived from the relatively in-flexible and immobile phenyl and S02 groups. Examples ofvarious polysulfones include bisphenol A polysulfone, polyarylethersulfone, polyethersulfone, polyphenylsulfone, and the like. These and other examples of polysulfones which can be utilized in the present invention are set forth in the Encyclopedia of Polymer Science and Enqineer-~, Vol. 13, John Wiley & Sons, Ins., New York, New York, 1988, pages 196-2~1, which is hereby fully incorporated by reference.
The various polybutylene polymers can also be utilized in the present invention and are derived essen-tially from high molecular weight, predominantly isotactic poly(1-butene) homopolymers or copolymers. These as well as other examples of various polybutylene polymers which can be utilized in the present invention are set forth in the Encyclopedia of Polymer Science and Enqineerinq, Vol.
2, John Wiley & Sons, Inc., New York, New York, lg85, pages 590-605, which is hereby fully incorporated by reference.
Polyethylene, and the various forms thereof, constitutes another class of thermoplastic copolymers which can be utilized with another thermoplastic copolymer which is immiscible therewith and, at a specific processing temperature, has a different viscosity therefrom. Examples of various types of polyethylene include linear polyethyl-ene such as ultra low density polyethylene, linear low density polyethylene, high density polyethylene, high molecular weight high density polyethylene, ultra high molecular weight polyethylene, and the various types of branched polyethylenes such as low density polyethylene, and the like. These and examples of other polyethylene polymers which can be utilized are set forth in the Enc~
_lopedia of Polymer Science and Enqineerinq, Vol~ 6, John ~ ~ 3~2~
, Wiley & Sons, Inc., New York, New York, 1986, pages 383-522, which is hereby fully incorporated by reference.
Still another type or class of thermoplastic polymer component which can be utllized in the present invention is the various polypropylene polymers, such as isotactic polypropylene and the like. It is ~o be under-stood that within the classification of polypropylene polymers and polyethylene polymers are the various copoly-mers of ethylene and propylene. A description of various polypropylene polymers can be found in the EncYcloPedia of Polymer Science and Engineerlng, Vol. 13, John Wiley &
Sons, Inc., New York, New York, 1988, pages 464-531, which is hereby fully incorporated by reference.
Another thermoplastic polymer component suitable for use in the present invention is polystyrene, including crystal polystyrene, impact polystyrene, and the like.
Such polymers are known to the art, and examples thereof suitable for use in the present invention are set forth in the Encycloe~dia of Polymer Science and Engineering, Vol.
16, John Wiley & Sons, Inc., New York, New York, 1989, pages 1-246, which is hereby fully incorporated by refer-ence.
In another aspect of the invention, it has been discovered that surprising improved results are obtained when a modified PET is used, particularly in combination with thermoplastic elastomers. The modified polyethylene terephthalate (M-PET) is a random mixed linear thermoplastic copolyester f ormed by the reaction of ethyle.ne glycol, terephthalic acid and at least one other glycol and/or dicarboxylic acid. The ~-PET has an intrinsic viscosity of from about 0.4 to about 1.2 and a melting point lower than unmodified PET (which is about 265C). Desirably the melting point of the M-PET is from about 200C to about 255C, preferably from about 225C to about 250C, and most desirably from about 235C to about 2~8C.
3~2~
Suitable glycols and dicarboxylic acids are any glycol or diacid which is reactive to form a copolyester with PET and interrupts the crystallinity of PET sufficient to lower its melting point. Suitable glycols include aliphatic, cycloaliphatic and aromatic glycols. Aliphatic glycols include straight or branched chain alkane and alkene diols, including 1,3-propanediol; 1,~-butanediol;
1,5-pentanediol; 1,6-hexanediol; 3-methyl-1,5-pentanediol;
2,2-dimethyl-1,3-propanediol; 2-methyl-1,3 propanediol; 3-octyl-1,6-hexanediol; and cyclohexane dimethanol. Aromat-ics include benzene glycol and ethoxylated bis-phenol A.
Polyether glycols such as diethylene glycol may also be used. Although less desirable, triols may be used. The preferred glycols are 1,5-pentanediol and 1,6-hexanediol.
Suitable dicarboxylic acids include aliphatic, straight and branched chain diacids, and aromatics. Exem-plary aliphatic diacids include C~ - C12 diacids, which carbons include the carboyl groups, such as adipic acid, glutaric acid, sebacic acid, azelaic acid, succinic acid, and 1,12-dodecanedioic acid. The preferred diacids are glutaric or azaleic acid.
Typically, the aromatic dicarboxylic acids have a molecular weight less than about 500 and are aromatic dicarboxylic acids includiny isophthalic acid (m-phthalic acid), phthalic acid (o-phthalic acid), t butyl isophthalic acid, 4,4'-dibenzoic acid, 4,4'-substituted dicarboxy compounds with two benzene nuclei such as bis(p- ;
carboxyphenyl)methane, p-oxy(p-carboxyphenyl)benzoic acid, ethylene-bis(p-oxybenzoic acid), 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-sulPonyl dibenzoic acid, and symmetrically substituted derivatives thereof, with substituents such as C1 ~ C~
alkyl, halo and alkoxy groups. The preferred aromatic dicarboxylic acid is isophthalic acid.
Dicarboxylic acids may also be used which have at last one side chain extending from them. The side chains can be aliphatic or cycloaliphatic and can contain one or ~1342~
more oxygen atoms as an additional element but at leas two (2) carbon atoms must be present between oxygens. The side chains may also contain one or more double bonds and can be straight or branched chain. Any common aliphatic, cycloal~
iphatic or aromatic dicarboxylic acid may be utilized when substituted with the above-described side chains. The molecular weight of the dicarboxylic acid should not be above about 500 excluding the contribution of the side chain.
Specific examples of suitable long chain acids include substituted succinic acids having alkyl or alkenyl radicals of 8-22 carbon atoms in the ~-position, 2~
dodecyloxy) terephthalic acid, 2-decyl-3-tridecyl succinic acid, 3-decyl-phthalic acid and 1-dodecyl-1,2-cyclohexane dicarboxylic acid.
The term "dicarboxylic acids" as used herein, includes e~uivalents of dicarboxylic acids having two functional carboxyl groups which perform substantially like dicarboxylic acids in reaction with glycols in forming copolyester polymers. These equivalents include esters and ester-forming derivatives, such as acid halides and anhyA
drides. While the molecular weight of the diacids suitable for use herein typically have a molecular weight of less than 500, the eguivalent ester and ester-forming deriva-tives may have molecular weight above 500.
Copolyesters of the invention can be prepared by conventional ester interchange and condensation reactions, as set forth in the Encyclopedia of Pol~mer Science and _qineerinq, Vol. 12, John Wiley & Sons, Inc., NY, NY, 1990 and in U.S. Patent No. 4,223,1~6 and U.S. Patent No.
3,890,279, all of which are incorporated herein by refer-ence.
The amount of glycol, other than ethylene glycol, and/or dicarboxylic acid, other than terephthalic acid, incorporated into the copolyester is an amount sufficient to lower the melting point of an unmodified polyethylene terephthalate, and may vary depending upon the glycol ` ~ 3~2~
..
and/or dicarboxylic acid. Generally, however, an amount of glycol and/or dicarboxylic acid from about 1 to about 20 percent by weight of the total copolyester is suitable.
Preferably, from about 1 to about 10 percent and most desirably from about 2 to about 6 percent of glycol and/or dicarboxylic acid is present.
In a preferred embodiment, the dicarboxylic acid, other than terephthalic acid, is present in an amount of from about 1~ to about 10%, most preferably from about 2%
to about 5%, based upon the total weight of acid present in the copolyester and the glycol, other than ethylene glycol, is present in an amount of from about 1~ to about 8~, most ~;
pre~erably from about 1% to about 4%, based upon the total glycol in the copolyester.
A preferred copolyester is one comprised o~ tere-phthalic acid, ethylene glycol and about 2-5% isophthalic acid, based upon the total weight of acid present. Dieth~
ylene glycol may additionally be present, in an amount of from about 1-4% of the total weight of glycol in the copol-yester. Such a preferred copolyester will have an intrin-sic viscosity of about 0.62 and is commercially available as TRAYTUF~ PET resins from The Goodyear Tire and Rubber Company, Akron, Ohio, U.S.A. Particularly suitable is TRAYTUF~ 6254C PET resin.
In addition to the polymers described hereinabove, particularly polyurethanes and polyester-ether polymers, other thermoplastic elastomers suitable for combination with the M-PET are block styrenic copolymers, polyether block amides (PEBA) and ethylene propylene diene (EPDM) terpolymers.
Suitable block styrenic copolymers are o~ the linear or A-B-A type. Basically, these are triblock polymers consisting of a soft rubber or elastomer midblock and hard thermoplastic polystyrene blocks attached to each end. These polymers ~all inko three basic categories and di~fer primarily in the type of rubber used in the midblock: styrene-butadiene-styrene (S-B-S); styrene-~:~3~2~
, isoprene-styrene (S-I-S); and styrene-ethylene/butylene-styrene (S-EB-S~. Such triblock styrenic copolymers are commercially available from Shell Chemical Company (Texas, U.S.A.) as Kraton~ thermoplastic rubber D series (S-B-S and S-I-S) and G series (S-EB-S). These examples of styrenic block copolymers are set forth in the ncyclo~edia of PolYmer Science and Engineerinq, Vol. 5, John Wiley & Sons, Inc., NY, NY, 1990, pages 416-430, which is hereby fully incorporated by reference.
The polyether block amides (PEBA), generally, have a structure consisting of regular and linear chains of rigid polyamide (nylon) block and flexible polyether blocks with the generalized formula O O
H0-t--C-PA-C-O-PE-0 ~ n~H
wherein PA represents the polyamide block, the PE repre-sents the polyether block, and "n" represents an integer such that the molecular weight of the polymer is between about 20,000 and 50, 000. Such polyether block amide copolymers are commercially available, such as Pebax~
polyether block amide, manufactured by Atochem Inc. (New Jersey, U.S.A.).
To make the ethylene propylene diene (EPDM) terpolymers, most commonly the dienes 5-ethylidene-2-norbornene (ENB); 1,4-hexadiene (HD); and dicyclopentadiene tDCPD) are used. Although the ratios for the monomers widely varies, most polymers contain 40-90 mol % ethylene and 0-~ mol % diene. Such EPDM terpolymers are commercially available such as Nordel~ thermoplastic rubber from DuPont and Vistalon~ by Exxon. These and other examples oP EPDM polymers are set ~orth in the Enc~clopedia of Polymer Science and Enqineerinq, Vol. 6, John Wiley &
Sons, Inc., NY, NY, 1990, pages 522-563, which is hereby fully incorporated by reference.
C
~3~2~
In accordance with the present invention, desir-ably two, or more, of the above~noted types of thermoplas-tic polymer components are selected, which, as noted previ-ously, are generally immiscible with respect to one anoth-er, have relatively different viscosities at a specificprocessing temperature, and generally do not degrade at the processing temperature, are blended under high shear to yield a two-phase or multiple-phase composition having fibers incorporated therein and wherein the two, or more, different thermoplastic polymers have good mechanical com-patibility to every component, that is, mutually good adhesive properties with respect to each component. Unex-pectedly, an extremely smooth surface layer is produced which is substantially and typically free of fibers.
Althouyh a large number of combinations of various specific thermoplastic polymers exist, desirable combinations ac-cording to the above guidelines can be readily determined by one skilled in the art. Thus, fiber reinforced blends of polyvinyl chloride (includiny chlorinated polyvinyl chloride) and polycarbonate can be utilized, fiber rein-forced blends of polyvinyl chloride (including chlorinated polyvinyl chloride) and ABS type copolymers can be uti-lized, as well as fiber reinforced blends, as noted above, wherein one component is polyurethane, and the second component is PET, PETG, polycarbonate, polyacetal, or an ABS copolymer. One skilled in the art will appreciate that it is advantageous to combine the M-PET with polymers having a lower melting point than PET. In other words, it is advantageous to use M-PET, instead of PET, in systems where the processing temperature is actuallv above the degradation temperature of the higher viscosity polymer if PEq' was used. The lower melting M-PET enables the injec-tion molder to operate within a wider processing window when combining a higher viscosity thermoplastic polymer which has a lower melting point than PET, with the M-PET.
I'hus, enhanced physical properties of the thermoplastic physical properties of the thermoplastic polymer due to ~13~
less degradation of the polymer at lower processing temper-atures results also. Such suitable combinations of poly-mers include M-PET combined with a block styrenic copoly-mer, a polyether block amide, an ethylene propylene diene (EPVM) terpolymer, and a thermoplastic polyurethane. It has been surprisingly discovered that when the modified PE~
is mixed with the modified TPU, Applicants obtain increased compatibility between the two immiscible components, and better processing.
Even though two component systems are generally preferred, the present invention also encompasses multi-component compositions having three or more of the above-noted thermoplastic polymer components which are blended under high shear in the presence of fibers. The amount of any thermoplastic polymer component with respect to an immiscible thermoplastic polymer component in a two compo-nent thermoplastic blend according to the preferred embodi-ment o~ the present invention is from about 15 percent to about 85 percent by weight, desirably from about 25 to about 75 percent by weight, and preferably from about ~0 percent to about 60 percent by weight with the remaining component constituting the difference. For systems using M-PET (thermoplastic copolyester), the amount of M-PET
component with respect to the immiscible thermoplastic polymer component is from about 10 percent to about 90 percent by weight, desirably from about 20 percent to about 80 percent, and preferably from about 30 percent to about 70 percent by weight with the remaining component constituting the difference. For systems using m-PET with m-TPU, the m TPU component in the range from about 10 to about 90 percent by weight is preferred. Preferably the range is from about 20 to about 80% by weight. Most pre~erably 30% by weight of mTPU is used with 70% by weight of the mPET.
When more than two thermoplastic polymer components are utilized, the amount of one of the thermoplastic polymer components is within the above ranges ~3~2~
_.~
with the remaining two or more thermoplastic componen-ts constituting the difference, i.e. the total of all components add up to 100 percent by weight Desirably, the remaining two or more components each exist in amounts of at least 15 percent, and desirably at least 20 percent or 25 percent by weight.
In accordance with the present invention, short fibers are added to the thermoplastic immiscible polymer components to provide a fiber~reinforced moldiny composi-tion. The types of organic fibers which can be utilized are limited to those which generally do not melt during blending of the thermoplastic polymer components of the present invention. Examples of such organic fibers include aramid, that is aromatic polyamide fibers, and various aramid hybrides such as aramid/carbon, aramid/carbon/glass, and aramid/glass composites. Generally, any type of inor-ganic fiber can be utilized including those known to the art and to the literature such as glass fibers. Glass fibers, either unsized or, preferably, sized, and particu-larly chopped, i.e., short, glass fibers in lengths of about one-eighth inch to two inches, are preferred where an average length of one-eighth to one-half inch fiber is most preferred. Due to the shear mixing with the matrix poly-mers, especially the viscous immiscible polymer, a majority of the short fibers are broken or sheared into shorter ~ibers whereby said sheared fibers are typically reduced in size to about 0.2 to about 3 millimeters in length. A
common glass fiber which can be utilized is "E" type glass fiber which is substantially free of alkali metal salts and has a tensile strength of about 500,000 psi, a modulus of alasticity of around 10.5 million psi, and a f`iber diameter between about 0.0001 and 0.001 inch. Continuous glass roving can also be utilized and subseguently chopped to a desired length. Smaller glass fibers, known as "S" milled ~ibers, are also commercially available, although the size range is smaller and more narrow, typically between 1/32 and lt8 inch in length. Other suitable inorganic fibers ~:~3~2~
."
include carbon fibers, carbon/glass hybrid fibers, boron fibers, graphite fibers, and the like. Various ceramic fibers can also be utilized such as alumina-silica fibers, alumina fibers, silicon carbide fibers, and the like, as well as various metallic fibers such as aluminum fibers, nickel fibers, steel, e.gO stainless steel fibers, and the like. The length of the non-glass fibers is generally the same as the glass fibers and hence ini.tially can be from about 1~8 inch to about 2 inches in length and more desir-ably have an average length of from about 1/8 to about 1/2inch before shear blending with the various thermoplastic polymer components. The fibers are combined with the two, or more, thermoplastic polymer components on a weight basis of from about 5 percent to about 60 percent, desirably from about 15 percent to about 50 percent, and preferably from about 25 percent to about 45 percent by weight based upon the total weight of the imm.iscible thermoplastic polymer components and the fibers. For systems using M-PET, the fibers are combined with the two, or more, thermoplastic polymer components on a weight basis of from about 5 percent to about 60 percent, desirably from about ~0 percent to about 50 percent, and preferably from about 20 percent to about 40 percent by weight based upon the total weight of the immiscible thermoplastic polymer components and the fibers.
The fiber-reinforced thermoplastic molding compo-sition blend, etc., is made by initially compounding the various ingredients and makiny them into a suitable form or shape for storage and subsequent use, and then processing the same at a suitable temperature to ~orm a moltled article or end product. The compounding step generally entails adcling the two, or more, immiscible thermoplastic compo-nents which are utilized as well as the fibers to a mixing or blending apparatus having at least moderate shear, such as a Banbury, a twin-screw extruder, a Buss Kneader, or the likel and mixing the same until generally a two-phase, or a multiple phase, blend having fibers incorporated therein is 3 L?~ 2 ~ ~
~,~
.
obtained. The mixing temperature is approximately the same as the processing temperature of the molding operation, al-though it can be higher or lower, e.g., by 10F or even 20F. In order to prevent the varioui fibers ~rom undue breakage, which reduces the physical properties of the molded end product, or composition, the fibers are general-ly added after a melt is developed in the blending appar-atus, as toward the end of the compounding process. Shear mixing is continued until the various components are gener-ally dispersed, and overmixing is avoided because it tendsto reduce the fibers to an undesirable short le.ngth. The resulting mixture or blend of thermoplastic polymer compo-nents and fibers is generally cooled to produce a solid mass and then pelletized or otherwise divided into suitable size particles for use in a molding apparatus used to form the final product or composition, i.e. article.
Moreover, it has been unexpectedly found that using the modified TPU in a blend with modified PET, no glass fibers are necessary. Delamination does not occur even if no glass is present.
On an optional basis, minor amounts of other molding additives can be intermixed with the immiscible thermoplastic compounded polymers. For instance, mold release agents can be added to obtain a clean release from the mold platen. Opacifying pigments such as titanium dioxide, or ~iller pigments such as calcium carbonate, talcs, carbon blacks, silicas, clays, and the like, can be added. Colorants such as tinting pigments or organic dyes can be added to provide color to the molded article.
Ordinarily such additives, if utilized, comprise less than about 25 percent, desirably less than 15 percent, and prePerably less than 10 or 5 percent by weight, of the molding composition based on the weight of matrix polymers plus reinforcing fibers. Other additives, such as up ko about 15 percent by weight of Teflon powder, or up to about 2 percent by weight of silicone oil, can be used for compo-sitions for bearings, or up to about 12 percent by weight 2 ~ ~
- ~
of stainless steel fibers can be used for conductivity purposes or for shielding against EMR waves.
The compounded immiscible thermoplastic molding compositions containing fibers incorporated therein, as well as the various optional molding additives, as noted above, are generally molded under high shear conditions.
Thak is, the compounding molding step utilizes a moderatè
to high shear range as from about at least 10, desirahly at least 100, desirably at least 500, etc., reciprocal sec-onds, whereas the actual end product or article formation step such as injection molding generally requires high shear such as a shear rate of at least lO0 or 200, desirably at least 500, more desirably at least ~00, etc., reciprocal seconds. High shear conditions, that is, shear rates of at least 100 reciprocal seconds, are generally required as a practical matter to obtain the unexpectant smooth surface characteristics of the present invention.
Any conventional processing device which typically generates the required high shear processing rates can be utilized. Examples include various injection molding machines including those utilizing a plunger or more preferably a reciprocating screw. As long as suitable high shear conditions are generated to produce smooth surface articles or products of the present invention, various injection blow molding machines, and to a lesser extent various compression molding machines, can also be utilized.
The processing temperature will naturally vary depending upon the type of specific diPferent thermoplastic components which are utilized and usually is from about 200C to about 300C although higher or lower temperatures can be utilized. For example, when a thermoplastic polyur-ethane is blended with a polycarbonate in the presence of glass fibers, the processing temperature can generally range from about 240C to about 260C. Blending of PVC
~5 with polycarbonate and glass fibers can be molded at tem-peratures at from about 225C to about 240C. Yet another example is a blend of a thermoplastic polyurethane, polyac-~13~
.~
etal, and glass fibers which typically can be blended at temperatures of from about 240C to abo~lt 255c. A blend of a thermoplastic urethane, PET, and glass fibers can be blended at temperatures of from about 245C to about 265C.
For a blend using PET, the injection molding proce.ssing window can be widened by using modified PET
instead of unmodified PET. The amount by which the pro-cessing window is widened will vary depending upon the thermoplastic polymer being used with the M-PET. However, generally the window is widened by 20-40F. For example when blending with PET, the window is widened from a range of 490F to 505F using unmodifi~d PET to 465F to 505F
with M-PET. Thus, M~PET allows a lowered processing tem-perature by about 15 to about 20 or 25 degrees.
Once the thermoplastic compositions have been molded in accordance with the various aspects of the pres-ent .invention, e.g. the high shear blending of immiscible thermoplastic components generally having relative di.ffer-ent viscosities at a processing temperature which is below the degradation temperature of the thermoplastic components with fibers, yields a mechanically compatible end product unexpectedly having a smooth surface layer containing essentially one thermoplastic component with an inter:ior portion having two phases and containing the fibers there in, have very high physical properties such as i.mpact resistance, high heat distortion temperatures, high tensile modulus, high flexural modulus, and the like. For example, when a thermoplastic polyurethane is compounded with PET on approximately a 50/50 percent weight basis and the two components contain approximately 25 percent hy weight of ~iber glass therein, the following physical properties are typical: notched Izod impact resistance of 1.0 ft. lbs./
inch or greater, and generally at least 2.0 ft. lbs./inch at room temperature; heat distortion temperatures of at least 200F and generally at least 250F at 26~ psi; a tensile modulus of at least 700,000 psi, generally at least 1,000,000 psi and even at least 1,500,000 psi; and a flex-- ~13~2~L
ural modulus of at least 700,000 psi, and generally at least 1,000,000 psi, and even at least 1,200,000 p5i.
Unexpectedly, by using M-PET with the polyurethane, superi-or improvement in the impact strength of such compositions is obtained such that the notched and unnotched Izod impact values are two times or greater than formulations with unmodified PET. (See Example 9, Table VI below).
In view of the exceptionally good physical proper-ties such as high stiffness (for example, high tensile modulus and high flexural modulus), high heat distortion temperatures, and excellent melt flow, numerous end uses exist. Moreover, with regard to the exceptionally smooth surface achieved, the same can be maintained, or dulled to provide a low sheen, or altered by texturing the mold surface to provide a pebbled grain or other decorative surface. A particularly desirable end use of the molded compositions of the present invention is for housings, fenders, etc., as well as for horizontal surfaces in a vehicle. Thus, the molded article can be an automotive hood, fender, truck, roof, and the like. The molded compo-sitions of the present invention, inasmuch as they can contain surfaces rich in polyurethane, provide excellent paint adhesion with respect to various industrial paint coatings such as polyurethane-based paints, without the need of a primer.
The invention will be better understood by refer-ring to the following illustrative examples.
Example 1 Thermoplastic Urethane/Polycarbonate/Glass Fibers A composite of 35 percent thermoplastic urethane (TPU), i.e., Estane 58137, manufactured by The BFGoodrich Company, which is made Prom a polyester intermediate uti-lizing MDI and 1,4-butane diol; 35 percent polycarbonate, i.e., Dow Calibre 300-22; and 30 percent glass fiber was made on a Werner-Pfleiderer compounding twin-screw extruder. The TPU was characterized by its low viscosity of 7-8 X 102 poise, on a 20/1, L/D, capillary rheom~ter at ~13~2~1~
lO0 sec~1 shear rate and 260C. The polycarbonate was characterized by its high viscosity of 7-9 X 103 poise at 260C. The glass was ~-inch "E" glass.
The TPU and polycarbonate were dried for 2 hours at 100C. Then the TPU and polycarbonate were mixed on the Warner-Pfliecler compounding twin-screw extruder, adding granules of these makerials at the rear port of the extrud-er. Downstream, after these materials were mixed and heated to about 240C, glass was added. Work and mixing continued on the compounding extruder. This composite blend at 260C was extruded through a spaghetti die, cooled in air, and chopped into pellets.
The pellets were dried 2 hours at 105C. The in~ection molding was carried out in a physical property mold. The mold temperature was set at 50C. The melt temperature achieved was 252C. The glass-filled TPU and , glass-filled polycarbonate were made under the same condi-tions.
Physical data are set ~orth in Table, I.
3 ~
~P ~tO
o ~n ~ n) m O m ~ ~ ~
g m ~ ~, O tn ~ E~ O ~ ~ ~
v ~ ~ In a~
~ ~O ~
O ~ 0U ~
.4 O # m ~~U Sm ~r~ o ~ ~ P. ,~ m u u a~ C a\~ ~~ 3 ~
~ ul o ~ o a~ ~ ~ o .c _ o ~
_~ 10 N rl O C ~ D~ ~1~ ~ Ll ~ ~ ~ ul ~ O O
~ ~ ~ ~ 1,,`D ~ oc~ 8 :,, ~ ~ ~ ~
o o o JJ ~ O ~ u~ E ~ ~ ~ a r ~ 3 ~ N ~1 o tu o ~ a~
a~ ~ O Q,~
I ) S o 4 U) a) ¦ ~ 3 r ~ u E~
I u ~ u~ ou) C~ U O
::~ ~ C u~ h~ ~ O a~ a u~
l ~ O Or-l ~1 O O r~ 0 0 S 't:1 ~ O
~n ~ E o o .,~ u~ S~c ~':1 ~P dPr,10 ~ d~ o U Q~ C U
m o . ", . ~ O o s n s ~ ~ o ~ J~ 3 Z ~o ~ s . 0 ~u O t~ I ra V
U) rl ~ O U CL~
u c ~ m ~ n ~ o ~. x Ul o . o ~ ~ U ~ o ~ O C) ~o ~
E~ ~ D~_~ ~ O O n ~I E ~ ~ u E o co o,~ u~
dD dP r~ O ~D t.) ~) O
E~ O O O --I ~I Lrl~1 C $ ~ ~ ~
O ~ o ~ c E t~
~a ~ ~ s O ~ c ~ ~ ~ a 1~ ~ h-~ (a t~ o u~ J (a (a o E ,-1 o ~ ,1 o a) a~
~ ~ J~ Q~ C a~ E ~
t4 n c x u ~0 u~ o o ~ c) u~ E o ~ E
_~ a) lUa u~ ~ ~a h g h r~l h O r ~ ,~ u~ (a ~ ~
O ~D ::1 3 N tJ~ la .c 0 a ~ u~ 41 U
(a E~ h CO ~J (a O .1 ~ (~ ; r~~
E~ ~ la .c ~ ~ la c a) U~ D C ~CI U~ C ~ ~ O
u` ~ '~ E a U a ~ ~ $ c ~ :, ~ D4 U1 (a ~ E-l E O h _I r-l h O _I ~( 1~ E-i s O s~ ~O ~ ~1 ~ Eo E ~;h a O C
~ _I c ~ ~ _l ou X -I u uJ E a-,~
O ~ U O ~ ~ O ~ (a o o~
E ,~ ~ t O u ~ ~ u~ ~-o~ c~ ~ u u n o x~ a~ o-,~ u~ o o ~ ~ .as u ~ ,1 ~a--~ Q N (Ulad~ Ul U~
(d h ~ C ~ UQl O ~I h O
~ v~ c c c'a ~ c o Q' s u s o o U~ E-l W E-l IC a~3 ~ D~ J --I U
3~24~
-39~
Example 2 Vinyl/PolYcarbo~ate~ ass Fiber A composite of 35 percent vinyl compound, i.e., Geon 87241, a polyvlnyl chloride compound manu-factured by The BFGoodrich Company; 35 percent polyca-rbonate, i.e., Dow Calibre 300-22; and 30 percent glass fiber was made on a Warner-Pflieder compounding twin-screw extruder. The vinyl was characterized by its low viscosity of 2-4 X 103 poise, on a 20/1, L/D, capillary rheometer at 100 sec~1 shear rate and 230C.
The polycarbonate .is characterized by its high viscos-ity of 3-5 X 104 poise at 230C. ~he glass fibers were ~-inch "E" glass.
The polycarbonate was dried for 2 hours at 100C; the vinyl WAS not dried ~urther. The vinyl and polycarbonate were then mixed on the Warner-Pflieder compounding twin-screw exkruder, adding granules of these materials at the rear port o~ the extruder.
Downstream, glass fibers were added. Working and mixing continued on the compounding extruder. At 237C, this composite blend was extruded through a spaghetti die, cooled in air, and chopped into pel lets.
A vinyl/glass fiber, at a 70:30 weight ra-tio, was produced under similar conditions. A
~5 polycarbonate/glass fiber control, 70:30 weight ratio, was produced under similar conditions except the melt temperature at the die was 277C.
The pellets were dried 2 hours at 105C.
The injection molding was carried out in a physical property mold at a temperature of 50C. The melt temperature was 229C.
A control compound of vinyl/glass, 70:30 weight ratio, was made under the same conclitions. A
control compound of polycarbonate/glass, 70:30 weight ratio, was made at 271C i~ a compounding extruder.
Physical data are set forth in Table II.
2 ~ 3 ~
--4 ~--h a~ ~: m 3 v ,~
~J 0~ S .C
C ~ m 0 ~ 3 O ~ C -1 S 0 ~ ~ O.ma~
U m ~ o m o C~ ~ S
~ u~ O c~ 4 n~
_I ~ C o ~ O ~ U al C
O '~ ~ F g O ~ ~ V ~ .
~~ dP 00 0 W
dP ~ J ~ D O
O O ~ o t) S~ ~
~: ~ V ~ O c V E
tn ~ Lq D~ o m ~,~ ~ ,a '' O ~D g-~~ ~ U
m ~ ~ ~ o .
~n~ U o ~, Q\ U.
~5 .. o E O OC~ a~ m m C~ e t~ ~ 0 r- ~ ~o ~ J la O o ~~ N ~ ~ ~ J ~ (d ~: ~, ~ E Id S t~' wl ~ U~ J ~ ~ ~ J a) W ~ _~ Ul Oq o c~ 0 ~ ~ ~a o ~1 ~ ~ ~a ~~ o 0 0 ~ ~a ~ _~
.¢ O C rd U O 0~ Id C Ul U~ .C U
E-~ _ ~ ~ EO O N C~ _I h I ~ ~d .1 In .-1 ~1 J C~ ~11 ~ 3 a o N ~ ON ~
w I~ ~ OI II CO Id S h ~ I J h a ~ c~tr N
O 0 ~ C4 ~O V U
O ~ ~ ~- U O ~
o oO~' ~.n o~ d L~ C
m 3, c O ^ N :> O V 0 Cll O a) tU~ C ~ e ~s L --~d nl a~ ~ a~ ~ J' '`-~ ~
a v ~ ~ V ~ D~.a C o C
nl~ d rd ~ 3 m '0~ LO~ rn ~~
U V:~ C ~ O ra E ~, m v o ~
rn Q.~ o o S ,~ I U .~ v rn ~ ~ ~eO a ~ ~ e rn D~ rna 'dl O~ ~ ~ ta o 01 a) Id U ~ U ~ t~ O
C v rn C ~ ~ ~ nl rd nl ~ m ~ S:~ E
v ,~ c ~ ~ o o ~ o o ~ . ~ ~ o 8 1:) U J V Id C4 8 0 .R .I P~ d U
E.U ~t~ o ~ ~a~U L~ r L~ rd n) ~D
tn C tn O ~ S U s U O S S .C r~
al L~ a\ v ~ d nl L, .,1 rd ~ Q ~ND # Q, C~- U ~) E -~
~a Cm ~ s: :~ s L~ n c: o c: ~d ~ ~ V ~ C
~nE~ WE-, ~: 41 ~ ~ ~ V P
~::
~:13~2~
" .
Example 3 Vinyl/Polycarbonate A composite of 35 percent vinyl compound, i.e., Geon 87241, a polyvinyl chloride compound manu-factured by The BFGoodrich Company; 35 pe.rcent polyca-rbonate, i.e., Dow Calibre 300-22; and 30 percent ~lass was made on a Buss Kneader rotating-reciprocat-ing compounding machine. The vinyl compound was char-acterized by its low viscosity 0O5-1.5 x 104 poise, on a 20/1, L/D capillary rheometer at 100 sec~1 shear rate at 210C. The polycarbonate was characterized by its high viscosity, 0.5-1.5 x 105 poise, on a 20/1, L/D
rheometer at 210C. The glass was ~-inch l'E" glass.
The vinyl compound and the polycarbonate were m.ixed on the Buss Kneader. After melting the blend, glass was added through a port on the Buss Kneader and mixe~ into the blend achieving a compound temperature of 210C. This compound was injection molded at 210C into a cold mold (50C) to form a smooth product. The surface roughness was 0.6 microns as measured on a Taylor-Hobson Surtronic 10 roughness gauge. These data show good surface appearance for vinyl/polycarbonate/
glass when compounded on a di~ferent type compounding machine.
Example 4 Vinyl/ABS/Glass A composite of 35 percent vinyl compound, that is, Geon 87241, a polyvinyl chloride compound manu~actured by Th~ BFGoodrich Company; 35 percent ABS, that is, Taitalac 6000, manuPactured by Bolcof;
and 30 percent glass was made on a Buss Kneader com-pounding machine~ The vinyl is characterized by a melt viscosity of 0.5-1.5 x 104 poise on a 20/1, L/D
capillary rheometer at 210C. The ~BS has only a slightly higher viscosity of 1.8 x 104 poise. The glass was ~-inch "E" glass.
3 L~9; 2 ~ 4 The vinyl compound and ~BS were mixed on a Buss Kneader compounding machine. After ~elting the blend, glass was added through a port on the barrel of the Buss Kneader and mixed to a melt temperatur~ of 207~C.
This compound was injection molded at 210C
into a cold mold (50C) to form a plaque with a sur~ace roughness of 0.7 microns as measured on a Taylor-Hobson Surtronic 10 roughness gauge. These data show good surface smoothness for v.inyl/ABS/glass when compounded on a different type compounding machine.
Example 5 Thermoplastic_Urethane/Polyacetal/~lass A composite of 53 percent polyurethan2 (Es-tane 58137), 17 percent polyacetal (Delrin 900), and 30 percent glass ~ibers was made on a Warner-Pflieder compounding twin-screw extruder. The glass was 1/4-inch chopped "E" glass.
The TPU and polyacetal were dried two hours at 100C. Then the TPU and polyacetal were mixed on the Warner-Pflieder compounding twin-screw extruder, adding granules of these materials at the rear extru~
der port. Downstream, after these materials were mixed and heated to about 240C, glass was added.
Work and mixing were continued on the compounding extruder. This composite blend was extruded through a spaghetti die at about 260C, cooled, and chopped into pellets.
The pellets were dried 4 hours at 105C.
The injection molding was carried out in a physical property mold. The mold temperature was set at 45C.
The melt temperature achieved was 250C.
Physical data are set forth in Table III. ~;
3~2~
43- ~:
TABLE III ~:
P~YSICAL PROPERTIES OF TPUl~POLYACETALlGhASS
Surface Sm~othness, Taylor-Hobson Surtronic 10 Gauge 0.2 microns Tensile 5trength, ASTM D638 7800 psi Elongation 8.5 Tensile Modulus 560,000 psi Flexural Strength, ASTM D790 14,700 psi Flexural Modulus 580,000 psi Vicat softening, ASTM D1525B 159C
Heat Deflection Temperature @264 ps.i, ASTM D698 Annealed at 120C 135C
Izod impact, ASTM D638 Unnotched 17.7 ft.lbs/in Notched 2.1 ft.lbs/in ~3~2~ :
This data shows the ability to have an out~
standingly smooth surface with 30 percent glass in this TPU/polyacetal blend and include generally good physical properties.
Exam~le 6 ThermoplaStic Vrethane~
Polyethylene Terephthalate~/Glass A composite of 35 percent thermoplastic urethane (Estane 58137), 35 percent polyethylene ter-ephthalate (recycled bottle resin), and 30 percent glass fiber was made on a laboratory-~ize Warner-Pfli-eder compounding twin-screw extruder. The TPU was characterized by its low viscosity of 7-~ X 1o2 poise, measured on a 20/1, L/D capillary rheometer at 100 sec 1 shear rate and 260C. The PET was characterized by its high viscosity of 6-15 x 103 poise, measured on a 20/1, L/D capillary rheometer at 100 sec~1 shear rate and 260C. The glass was 1/4-inch chopped "E" glass.
The TPU and PET were dried for 2 hours at 2 0 100C . Then the TPU and PET were mixed on a Warner-Pflieder compounding twin-screw extruder, adding gran-ules of these materials at the rear extruder portO
Downstream, after these materials were mixed and heated to about 240C, glass was added. Work and mixing were continued on the compounding extruder. At 260C, this composite blend was extruded through a spaghetti die, cooled in air, and chopped into pellets.
The pellets were dried 2 hours at 105C.
The injection molding was carried out in a physical property mold. The mold temperature was set at 45C.
The melt temperature achieved was 250C. The q.lass-f`illed thermoplastic urethane and glass-filled PET
were made under these same conditions~
Physical data are set ~orth in Table IV.
C
E O a ~
E E~ m u) O O ~
~ 3 ~q O OU) O
~a ~ u~ D. O
~O O ~ 3 _~ ~ o o o ~ ~ ~ 0 v dP dP 3 ~ o ,, o ,, ~ v .~ ~, C~O ~,~ ~ `
r~
E~ ~ lU
D~
a u~ u ~~, ~
E~ .'C E~ ~ o o ~ C~ dP dP dP ~ ~o 1 ~ In Ln O r~) O ,1:: ,r 41 r~ o a~ , ~ O
E-~ ~S ,W :1 1 ~ ¢ @ U~ V~
~1O U, Ul g11) C4 ~ r ~1 O.
^1~ 1~1 ~ ~ ~ ~ O W Q) a :~: E~ ~ '1 ~3 ~
E~ ~1 E~ C~ E ~D ~ W E R
O Z o o t~l ` O ~D tr. u) O _I
~ ~ ~ o,1 _1 u~ E .
~n~ 5~, ~ 3 ~
o o ~, C~V ~
o ~ ~ o o , ~, W ~ .
C 1~ X ~ C W C
.R ~ rl V~
a~ ~ _I S O
~ ~ e J' ~ a ul p --l a v tn w ~
~a w ~ C C C E ~
ul 3 W ~ o --I ~ a~ V I
~ C~ C ~ ~I 0~ Q~V ~ ~~ C
CV u~ C E~ ~1 3 e o n v.,~
.C: O t~ 0 U~ ~d C la r v ~I C ~ 1 ~ V E~ X C ~ 1:: -3 O~ 3 v ~ W ~
E d v C O W ~ C ~o u~ C ~n o X -~ ~ w ~ a o o W ~ ~ W ~ ~ ~Oc~
N C 1` al-rl 3 3 3 0 v~ C ~ O
a) ~ c-,l u~ w 3 u~ 3.Q
2 ~ ~
~4~-Examples 7 and 8 3~-,~
Polvethyl~ne Terephthalake/Glass A composi,e of 35 percent thermoplastic urethane (Estane 58137), 35 percent polyethylene terephthalate (recycled bottle resin), and 30 percent glass was made on a Warner-Pflieder compounding twin-screw extruder. The TPU was characterized by its low viscosity o~ 7-8 X 102 poise, measured on a 20/1, L/D
capillary rheometer at 100 sec~~ shear rate and 260C.
The PET was characteri.zed by its high viscosity of 6 -15 x 103 poise, measured on a 20/1, L/D capillary rheometer at 100 sec~1 shear rate and 260C. The glass was 1/4 inch chopped "E" glass.
The TPU and PET were dried for two hours at 100C. Then the TPU and PET were mixed on the Warner-Pflieder compounding twin-screw extruder, adding gran-ules of these materials at the rear extruder port.
~own stream, after these materials were mixed and heated to about 240C, glass was added. Work and mixing were continued on the compounding extruder.
This composite blend was extruded through an underwater pelletizing die at the end of the extruder, set at about 260C. The knife chopped the strands into pellets at the die face.
The pelle.ts were dried 4 hours at 105C.
The injection molding was carried out in a physical property mold. The mold temperature was set at ~5c.
The melt temperature achieved was 250C. A second similar example was made wherein the TPU was 30 percent weight, the PET was 30 percent weight, and the glass was 40 percent weight. The molded properties are set forth below:
Physical data are set forth .in Table V.
--` 2. 1 3~2/-1~
.
--~7--.,.1 .,~ ~, 0 ~
Gl D. ~ ~ 0 a~ 0 c ,~ 0.a a ~ o o ~1 ~1 ,/ o ~ o ~ . u C6~ 6 8 dP $ $ 8 U
o ~ ~ r O r1 0 -,~ ~
w ~, .,~ , r 0 o 0 o 0~ 0 0 ~ 40 I-,~ ~1 o ~ oo o e ~ E oO g g O U ~ u ¦ X g . r~ N Ir) r ~ O ~ r IY 1~ ~ O ~1 Irl~1 ~ 1N 1~1 C~
:':
O
O X
O O ~ '. `
r al e ~D
o O
~ ~ ~ C ~ , U ,;
o ~ ~, ~ J O a) t~ 0'10~ a) J- +
E~ O ~ E ~
0 1: U~ OE~ , ~ S .~
~ 0 ~ o ~ ~
Crl ~ o w ~ 0 X x ~ C ~ I
U~ C O C ~ O ~\
3~2~
--4fi--As apparent from Table V, fiber-reinforced thermoplastic molding compositions were obtained having extremely high tensile modulus, flexural modulus, heat deflection temperatures, impact resistance, and the like, and yet, the surface was extremely smooth. Inasmuch as the surface is essentially urethane-rich, it is readily paintable without being pr.imed. ..
Examples 9, lo, 11 a.nd 12 TPU/unmodified PET/qlass vs.
lo TPU/modified PET/~lass vs. modified PTU/PET/qlass A composite of thermoplastic polyurethane, polyethylene terephthalate, and glass fiber, in the percentages indicated in Table VI, was made on a pilot scale Werner-Pfleiderer compounding twin screw e.xtruder. The polyurethane was made from a polyester intermediate utilizing MDI and 1,4-butane diol and sold by The BFGoodrich Company as Estane~ 581~2 polyurethane. The TPU was characterized by its low viscosity of 38 poise, measured on a 20/1, L/D
capillary rheometer at 400-500 sec~l shear rate and 250C. For the mTPU used in Comparative Examples lO(a) and 12(a), the polyurethane was modified with Traytuf ~5/200/28 polyethylene terephthalate having a molecular we.ight (Mn) of 9200 and an inherent viscosity of 0.37 as produced by Shell Oil. The polyethylene terephthalate in Examples 9 and 11 was unmodified PET sold by The Goodyear Tire and Rubber Company as TRAYTUF~ 5900C resin. The unmodified PET
was characterized by its hiyh viscosity of 2000 poise, mea~ured on a 20/1, L/D capillary rheometer at 100 sec~1 shear rate and 260C. The PET in Exampl.es 10 and 12 was modi~ied PET, that i5, a random mixed linear copolyester f ormed by the reaction of ethylene glycol, terephthalic acid, 205% (based on total acid) ~5 isophthalic acid and 1-4% (based upon total glycol) diethylene glycol, sold as TRAYTUF~ 6254C resin by The 3l-~2 ., Goodyear Tire and Rubber Company. The modified PET
was characterized by its high viscosity of 2,200 poise, measured on a 20/1, L/D capillary rheometer at 400-500 sec~l shear rate and 270C. The glass was 1/8-inch chopped "E" glass. 0.1-0.3% of carbon black as colorant.
Prior to compounding the TPU and PET were dried for 6 hours at 100C. Then the TPU and PET were mixed on a Werner-Pfleiderer compounding twin-screw extruder, adding granules of thesei materials at the rear extruder port. Downstream, after these ma~erials were mixed and heated to about 240C, glass was added.
Mixing and compounding was continued in the extruder and at 260~C, this composite blend was extruded through a spaghetti die, cooled in air, and chopped into pellets.
The pellets were dried 6 hours at 105C.
The injection molding was carried out in a physical property mold. The mold temperature was set at 45C.
The melt temperature achieved was 250~C.
Physical data are set forth in Table VI.
r ~ 2 4 ~
-50- .
U: _ , _ _ ~ ~
c ~ = ~ E Z~ 1~ ~ 8 ~ .. , ~
~ . . ~ _. . ~
E E E ~ 8 8 ¢ ~ L~ D ~ E ~:^ o o ~ ~ ~ ~ ,~;~
~ ~ __ . - I
~1 D _ ~; E o E, N ~ _.. _.. __ U~ l ~ o ~ l O G l L. ~ 52 C _ ~ _, ~3 ~ 1`~ ' ,, ~ _ __ _ ~
~ ~ ~ ~eo ~ ~ t`'~ '' r~ "';'`
U~ _ ___ _ -- ~..._._ tr: I ~
~ l ~ Q~ 1~ CL
. ~ ~Z~
~. 13 ll2~1 ~
Example 13 The ratio of viscosity of M-PET to TPU was determined for shear rates considered standard for high shear compounding and injection molding. The results are summarized below in Table VII.
- - 2 ~ 3 L~l 2 l~ ~
C ~ , I ~E~
H W ~ OD t`~ ~D
U~ ~ ,1 ~1 ,~
~ U~ ~
~: H
E~ .,,'~
H P~ ~ r c~
:~' ~
~:1 0 H U~
~ ~ 8~
^~ ~ ~1 m o OD 1 U~
~ ,, ~1 .
u ~n ~ o o o ~ U$
~ :~ 3 ~
Examples 14-21 Composite of modified thermoplastic polyurethane, polyethylene terephthalate (modified and unmodified) with and without glass fiber, in the percentages indicated in Tables VIII-XI were made on a pilot scale Werner-Pfleiderer compounding twin screw extruder.
The polyurethane was made from a polyes~er intermediate utilizing MDI and 1,4 butane diol sold by The B.F.Goodrich Co. as ESTANE0 58142 polyurethane.
The TPU is characterized by its low viscosity of 38 poise, measured on a 20/1, C/D capillary rheometer at 400-500 sec 1 shear rate and 250C.
The polyurethane ESTANE~ 58142 polyurethane was modified with TRAYTUF 85/200/~8 polyethylene kerephthalate having a molecular weight (Mn) of 9200, and an inherent viscosity of .37 as produced by the Shell Oil Co.
The polyethylene terephthalate (PET) in the examples was unmodified PET sold by the Shell Oil Co.
as TRAYTUF~ 5900C resin. The unmodified PET was characterized by its high viscosity of 2000 poise, measured on a 20/1 L/D capillary rheometer at 100 sec 1 shear rate and 260C. The random mixed linear copolyester formed by the reaction of ethylene glycol, terephthalic acid, 2056 (based on total acid) isophthalic acid and 1-~% (based upon total glycol) diethylene glycol, sold as TRAYTUF~ 625~C resin by Shell Oil Co. The modified PET was characterized by its high viscosity of 2,200 poise, measured on a 20/1, I./D capillary rheomeker at ~00-500 secl shear rate and 270C. The glass, if added, was 1/8-inch chopped l'E"
ylass. 0.1-0.3% of carbon black was colorant.
Prior to compounding, the TPU and PET were dried for 6 hours at 100C. Then the TPU and PET were mixed on a Werner~Pfleiderer compounding twin-screw extruder, adding granules of these materials at the ~ 3~2~
rear extruder port. Downstream, after these materials were mixed and heated to about 240~C, glass was added. ,~
Mixing and compounding was continued in the extruder and at 260OC, this composi-te blend was extruded through a spaghetti die, cooled in air, and chopped into pellets.
The pellets were dried 6 hours at 105C.
The injection molding was carried out in a physical property mold. The mold temperature was set at 450C.
The melt temperature achieved was 250C~
Physical data are set forth in Tables VIII-XI.
~3~2~
~ r-_ _ ~- = 0~ ~ _ O ~
3 ~ ~ ~_ ~--xl ~ E ~, ~ ~3, _ ~ o . ~33~
= ~
In o u~ o M
~3~2~
_~ -56- ` `
1~ ~T~
~ ~I E ~ 8 ~' o ~ ~ v~ ~ ~^
~ _ x ~ L _ _ _ 9 _~ ' '~ _ L _ _ ~~ ~i ~t _, e o ~- -57- ~ ~3~4 ~ _ . = _ .
~ ~ E ¦ 8 ~ ~ 1` R ~j? ~ ~
~_ -~ _ ___ _l , ~,:
~e " ~ ~ r~ x o t_ ~ o ~3 l E
X ~ E ~ _ _ --~ = ~g~ ~ ~ I
~ ~ ~ ._. _ . .. .___ _ E De i ~ _ _ ....... __ É~ É7 ~: E ' ~ _ A.
1~
U7 o ~ o 2 ~ 4 4 : - 5 8 -_ . _ __ _ ~E 18~ æ ~r~ ~ v~ ~ 0~
~7 C~ I
C~ _ _ U~ I
I
E ~ e I ~} ~ ~o v~ ~3 o 1-E l ~ ;. _ _ _ ,_ ~ _ I
x~ ~ ~1 ~ c ~e I ~ o~ O x ~ ~ ~0 O
.~ E
.~, I
.,.__ _ __ o Xl~ I ~ ~ o~ ~ ~ æ`
~ ~1 ~, I
. - - ~ - - - . .
Ln o Ln C) L 3 L~
;
While in accordance with the Patent Statutes, the best mode and preferred embodiment has been set forth, the scope of the invention is not limited thereto, but rather by the scope of the attached claims.
Suitable extender glycols (i.e., chain extenders) are saturated low molecular weight glycols, preferably aliphatic, and in particular, alkylene glycols containing ~rom 2 to about 1~ carbon atoms. These normally have molecular weights not over about 300. Representative glycols include ethylene glycol, diethylene glycol, propyl-ene glycol, dipropylene glycol, 1,4- butanediol, 1,6-hexanediol, 1,3-butanediol, 1,5-pentanediol, l,qt-cyclohex-ane-dimethanol, hydroquinone di(hydroxyethyl)ether, dieth-ylene glycol, neopentyl glycol and 3-methyl-1,5-pentane-diol, as well as cycloaliphatic and aromatic glycols, and combinations thereof, with 1,4-butanediol btsing preferred.
In the one-shot polymerization process, a simulta-neous reaction occurs between three componPnts: one or more polyol prepolymers, polyisocyanate, and extender glycol.
~3~2~4 The reaction is generally initiated at temperatures above 100C and desirably above 120C. Inasmuch as the reaction is exothermic, the reaction temperature generally increases to about 200c to 280c. Similar reaction temperatures are utilized when the polyurethane is made in a two-step pro-cess.
Examples of the above, as well as other suitablè
thermoplastio polyurethanes which can be utilized, are set ~orth in Vol. 13 of the EncycloPedia of Polvmer Science and Enqinee~n~, John Wiley & Sons, Inc., New York, New York, 1988, pages 243-303, which is hereby fully incorporated by reference.
~ dditionally, it has been discovered that surprising improved processing results and increased compatibility can be obtained when a modified TPU is used.
The modi~ied TPU is any thermoplastic TPU as described above containing an aromatic polyester polyol. The number average molecular weight of the aromatic polyester polyol is about 2,000 to about 20,000. Examples of aromatic polyester polyols include terephthalate based aromatic polyester polyol such as polyethy]ene terephthalate. Other copolyester can be formed from suitable glycols and dicarboxylic acids. Any glycol or diacid which is reactive to form a copolyester can be used. Suitable glycols include aliphatic, cycloaliphatic and aromatic glycols.
Aliphatic glycols include straight or branched chain alkane and alkene diols, including 1,3-propanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 3-methyl-1,5-pentanediol; 2,2-dimethyl-1,3-propanediol; 2-methyl~1,3-propanediol; 3-octyl-1,6-hexanediol; and cyclohexane dimethanol. Aromatics include benzene glycol and ethoxylated bis-phenol A. Polyether glycols such as diethylene g].ycol may also be used. Although less desirable, triols may be u~ed. The preferred glycols are 1,5-pentanediol and 1,6-hexanediol.
Suitable dicarboxylic acids include aliphatic, straight and branched chain diacids, and aromatics. Exem-~` 1 3~L2~
,",..~
-16- .
plary aliphatic diacids include C4 - Cl2 diacids, which c~rbons include the carboxyl groups, such as adipic acid, glutaric acid, sebacic acid, aæelaic acid, succinic acid, and 1,12-dodecanedioic acid. The preferred diacids are glutaric or azaleic acid.
Typically, the aromatic dicarboxylic acids have a molecular weight less than about 500 and are aromatic dicarboxylic acids including isophthalic acid (m-phthalic acid), phthalic acid (o-phthalic acid), t-butyl isophthalic :
acid, 4,4'-dibenzoic acid, 4,4'-substituted dicarboxy :.
compounds with two benzene nuclei such as bis(p-carboxyphenyl)methane, p-oxy(p-carboxyphenyl)benzoic acid, ethylene-bis(p-oxybenzoic acid), 1~5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-sul~onyl dibenzoic acid, and symmetrically substituted derivatives thereof, with substituents such as Cl - C4 alkyl, halo and alkoxy groups. The preferred aromatic dicarboxylic acid is isophthalic acid.
A preferred aromatic polyester polyol is one comprised of polyethylene terephthalate. An example of such a preferred aromatic polyester polyol will have an intrinsic viscosity of about .37, a molecular weight (Mn) of 9200, and a melting point of 255C.
The modified TPU can be made in the one step polymerization process as described above for the polyurethanes. In addition, the two step process may be used to form the modi~ied TPU. The polyurethane can be modified with about 2 to about 20 mole % of the aromatic polyester polyol. Most preferably, the amount of polyol used is from about 5 to about 15 mole %.
Another specific thermoplastic component which can be utiliæed is polyethylene terephthalate (PET), known to the art and to the literature, and yenerally made from the reaction product oP ethylene glycol and dimethyl terephtha-late or by direct esterification between ethylene glycoland terephthalic acid under heat and a high vacuum. More-over, PETG polymers can also be utilized, as known to the r ~ 1 3 ~L 2 ~
art and to the literature, and generally are the reaction products of ethylene glycol, a short-chain glycol other than ethylene glycol, and dimethyl terephthalate or tere- ~i.
phthalic acid. Examples of other polyesters which can be utilized are set forth in Encyclopedia of Pol~r Science and Enqineerina, Vol. 12, John Wiley ~ Sons, Inc., New York, New York, 1988, pages 217-256, which is hereby fully incorporated by reference.
Another use~ul class of thermoplastic polymers are polyacetals, i.e., polyoxymethylene, including homopolymers or copolymers thereof which are known to the art and to the literature. Inasmuch as the homopolymer, which is usually made from formaldehyde, must generally be processed at temperatures below about 185F, copolymers are generally utilized because they have better processing character-istics. Acetal copolymers are made by a reaction between trioxane, a trimer of formaldehyde, and another monomer such as formaldehyde. An example of a commercially avail-able polyacetal copolymer is Celcon, made by Celanese Chemical Company. These and examples of other polyacetals which can be utilized are set forth in the nc~clopedia of PolYmer Science and Engineerinq, Vol. 11, John Wiley &
sons, Inc., New York, New York, 1988, page 286, which is hereby ~ully incorporated by reference, as well as in U.S.
Patent Nos. 3,850,373 and ~,017,558, which are also fully incorporated by reference.
Another thermoplastic component is the various polycarbonates, including those which are known to the art and to the literature. Polycarbonates are generally esters derived from a diol, or preferably a dihydric or polyhydric phenol such as bisphenol A, and carhonic acid, phosgene, and the like~ Polycarbonates generally have a repeating carbonate group, i.e., o O C--O--and generally always have a - ~ radical attached r J 1 3 41 2 ~L ~
to the carbonate group. Polycarbonates are well known and described in many patents and other technical references.
Desirably, the polycarbonate can be characterized by the formula (R1)n (R2)n ~ rt\
_ 0 ~ O~ ~ Z ~(\O~
wherein Z is a single bond, an alkylene or alkylidene radical with 1 to 7 carbon atoms, a cycloalkylene or cyclo-alkylidene radical with 5 to 12 carbon atoms,-O-, -CO-, -SO or SO2-, preferably methylene or isopro-pylidene; R1 and R2 are hydrogen, halogen or an alkylene or alkylidene radical having 1 to 7 carbon atoms; and n equals 0 to 4. Most preferahly, the aromatic polycarbonates useful in the practice of the invention have a melt flow rate range of about 1 to 60 gms/10 min. at 300C, as measured by ASTM D 1238. The most important aromatic polycarbonate which is commercially available from many different sources is the polycarbonate of bis(4 hydroxy-phenyl) 2,2-p~opane, known as bisphenol-A polycarbonate.
These and examples of other polycarbonates which can be utilized are set forth in the EncvcloPedia af Pol~mer Science and_ Engineerin~, Vol. 11, John Wiley & Sons, Inc., New York, New York, 1988, pages 648-718, which is hereby fully incorporated by reference.
Other thermoplastic polymers suitable for use in the present invention are the various ABS type copolymers which are known in the art and to the literature. Such polymers are generally graft copolymers of acrylonitrile, conjugated dienes having from 4 to 8 carbon atoms with butadiene being highly preferred, and a vinyl substituted aromatic having from 8 to about 12 carbon atoms, with styrene being preferred, often referred to as an acrylonitrile-butadiene~styrene copolymer. The amount of the acrylonitrile is generally from about 10 to about 40 percent by weight; the amount of styrene is generally from IL3~2~
--19-- ..
about 20 to about 70 percent by weight; and the amount of butadiene is generally from about 20 to about 60 percent by weight based upon the total weight of the three-component mixture. Although ABS copolymers are generally a mixture of a styrene-acrylon.itrile copolymer and a styrene-acrylo-nitrile grafted polybutadiene rubber, a terpolymer made from acrylonitrile, butadiene, and styrene monomers can also be used. In lieu of butadiene, other conjugated dienes such as isoprene, pentadiene, dimethylbutadiene, di-methyl pentadiene, and the like can also be utilized. Simi-larly, in lieu of styrene, vinyl toluene, alpha methyl vinyl toluene, alpha methyl styrene, and the like can be utilized. Although acrylonitrile is normally always uti-lized, other vinyl cyanides can be utilized such as methac-rylonitrile, ethacrylonitrile, and the like. These andexamples of other ABS type polymers which can be utilized are set ~orth in the Encyclopedia of_Polymer science and Enqineerinq, Vol. 1, John Wiley ~ Sons, Inc., New York, New York, 1985, pages 388-426, which is hereby fully incorpo-rated by reference.
Another thermoplastic polymer component which canbe utilized in the present invention is polyvinyl chloride and the various copolymers thereof which are known to the art and to the literature. Polyvinyl chloride copolymers are generally made from a majority of vinyl chloride mono-mers and a vinyl component monomer. By the term "vinyl component," it is meant a vinyl-type monomer other than vinyl chlor.ide. Such monomers are well known to the art and to the literature and include esters of acrylic acicl wherein the ester portion has from l to 12 carbon atoms, for example, methyl acrylate, ethyl acrylate, butyl acry-late, octyl acrylate, cyanoethyl acrylate, and the like;
vinyl acetate; esters of methacrylic acid wherein the ester /;~
portion has erom l to 12 carbon atoms, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like; styrene and styrene derivatives having a total of from 8 to 15 carbon atoms such as alpha methyl styrene, ~3~124~
~20-vinyl toluene, chlorostyrene; vinyl; naphthalene; diolefins having a total of from 4 to 8 carbon atoms such as butadiene, isoprene, and including halogenated diole~ins such as chloroprene; monoolefins having ~rom 2 to 10 carbon atoms and preferably 2 to 4 carbon atoms; and the like, and mixtures thereof. An amount of vinyl chloride monomer is utilized to produce a copolymer containing at least aboùt 70 percent by weiyht, and preferably from about 80 to about 93 percent by weight of vinyl chloride repeating units therein. The remainder of the copolymer is made up of the one or more above-noted vinyl component monomers, for example, vinyl acetate. Thus, an amount of vinyl component monomer, when utilized to produce a copolymer, is from up to about 30 percent and preferably from about 7 to about 20 percent by weight of vinyl component repeating units there-in. Also included within the definition of the polyvinyl chloride type polymers and copolymers as set forth above are chlorinated polyvinyl chloride polymers (CPVC) and copolymers having a total chlorine content of from about 57 to about 72 percent by weight. These and examples of other polyvinyl chloride type polymers and copolymers which can be utilized are set forth in the Encyclopedia of Polymer Science and Enqineerinq, Vol. 17, John Wiley & Sons, Inc., New York, New York, 1989, pages 295~376, which is hereby fully incorporated by reference.
Another thermoplastic polymer component which can be utilized in the present invention is a polyester-ether polymer which in reality is a copolyetherester block copol-ymer generally comprising one or more riny containing polyester blocks as well as one or more acyclic polyether block~. The polyester block is generally made ~rom an aromatic containing dicarboxylic acid or diester such as terephthalic acid, dimethyl terephthalate, and the like, with a diol generally containing from about 2 to about 10 carbon atoms. The acyclic polyether is generally made ~rom polyalkylene oxide glycols having a total of from about 3 to about 12 atoms including up to about 3 or ~ oxygen atoms ~ L 3 ~
with remaining atoms being hydrocarbon atoms. The polyes-ter-ether polymers can be represented by the following formula:
-(ring containing polyester-b-acyclic polyether) n.
Such polyester-ether copolymers are commercially available such as Hytrel, manufactured by DuPont, and the like, w~th polybutyleneterephthalate-b-poly(oxytetramethylen~) block copolymer being preferred. These and other examples of other polyester-ether copolymers which can be utilized are set forth in the EncYclopedia of Pol~mer ~cience and Enqi-neering, Vol. 12, John Wiley & Sons, Inc., NY, NY, ~98~, pages 49 52, which is hereby fully incorporated by refer-ence as well as U.S. Patent Nos. 2,623,031; 3,651,014;
3,763,109; and 3,896,078.
Another thermoplastic polymer component which can be utilized in the present invention is copolymers of generally styrene and acrylonitrile, typically known as SAN, that is, styrene-acrylonitrile copolymers. Such copolymers can generally be produced by either emulsion, suspension, or continuous mass polymerization, and usually are made from a majority, by weight, of styrene monomers.
Comonomers other than styrene which can be utilized include vinvl acetate, methyl acrylate, and vinyl chloride. These and a further detailed description of SAN type polymers in general are set forth in the Encyclopnedia_of Polymer sci-ence and Enqineering, Vol. 1, John Wiley & Sons, Inc., New York, New York, 1985, pages 452-470, which is hereby fully incorporated by reference.
Another thermoplastic polymer component which can be utilized in the present invention are the various esters of acrylic or methacrylic acid where the ester portion is typically an alkyl containing from 1 to about 16 carbon atoms, a secondary branched-chain alkyl ester containing from 3 to about 10 carbon atoms, an ester of an olefinic alcohol containing from 3 to about 8 carbon atoms, an aminoalkyl ester containing from about 3 to about 10 carbon 2134~
atoms, an ester of ether alcohols containing from about 2 to about 10 carbon atoms, a cycloalkyl ester containing from about 4 to about 12 carbon atoms, or a glycol diacryl-ate containing from about 2 to about lo carbon atoms, and the like. very often, copolymers of various acrylates and blends thereof can be utilized. Examples of common, com-mercially available, acrylates include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylat~, 2-ethylhexyl acrylate, and the like. Examples of the various methacrylates include methyl methacrylate, ethyl methacry~
late, n-butyl methacrylate, isodecyl methacrylate, stearyl methacrylate, and the like. These and examples of other acrylate or methacrylate esters which can be utilized are set forth in the Encyclopedia of Polvmer scien~e and Enqineerin~, Vol. 1, John Wiley & Sons, Inc., New York, New York, 1985, pages 234-325, which is hereby fully incorpo-rated by reference.
Another thermoplastic which can be utilized in the present invention is poly(phenylene ether). The most important polymer which can be utilized is poly(2,6-dimeth-yl-1,4-phenylene ether). Other polymers include poly(2,6-diphenyl-1,4-phenylene ether), poly(2-methyl-6-phenylphen-ol), as well as copolymers of 2,6-dimethylphenol and 2,6-diphenylphenol. Blends of polystyrene with poly(phenylene ether) can also be utilized. These and examples of other -poly(phenylene ether) compounds which can be utilized are set forth in the Encyclopedia of Polymer Science and En~i-neering, Vol. 13, John Wiley & Sons, Inc., NY~ NY, 1988, pages 1 through 30, which is hereby fully incorporated by reference.
The polysulfones constitute yet another class of thermoplastic polymer components which can be utilized in the present invention. Polysulfones are generally classi-fied as high molecular weight polymers containing sulfone groups and aromatic nuclei in the main polymer chain. The term "polysulfone" also denotes a class of polymers pre-pared by radical-induced copolymerization of olefins and ~ " ~ A
~ :~ 3 ~ 4 sulfur dioxide. Polysulfones are generally clear, rigid, tough thermoplastics with generally high glass transition temperatures, i.e., 180C to about 250C, with a chain rigidity generally being derived from the relatively in-flexible and immobile phenyl and S02 groups. Examples ofvarious polysulfones include bisphenol A polysulfone, polyarylethersulfone, polyethersulfone, polyphenylsulfone, and the like. These and other examples of polysulfones which can be utilized in the present invention are set forth in the Encyclopedia of Polymer Science and Enqineer-~, Vol. 13, John Wiley & Sons, Ins., New York, New York, 1988, pages 196-2~1, which is hereby fully incorporated by reference.
The various polybutylene polymers can also be utilized in the present invention and are derived essen-tially from high molecular weight, predominantly isotactic poly(1-butene) homopolymers or copolymers. These as well as other examples of various polybutylene polymers which can be utilized in the present invention are set forth in the Encyclopedia of Polymer Science and Enqineerinq, Vol.
2, John Wiley & Sons, Inc., New York, New York, lg85, pages 590-605, which is hereby fully incorporated by reference.
Polyethylene, and the various forms thereof, constitutes another class of thermoplastic copolymers which can be utilized with another thermoplastic copolymer which is immiscible therewith and, at a specific processing temperature, has a different viscosity therefrom. Examples of various types of polyethylene include linear polyethyl-ene such as ultra low density polyethylene, linear low density polyethylene, high density polyethylene, high molecular weight high density polyethylene, ultra high molecular weight polyethylene, and the various types of branched polyethylenes such as low density polyethylene, and the like. These and examples of other polyethylene polymers which can be utilized are set forth in the Enc~
_lopedia of Polymer Science and Enqineerinq, Vol~ 6, John ~ ~ 3~2~
, Wiley & Sons, Inc., New York, New York, 1986, pages 383-522, which is hereby fully incorporated by reference.
Still another type or class of thermoplastic polymer component which can be utllized in the present invention is the various polypropylene polymers, such as isotactic polypropylene and the like. It is ~o be under-stood that within the classification of polypropylene polymers and polyethylene polymers are the various copoly-mers of ethylene and propylene. A description of various polypropylene polymers can be found in the EncYcloPedia of Polymer Science and Engineerlng, Vol. 13, John Wiley &
Sons, Inc., New York, New York, 1988, pages 464-531, which is hereby fully incorporated by reference.
Another thermoplastic polymer component suitable for use in the present invention is polystyrene, including crystal polystyrene, impact polystyrene, and the like.
Such polymers are known to the art, and examples thereof suitable for use in the present invention are set forth in the Encycloe~dia of Polymer Science and Engineering, Vol.
16, John Wiley & Sons, Inc., New York, New York, 1989, pages 1-246, which is hereby fully incorporated by refer-ence.
In another aspect of the invention, it has been discovered that surprising improved results are obtained when a modified PET is used, particularly in combination with thermoplastic elastomers. The modified polyethylene terephthalate (M-PET) is a random mixed linear thermoplastic copolyester f ormed by the reaction of ethyle.ne glycol, terephthalic acid and at least one other glycol and/or dicarboxylic acid. The ~-PET has an intrinsic viscosity of from about 0.4 to about 1.2 and a melting point lower than unmodified PET (which is about 265C). Desirably the melting point of the M-PET is from about 200C to about 255C, preferably from about 225C to about 250C, and most desirably from about 235C to about 2~8C.
3~2~
Suitable glycols and dicarboxylic acids are any glycol or diacid which is reactive to form a copolyester with PET and interrupts the crystallinity of PET sufficient to lower its melting point. Suitable glycols include aliphatic, cycloaliphatic and aromatic glycols. Aliphatic glycols include straight or branched chain alkane and alkene diols, including 1,3-propanediol; 1,~-butanediol;
1,5-pentanediol; 1,6-hexanediol; 3-methyl-1,5-pentanediol;
2,2-dimethyl-1,3-propanediol; 2-methyl-1,3 propanediol; 3-octyl-1,6-hexanediol; and cyclohexane dimethanol. Aromat-ics include benzene glycol and ethoxylated bis-phenol A.
Polyether glycols such as diethylene glycol may also be used. Although less desirable, triols may be used. The preferred glycols are 1,5-pentanediol and 1,6-hexanediol.
Suitable dicarboxylic acids include aliphatic, straight and branched chain diacids, and aromatics. Exem-plary aliphatic diacids include C~ - C12 diacids, which carbons include the carboyl groups, such as adipic acid, glutaric acid, sebacic acid, azelaic acid, succinic acid, and 1,12-dodecanedioic acid. The preferred diacids are glutaric or azaleic acid.
Typically, the aromatic dicarboxylic acids have a molecular weight less than about 500 and are aromatic dicarboxylic acids includiny isophthalic acid (m-phthalic acid), phthalic acid (o-phthalic acid), t butyl isophthalic acid, 4,4'-dibenzoic acid, 4,4'-substituted dicarboxy compounds with two benzene nuclei such as bis(p- ;
carboxyphenyl)methane, p-oxy(p-carboxyphenyl)benzoic acid, ethylene-bis(p-oxybenzoic acid), 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-sulPonyl dibenzoic acid, and symmetrically substituted derivatives thereof, with substituents such as C1 ~ C~
alkyl, halo and alkoxy groups. The preferred aromatic dicarboxylic acid is isophthalic acid.
Dicarboxylic acids may also be used which have at last one side chain extending from them. The side chains can be aliphatic or cycloaliphatic and can contain one or ~1342~
more oxygen atoms as an additional element but at leas two (2) carbon atoms must be present between oxygens. The side chains may also contain one or more double bonds and can be straight or branched chain. Any common aliphatic, cycloal~
iphatic or aromatic dicarboxylic acid may be utilized when substituted with the above-described side chains. The molecular weight of the dicarboxylic acid should not be above about 500 excluding the contribution of the side chain.
Specific examples of suitable long chain acids include substituted succinic acids having alkyl or alkenyl radicals of 8-22 carbon atoms in the ~-position, 2~
dodecyloxy) terephthalic acid, 2-decyl-3-tridecyl succinic acid, 3-decyl-phthalic acid and 1-dodecyl-1,2-cyclohexane dicarboxylic acid.
The term "dicarboxylic acids" as used herein, includes e~uivalents of dicarboxylic acids having two functional carboxyl groups which perform substantially like dicarboxylic acids in reaction with glycols in forming copolyester polymers. These equivalents include esters and ester-forming derivatives, such as acid halides and anhyA
drides. While the molecular weight of the diacids suitable for use herein typically have a molecular weight of less than 500, the eguivalent ester and ester-forming deriva-tives may have molecular weight above 500.
Copolyesters of the invention can be prepared by conventional ester interchange and condensation reactions, as set forth in the Encyclopedia of Pol~mer Science and _qineerinq, Vol. 12, John Wiley & Sons, Inc., NY, NY, 1990 and in U.S. Patent No. 4,223,1~6 and U.S. Patent No.
3,890,279, all of which are incorporated herein by refer-ence.
The amount of glycol, other than ethylene glycol, and/or dicarboxylic acid, other than terephthalic acid, incorporated into the copolyester is an amount sufficient to lower the melting point of an unmodified polyethylene terephthalate, and may vary depending upon the glycol ` ~ 3~2~
..
and/or dicarboxylic acid. Generally, however, an amount of glycol and/or dicarboxylic acid from about 1 to about 20 percent by weight of the total copolyester is suitable.
Preferably, from about 1 to about 10 percent and most desirably from about 2 to about 6 percent of glycol and/or dicarboxylic acid is present.
In a preferred embodiment, the dicarboxylic acid, other than terephthalic acid, is present in an amount of from about 1~ to about 10%, most preferably from about 2%
to about 5%, based upon the total weight of acid present in the copolyester and the glycol, other than ethylene glycol, is present in an amount of from about 1~ to about 8~, most ~;
pre~erably from about 1% to about 4%, based upon the total glycol in the copolyester.
A preferred copolyester is one comprised o~ tere-phthalic acid, ethylene glycol and about 2-5% isophthalic acid, based upon the total weight of acid present. Dieth~
ylene glycol may additionally be present, in an amount of from about 1-4% of the total weight of glycol in the copol-yester. Such a preferred copolyester will have an intrin-sic viscosity of about 0.62 and is commercially available as TRAYTUF~ PET resins from The Goodyear Tire and Rubber Company, Akron, Ohio, U.S.A. Particularly suitable is TRAYTUF~ 6254C PET resin.
In addition to the polymers described hereinabove, particularly polyurethanes and polyester-ether polymers, other thermoplastic elastomers suitable for combination with the M-PET are block styrenic copolymers, polyether block amides (PEBA) and ethylene propylene diene (EPDM) terpolymers.
Suitable block styrenic copolymers are o~ the linear or A-B-A type. Basically, these are triblock polymers consisting of a soft rubber or elastomer midblock and hard thermoplastic polystyrene blocks attached to each end. These polymers ~all inko three basic categories and di~fer primarily in the type of rubber used in the midblock: styrene-butadiene-styrene (S-B-S); styrene-~:~3~2~
, isoprene-styrene (S-I-S); and styrene-ethylene/butylene-styrene (S-EB-S~. Such triblock styrenic copolymers are commercially available from Shell Chemical Company (Texas, U.S.A.) as Kraton~ thermoplastic rubber D series (S-B-S and S-I-S) and G series (S-EB-S). These examples of styrenic block copolymers are set forth in the ncyclo~edia of PolYmer Science and Engineerinq, Vol. 5, John Wiley & Sons, Inc., NY, NY, 1990, pages 416-430, which is hereby fully incorporated by reference.
The polyether block amides (PEBA), generally, have a structure consisting of regular and linear chains of rigid polyamide (nylon) block and flexible polyether blocks with the generalized formula O O
H0-t--C-PA-C-O-PE-0 ~ n~H
wherein PA represents the polyamide block, the PE repre-sents the polyether block, and "n" represents an integer such that the molecular weight of the polymer is between about 20,000 and 50, 000. Such polyether block amide copolymers are commercially available, such as Pebax~
polyether block amide, manufactured by Atochem Inc. (New Jersey, U.S.A.).
To make the ethylene propylene diene (EPDM) terpolymers, most commonly the dienes 5-ethylidene-2-norbornene (ENB); 1,4-hexadiene (HD); and dicyclopentadiene tDCPD) are used. Although the ratios for the monomers widely varies, most polymers contain 40-90 mol % ethylene and 0-~ mol % diene. Such EPDM terpolymers are commercially available such as Nordel~ thermoplastic rubber from DuPont and Vistalon~ by Exxon. These and other examples oP EPDM polymers are set ~orth in the Enc~clopedia of Polymer Science and Enqineerinq, Vol. 6, John Wiley &
Sons, Inc., NY, NY, 1990, pages 522-563, which is hereby fully incorporated by reference.
C
~3~2~
In accordance with the present invention, desir-ably two, or more, of the above~noted types of thermoplas-tic polymer components are selected, which, as noted previ-ously, are generally immiscible with respect to one anoth-er, have relatively different viscosities at a specificprocessing temperature, and generally do not degrade at the processing temperature, are blended under high shear to yield a two-phase or multiple-phase composition having fibers incorporated therein and wherein the two, or more, different thermoplastic polymers have good mechanical com-patibility to every component, that is, mutually good adhesive properties with respect to each component. Unex-pectedly, an extremely smooth surface layer is produced which is substantially and typically free of fibers.
Althouyh a large number of combinations of various specific thermoplastic polymers exist, desirable combinations ac-cording to the above guidelines can be readily determined by one skilled in the art. Thus, fiber reinforced blends of polyvinyl chloride (includiny chlorinated polyvinyl chloride) and polycarbonate can be utilized, fiber rein-forced blends of polyvinyl chloride (including chlorinated polyvinyl chloride) and ABS type copolymers can be uti-lized, as well as fiber reinforced blends, as noted above, wherein one component is polyurethane, and the second component is PET, PETG, polycarbonate, polyacetal, or an ABS copolymer. One skilled in the art will appreciate that it is advantageous to combine the M-PET with polymers having a lower melting point than PET. In other words, it is advantageous to use M-PET, instead of PET, in systems where the processing temperature is actuallv above the degradation temperature of the higher viscosity polymer if PEq' was used. The lower melting M-PET enables the injec-tion molder to operate within a wider processing window when combining a higher viscosity thermoplastic polymer which has a lower melting point than PET, with the M-PET.
I'hus, enhanced physical properties of the thermoplastic physical properties of the thermoplastic polymer due to ~13~
less degradation of the polymer at lower processing temper-atures results also. Such suitable combinations of poly-mers include M-PET combined with a block styrenic copoly-mer, a polyether block amide, an ethylene propylene diene (EPVM) terpolymer, and a thermoplastic polyurethane. It has been surprisingly discovered that when the modified PE~
is mixed with the modified TPU, Applicants obtain increased compatibility between the two immiscible components, and better processing.
Even though two component systems are generally preferred, the present invention also encompasses multi-component compositions having three or more of the above-noted thermoplastic polymer components which are blended under high shear in the presence of fibers. The amount of any thermoplastic polymer component with respect to an immiscible thermoplastic polymer component in a two compo-nent thermoplastic blend according to the preferred embodi-ment o~ the present invention is from about 15 percent to about 85 percent by weight, desirably from about 25 to about 75 percent by weight, and preferably from about ~0 percent to about 60 percent by weight with the remaining component constituting the difference. For systems using M-PET (thermoplastic copolyester), the amount of M-PET
component with respect to the immiscible thermoplastic polymer component is from about 10 percent to about 90 percent by weight, desirably from about 20 percent to about 80 percent, and preferably from about 30 percent to about 70 percent by weight with the remaining component constituting the difference. For systems using m-PET with m-TPU, the m TPU component in the range from about 10 to about 90 percent by weight is preferred. Preferably the range is from about 20 to about 80% by weight. Most pre~erably 30% by weight of mTPU is used with 70% by weight of the mPET.
When more than two thermoplastic polymer components are utilized, the amount of one of the thermoplastic polymer components is within the above ranges ~3~2~
_.~
with the remaining two or more thermoplastic componen-ts constituting the difference, i.e. the total of all components add up to 100 percent by weight Desirably, the remaining two or more components each exist in amounts of at least 15 percent, and desirably at least 20 percent or 25 percent by weight.
In accordance with the present invention, short fibers are added to the thermoplastic immiscible polymer components to provide a fiber~reinforced moldiny composi-tion. The types of organic fibers which can be utilized are limited to those which generally do not melt during blending of the thermoplastic polymer components of the present invention. Examples of such organic fibers include aramid, that is aromatic polyamide fibers, and various aramid hybrides such as aramid/carbon, aramid/carbon/glass, and aramid/glass composites. Generally, any type of inor-ganic fiber can be utilized including those known to the art and to the literature such as glass fibers. Glass fibers, either unsized or, preferably, sized, and particu-larly chopped, i.e., short, glass fibers in lengths of about one-eighth inch to two inches, are preferred where an average length of one-eighth to one-half inch fiber is most preferred. Due to the shear mixing with the matrix poly-mers, especially the viscous immiscible polymer, a majority of the short fibers are broken or sheared into shorter ~ibers whereby said sheared fibers are typically reduced in size to about 0.2 to about 3 millimeters in length. A
common glass fiber which can be utilized is "E" type glass fiber which is substantially free of alkali metal salts and has a tensile strength of about 500,000 psi, a modulus of alasticity of around 10.5 million psi, and a f`iber diameter between about 0.0001 and 0.001 inch. Continuous glass roving can also be utilized and subseguently chopped to a desired length. Smaller glass fibers, known as "S" milled ~ibers, are also commercially available, although the size range is smaller and more narrow, typically between 1/32 and lt8 inch in length. Other suitable inorganic fibers ~:~3~2~
."
include carbon fibers, carbon/glass hybrid fibers, boron fibers, graphite fibers, and the like. Various ceramic fibers can also be utilized such as alumina-silica fibers, alumina fibers, silicon carbide fibers, and the like, as well as various metallic fibers such as aluminum fibers, nickel fibers, steel, e.gO stainless steel fibers, and the like. The length of the non-glass fibers is generally the same as the glass fibers and hence ini.tially can be from about 1~8 inch to about 2 inches in length and more desir-ably have an average length of from about 1/8 to about 1/2inch before shear blending with the various thermoplastic polymer components. The fibers are combined with the two, or more, thermoplastic polymer components on a weight basis of from about 5 percent to about 60 percent, desirably from about 15 percent to about 50 percent, and preferably from about 25 percent to about 45 percent by weight based upon the total weight of the imm.iscible thermoplastic polymer components and the fibers. For systems using M-PET, the fibers are combined with the two, or more, thermoplastic polymer components on a weight basis of from about 5 percent to about 60 percent, desirably from about ~0 percent to about 50 percent, and preferably from about 20 percent to about 40 percent by weight based upon the total weight of the immiscible thermoplastic polymer components and the fibers.
The fiber-reinforced thermoplastic molding compo-sition blend, etc., is made by initially compounding the various ingredients and makiny them into a suitable form or shape for storage and subsequent use, and then processing the same at a suitable temperature to ~orm a moltled article or end product. The compounding step generally entails adcling the two, or more, immiscible thermoplastic compo-nents which are utilized as well as the fibers to a mixing or blending apparatus having at least moderate shear, such as a Banbury, a twin-screw extruder, a Buss Kneader, or the likel and mixing the same until generally a two-phase, or a multiple phase, blend having fibers incorporated therein is 3 L?~ 2 ~ ~
~,~
.
obtained. The mixing temperature is approximately the same as the processing temperature of the molding operation, al-though it can be higher or lower, e.g., by 10F or even 20F. In order to prevent the varioui fibers ~rom undue breakage, which reduces the physical properties of the molded end product, or composition, the fibers are general-ly added after a melt is developed in the blending appar-atus, as toward the end of the compounding process. Shear mixing is continued until the various components are gener-ally dispersed, and overmixing is avoided because it tendsto reduce the fibers to an undesirable short le.ngth. The resulting mixture or blend of thermoplastic polymer compo-nents and fibers is generally cooled to produce a solid mass and then pelletized or otherwise divided into suitable size particles for use in a molding apparatus used to form the final product or composition, i.e. article.
Moreover, it has been unexpectedly found that using the modified TPU in a blend with modified PET, no glass fibers are necessary. Delamination does not occur even if no glass is present.
On an optional basis, minor amounts of other molding additives can be intermixed with the immiscible thermoplastic compounded polymers. For instance, mold release agents can be added to obtain a clean release from the mold platen. Opacifying pigments such as titanium dioxide, or ~iller pigments such as calcium carbonate, talcs, carbon blacks, silicas, clays, and the like, can be added. Colorants such as tinting pigments or organic dyes can be added to provide color to the molded article.
Ordinarily such additives, if utilized, comprise less than about 25 percent, desirably less than 15 percent, and prePerably less than 10 or 5 percent by weight, of the molding composition based on the weight of matrix polymers plus reinforcing fibers. Other additives, such as up ko about 15 percent by weight of Teflon powder, or up to about 2 percent by weight of silicone oil, can be used for compo-sitions for bearings, or up to about 12 percent by weight 2 ~ ~
- ~
of stainless steel fibers can be used for conductivity purposes or for shielding against EMR waves.
The compounded immiscible thermoplastic molding compositions containing fibers incorporated therein, as well as the various optional molding additives, as noted above, are generally molded under high shear conditions.
Thak is, the compounding molding step utilizes a moderatè
to high shear range as from about at least 10, desirahly at least 100, desirably at least 500, etc., reciprocal sec-onds, whereas the actual end product or article formation step such as injection molding generally requires high shear such as a shear rate of at least lO0 or 200, desirably at least 500, more desirably at least ~00, etc., reciprocal seconds. High shear conditions, that is, shear rates of at least 100 reciprocal seconds, are generally required as a practical matter to obtain the unexpectant smooth surface characteristics of the present invention.
Any conventional processing device which typically generates the required high shear processing rates can be utilized. Examples include various injection molding machines including those utilizing a plunger or more preferably a reciprocating screw. As long as suitable high shear conditions are generated to produce smooth surface articles or products of the present invention, various injection blow molding machines, and to a lesser extent various compression molding machines, can also be utilized.
The processing temperature will naturally vary depending upon the type of specific diPferent thermoplastic components which are utilized and usually is from about 200C to about 300C although higher or lower temperatures can be utilized. For example, when a thermoplastic polyur-ethane is blended with a polycarbonate in the presence of glass fibers, the processing temperature can generally range from about 240C to about 260C. Blending of PVC
~5 with polycarbonate and glass fibers can be molded at tem-peratures at from about 225C to about 240C. Yet another example is a blend of a thermoplastic polyurethane, polyac-~13~
.~
etal, and glass fibers which typically can be blended at temperatures of from about 240C to abo~lt 255c. A blend of a thermoplastic urethane, PET, and glass fibers can be blended at temperatures of from about 245C to about 265C.
For a blend using PET, the injection molding proce.ssing window can be widened by using modified PET
instead of unmodified PET. The amount by which the pro-cessing window is widened will vary depending upon the thermoplastic polymer being used with the M-PET. However, generally the window is widened by 20-40F. For example when blending with PET, the window is widened from a range of 490F to 505F using unmodifi~d PET to 465F to 505F
with M-PET. Thus, M~PET allows a lowered processing tem-perature by about 15 to about 20 or 25 degrees.
Once the thermoplastic compositions have been molded in accordance with the various aspects of the pres-ent .invention, e.g. the high shear blending of immiscible thermoplastic components generally having relative di.ffer-ent viscosities at a processing temperature which is below the degradation temperature of the thermoplastic components with fibers, yields a mechanically compatible end product unexpectedly having a smooth surface layer containing essentially one thermoplastic component with an inter:ior portion having two phases and containing the fibers there in, have very high physical properties such as i.mpact resistance, high heat distortion temperatures, high tensile modulus, high flexural modulus, and the like. For example, when a thermoplastic polyurethane is compounded with PET on approximately a 50/50 percent weight basis and the two components contain approximately 25 percent hy weight of ~iber glass therein, the following physical properties are typical: notched Izod impact resistance of 1.0 ft. lbs./
inch or greater, and generally at least 2.0 ft. lbs./inch at room temperature; heat distortion temperatures of at least 200F and generally at least 250F at 26~ psi; a tensile modulus of at least 700,000 psi, generally at least 1,000,000 psi and even at least 1,500,000 psi; and a flex-- ~13~2~L
ural modulus of at least 700,000 psi, and generally at least 1,000,000 psi, and even at least 1,200,000 p5i.
Unexpectedly, by using M-PET with the polyurethane, superi-or improvement in the impact strength of such compositions is obtained such that the notched and unnotched Izod impact values are two times or greater than formulations with unmodified PET. (See Example 9, Table VI below).
In view of the exceptionally good physical proper-ties such as high stiffness (for example, high tensile modulus and high flexural modulus), high heat distortion temperatures, and excellent melt flow, numerous end uses exist. Moreover, with regard to the exceptionally smooth surface achieved, the same can be maintained, or dulled to provide a low sheen, or altered by texturing the mold surface to provide a pebbled grain or other decorative surface. A particularly desirable end use of the molded compositions of the present invention is for housings, fenders, etc., as well as for horizontal surfaces in a vehicle. Thus, the molded article can be an automotive hood, fender, truck, roof, and the like. The molded compo-sitions of the present invention, inasmuch as they can contain surfaces rich in polyurethane, provide excellent paint adhesion with respect to various industrial paint coatings such as polyurethane-based paints, without the need of a primer.
The invention will be better understood by refer-ring to the following illustrative examples.
Example 1 Thermoplastic Urethane/Polycarbonate/Glass Fibers A composite of 35 percent thermoplastic urethane (TPU), i.e., Estane 58137, manufactured by The BFGoodrich Company, which is made Prom a polyester intermediate uti-lizing MDI and 1,4-butane diol; 35 percent polycarbonate, i.e., Dow Calibre 300-22; and 30 percent glass fiber was made on a Werner-Pfleiderer compounding twin-screw extruder. The TPU was characterized by its low viscosity of 7-8 X 102 poise, on a 20/1, L/D, capillary rheom~ter at ~13~2~1~
lO0 sec~1 shear rate and 260C. The polycarbonate was characterized by its high viscosity of 7-9 X 103 poise at 260C. The glass was ~-inch "E" glass.
The TPU and polycarbonate were dried for 2 hours at 100C. Then the TPU and polycarbonate were mixed on the Warner-Pfliecler compounding twin-screw extruder, adding granules of these makerials at the rear port of the extrud-er. Downstream, after these materials were mixed and heated to about 240C, glass was added. Work and mixing continued on the compounding extruder. This composite blend at 260C was extruded through a spaghetti die, cooled in air, and chopped into pellets.
The pellets were dried 2 hours at 105C. The in~ection molding was carried out in a physical property mold. The mold temperature was set at 50C. The melt temperature achieved was 252C. The glass-filled TPU and , glass-filled polycarbonate were made under the same condi-tions.
Physical data are set ~orth in Table, I.
3 ~
~P ~tO
o ~n ~ n) m O m ~ ~ ~
g m ~ ~, O tn ~ E~ O ~ ~ ~
v ~ ~ In a~
~ ~O ~
O ~ 0U ~
.4 O # m ~~U Sm ~r~ o ~ ~ P. ,~ m u u a~ C a\~ ~~ 3 ~
~ ul o ~ o a~ ~ ~ o .c _ o ~
_~ 10 N rl O C ~ D~ ~1~ ~ Ll ~ ~ ~ ul ~ O O
~ ~ ~ ~ 1,,`D ~ oc~ 8 :,, ~ ~ ~ ~
o o o JJ ~ O ~ u~ E ~ ~ ~ a r ~ 3 ~ N ~1 o tu o ~ a~
a~ ~ O Q,~
I ) S o 4 U) a) ¦ ~ 3 r ~ u E~
I u ~ u~ ou) C~ U O
::~ ~ C u~ h~ ~ O a~ a u~
l ~ O Or-l ~1 O O r~ 0 0 S 't:1 ~ O
~n ~ E o o .,~ u~ S~c ~':1 ~P dPr,10 ~ d~ o U Q~ C U
m o . ", . ~ O o s n s ~ ~ o ~ J~ 3 Z ~o ~ s . 0 ~u O t~ I ra V
U) rl ~ O U CL~
u c ~ m ~ n ~ o ~. x Ul o . o ~ ~ U ~ o ~ O C) ~o ~
E~ ~ D~_~ ~ O O n ~I E ~ ~ u E o co o,~ u~
dD dP r~ O ~D t.) ~) O
E~ O O O --I ~I Lrl~1 C $ ~ ~ ~
O ~ o ~ c E t~
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~ ~ J~ Q~ C a~ E ~
t4 n c x u ~0 u~ o o ~ c) u~ E o ~ E
_~ a) lUa u~ ~ ~a h g h r~l h O r ~ ,~ u~ (a ~ ~
O ~D ::1 3 N tJ~ la .c 0 a ~ u~ 41 U
(a E~ h CO ~J (a O .1 ~ (~ ; r~~
E~ ~ la .c ~ ~ la c a) U~ D C ~CI U~ C ~ ~ O
u` ~ '~ E a U a ~ ~ $ c ~ :, ~ D4 U1 (a ~ E-l E O h _I r-l h O _I ~( 1~ E-i s O s~ ~O ~ ~1 ~ Eo E ~;h a O C
~ _I c ~ ~ _l ou X -I u uJ E a-,~
O ~ U O ~ ~ O ~ (a o o~
E ,~ ~ t O u ~ ~ u~ ~-o~ c~ ~ u u n o x~ a~ o-,~ u~ o o ~ ~ .as u ~ ,1 ~a--~ Q N (Ulad~ Ul U~
(d h ~ C ~ UQl O ~I h O
~ v~ c c c'a ~ c o Q' s u s o o U~ E-l W E-l IC a~3 ~ D~ J --I U
3~24~
-39~
Example 2 Vinyl/PolYcarbo~ate~ ass Fiber A composite of 35 percent vinyl compound, i.e., Geon 87241, a polyvlnyl chloride compound manu-factured by The BFGoodrich Company; 35 percent polyca-rbonate, i.e., Dow Calibre 300-22; and 30 percent glass fiber was made on a Warner-Pflieder compounding twin-screw extruder. The vinyl was characterized by its low viscosity of 2-4 X 103 poise, on a 20/1, L/D, capillary rheometer at 100 sec~1 shear rate and 230C.
The polycarbonate .is characterized by its high viscos-ity of 3-5 X 104 poise at 230C. ~he glass fibers were ~-inch "E" glass.
The polycarbonate was dried for 2 hours at 100C; the vinyl WAS not dried ~urther. The vinyl and polycarbonate were then mixed on the Warner-Pflieder compounding twin-screw exkruder, adding granules of these materials at the rear port o~ the extruder.
Downstream, glass fibers were added. Working and mixing continued on the compounding extruder. At 237C, this composite blend was extruded through a spaghetti die, cooled in air, and chopped into pel lets.
A vinyl/glass fiber, at a 70:30 weight ra-tio, was produced under similar conditions. A
~5 polycarbonate/glass fiber control, 70:30 weight ratio, was produced under similar conditions except the melt temperature at the die was 277C.
The pellets were dried 2 hours at 105C.
The injection molding was carried out in a physical property mold at a temperature of 50C. The melt temperature was 229C.
A control compound of vinyl/glass, 70:30 weight ratio, was made under the same conclitions. A
control compound of polycarbonate/glass, 70:30 weight ratio, was made at 271C i~ a compounding extruder.
Physical data are set forth in Table II.
2 ~ 3 ~
--4 ~--h a~ ~: m 3 v ,~
~J 0~ S .C
C ~ m 0 ~ 3 O ~ C -1 S 0 ~ ~ O.ma~
U m ~ o m o C~ ~ S
~ u~ O c~ 4 n~
_I ~ C o ~ O ~ U al C
O '~ ~ F g O ~ ~ V ~ .
~~ dP 00 0 W
dP ~ J ~ D O
O O ~ o t) S~ ~
~: ~ V ~ O c V E
tn ~ Lq D~ o m ~,~ ~ ,a '' O ~D g-~~ ~ U
m ~ ~ ~ o .
~n~ U o ~, Q\ U.
~5 .. o E O OC~ a~ m m C~ e t~ ~ 0 r- ~ ~o ~ J la O o ~~ N ~ ~ ~ J ~ (d ~: ~, ~ E Id S t~' wl ~ U~ J ~ ~ ~ J a) W ~ _~ Ul Oq o c~ 0 ~ ~ ~a o ~1 ~ ~ ~a ~~ o 0 0 ~ ~a ~ _~
.¢ O C rd U O 0~ Id C Ul U~ .C U
E-~ _ ~ ~ EO O N C~ _I h I ~ ~d .1 In .-1 ~1 J C~ ~11 ~ 3 a o N ~ ON ~
w I~ ~ OI II CO Id S h ~ I J h a ~ c~tr N
O 0 ~ C4 ~O V U
O ~ ~ ~- U O ~
o oO~' ~.n o~ d L~ C
m 3, c O ^ N :> O V 0 Cll O a) tU~ C ~ e ~s L --~d nl a~ ~ a~ ~ J' '`-~ ~
a v ~ ~ V ~ D~.a C o C
nl~ d rd ~ 3 m '0~ LO~ rn ~~
U V:~ C ~ O ra E ~, m v o ~
rn Q.~ o o S ,~ I U .~ v rn ~ ~ ~eO a ~ ~ e rn D~ rna 'dl O~ ~ ~ ta o 01 a) Id U ~ U ~ t~ O
C v rn C ~ ~ ~ nl rd nl ~ m ~ S:~ E
v ,~ c ~ ~ o o ~ o o ~ . ~ ~ o 8 1:) U J V Id C4 8 0 .R .I P~ d U
E.U ~t~ o ~ ~a~U L~ r L~ rd n) ~D
tn C tn O ~ S U s U O S S .C r~
al L~ a\ v ~ d nl L, .,1 rd ~ Q ~ND # Q, C~- U ~) E -~
~a Cm ~ s: :~ s L~ n c: o c: ~d ~ ~ V ~ C
~nE~ WE-, ~: 41 ~ ~ ~ V P
~::
~:13~2~
" .
Example 3 Vinyl/Polycarbonate A composite of 35 percent vinyl compound, i.e., Geon 87241, a polyvinyl chloride compound manu-factured by The BFGoodrich Company; 35 pe.rcent polyca-rbonate, i.e., Dow Calibre 300-22; and 30 percent ~lass was made on a Buss Kneader rotating-reciprocat-ing compounding machine. The vinyl compound was char-acterized by its low viscosity 0O5-1.5 x 104 poise, on a 20/1, L/D capillary rheometer at 100 sec~1 shear rate at 210C. The polycarbonate was characterized by its high viscosity, 0.5-1.5 x 105 poise, on a 20/1, L/D
rheometer at 210C. The glass was ~-inch l'E" glass.
The vinyl compound and the polycarbonate were m.ixed on the Buss Kneader. After melting the blend, glass was added through a port on the Buss Kneader and mixe~ into the blend achieving a compound temperature of 210C. This compound was injection molded at 210C into a cold mold (50C) to form a smooth product. The surface roughness was 0.6 microns as measured on a Taylor-Hobson Surtronic 10 roughness gauge. These data show good surface appearance for vinyl/polycarbonate/
glass when compounded on a di~ferent type compounding machine.
Example 4 Vinyl/ABS/Glass A composite of 35 percent vinyl compound, that is, Geon 87241, a polyvinyl chloride compound manu~actured by Th~ BFGoodrich Company; 35 percent ABS, that is, Taitalac 6000, manuPactured by Bolcof;
and 30 percent glass was made on a Buss Kneader com-pounding machine~ The vinyl is characterized by a melt viscosity of 0.5-1.5 x 104 poise on a 20/1, L/D
capillary rheometer at 210C. The ~BS has only a slightly higher viscosity of 1.8 x 104 poise. The glass was ~-inch "E" glass.
3 L~9; 2 ~ 4 The vinyl compound and ~BS were mixed on a Buss Kneader compounding machine. After ~elting the blend, glass was added through a port on the barrel of the Buss Kneader and mixed to a melt temperatur~ of 207~C.
This compound was injection molded at 210C
into a cold mold (50C) to form a plaque with a sur~ace roughness of 0.7 microns as measured on a Taylor-Hobson Surtronic 10 roughness gauge. These data show good surface smoothness for v.inyl/ABS/glass when compounded on a different type compounding machine.
Example 5 Thermoplastic_Urethane/Polyacetal/~lass A composite of 53 percent polyurethan2 (Es-tane 58137), 17 percent polyacetal (Delrin 900), and 30 percent glass ~ibers was made on a Warner-Pflieder compounding twin-screw extruder. The glass was 1/4-inch chopped "E" glass.
The TPU and polyacetal were dried two hours at 100C. Then the TPU and polyacetal were mixed on the Warner-Pflieder compounding twin-screw extruder, adding granules of these materials at the rear extru~
der port. Downstream, after these materials were mixed and heated to about 240C, glass was added.
Work and mixing were continued on the compounding extruder. This composite blend was extruded through a spaghetti die at about 260C, cooled, and chopped into pellets.
The pellets were dried 4 hours at 105C.
The injection molding was carried out in a physical property mold. The mold temperature was set at 45C.
The melt temperature achieved was 250C.
Physical data are set forth in Table III. ~;
3~2~
43- ~:
TABLE III ~:
P~YSICAL PROPERTIES OF TPUl~POLYACETALlGhASS
Surface Sm~othness, Taylor-Hobson Surtronic 10 Gauge 0.2 microns Tensile 5trength, ASTM D638 7800 psi Elongation 8.5 Tensile Modulus 560,000 psi Flexural Strength, ASTM D790 14,700 psi Flexural Modulus 580,000 psi Vicat softening, ASTM D1525B 159C
Heat Deflection Temperature @264 ps.i, ASTM D698 Annealed at 120C 135C
Izod impact, ASTM D638 Unnotched 17.7 ft.lbs/in Notched 2.1 ft.lbs/in ~3~2~ :
This data shows the ability to have an out~
standingly smooth surface with 30 percent glass in this TPU/polyacetal blend and include generally good physical properties.
Exam~le 6 ThermoplaStic Vrethane~
Polyethylene Terephthalate~/Glass A composite of 35 percent thermoplastic urethane (Estane 58137), 35 percent polyethylene ter-ephthalate (recycled bottle resin), and 30 percent glass fiber was made on a laboratory-~ize Warner-Pfli-eder compounding twin-screw extruder. The TPU was characterized by its low viscosity of 7-~ X 1o2 poise, measured on a 20/1, L/D capillary rheometer at 100 sec 1 shear rate and 260C. The PET was characterized by its high viscosity of 6-15 x 103 poise, measured on a 20/1, L/D capillary rheometer at 100 sec~1 shear rate and 260C. The glass was 1/4-inch chopped "E" glass.
The TPU and PET were dried for 2 hours at 2 0 100C . Then the TPU and PET were mixed on a Warner-Pflieder compounding twin-screw extruder, adding gran-ules of these materials at the rear extruder portO
Downstream, after these materials were mixed and heated to about 240C, glass was added. Work and mixing were continued on the compounding extruder. At 260C, this composite blend was extruded through a spaghetti die, cooled in air, and chopped into pellets.
The pellets were dried 2 hours at 105C.
The injection molding was carried out in a physical property mold. The mold temperature was set at 45C.
The melt temperature achieved was 250C. The q.lass-f`illed thermoplastic urethane and glass-filled PET
were made under these same conditions~
Physical data are set ~orth in Table IV.
C
E O a ~
E E~ m u) O O ~
~ 3 ~q O OU) O
~a ~ u~ D. O
~O O ~ 3 _~ ~ o o o ~ ~ ~ 0 v dP dP 3 ~ o ,, o ,, ~ v .~ ~, C~O ~,~ ~ `
r~
E~ ~ lU
D~
a u~ u ~~, ~
E~ .'C E~ ~ o o ~ C~ dP dP dP ~ ~o 1 ~ In Ln O r~) O ,1:: ,r 41 r~ o a~ , ~ O
E-~ ~S ,W :1 1 ~ ¢ @ U~ V~
~1O U, Ul g11) C4 ~ r ~1 O.
^1~ 1~1 ~ ~ ~ ~ O W Q) a :~: E~ ~ '1 ~3 ~
E~ ~1 E~ C~ E ~D ~ W E R
O Z o o t~l ` O ~D tr. u) O _I
~ ~ ~ o,1 _1 u~ E .
~n~ 5~, ~ 3 ~
o o ~, C~V ~
o ~ ~ o o , ~, W ~ .
C 1~ X ~ C W C
.R ~ rl V~
a~ ~ _I S O
~ ~ e J' ~ a ul p --l a v tn w ~
~a w ~ C C C E ~
ul 3 W ~ o --I ~ a~ V I
~ C~ C ~ ~I 0~ Q~V ~ ~~ C
CV u~ C E~ ~1 3 e o n v.,~
.C: O t~ 0 U~ ~d C la r v ~I C ~ 1 ~ V E~ X C ~ 1:: -3 O~ 3 v ~ W ~
E d v C O W ~ C ~o u~ C ~n o X -~ ~ w ~ a o o W ~ ~ W ~ ~ ~Oc~
N C 1` al-rl 3 3 3 0 v~ C ~ O
a) ~ c-,l u~ w 3 u~ 3.Q
2 ~ ~
~4~-Examples 7 and 8 3~-,~
Polvethyl~ne Terephthalake/Glass A composi,e of 35 percent thermoplastic urethane (Estane 58137), 35 percent polyethylene terephthalate (recycled bottle resin), and 30 percent glass was made on a Warner-Pflieder compounding twin-screw extruder. The TPU was characterized by its low viscosity o~ 7-8 X 102 poise, measured on a 20/1, L/D
capillary rheometer at 100 sec~~ shear rate and 260C.
The PET was characteri.zed by its high viscosity of 6 -15 x 103 poise, measured on a 20/1, L/D capillary rheometer at 100 sec~1 shear rate and 260C. The glass was 1/4 inch chopped "E" glass.
The TPU and PET were dried for two hours at 100C. Then the TPU and PET were mixed on the Warner-Pflieder compounding twin-screw extruder, adding gran-ules of these materials at the rear extruder port.
~own stream, after these materials were mixed and heated to about 240C, glass was added. Work and mixing were continued on the compounding extruder.
This composite blend was extruded through an underwater pelletizing die at the end of the extruder, set at about 260C. The knife chopped the strands into pellets at the die face.
The pelle.ts were dried 4 hours at 105C.
The injection molding was carried out in a physical property mold. The mold temperature was set at ~5c.
The melt temperature achieved was 250C. A second similar example was made wherein the TPU was 30 percent weight, the PET was 30 percent weight, and the glass was 40 percent weight. The molded properties are set forth below:
Physical data are set forth .in Table V.
--` 2. 1 3~2/-1~
.
--~7--.,.1 .,~ ~, 0 ~
Gl D. ~ ~ 0 a~ 0 c ,~ 0.a a ~ o o ~1 ~1 ,/ o ~ o ~ . u C6~ 6 8 dP $ $ 8 U
o ~ ~ r O r1 0 -,~ ~
w ~, .,~ , r 0 o 0 o 0~ 0 0 ~ 40 I-,~ ~1 o ~ oo o e ~ E oO g g O U ~ u ¦ X g . r~ N Ir) r ~ O ~ r IY 1~ ~ O ~1 Irl~1 ~ 1N 1~1 C~
:':
O
O X
O O ~ '. `
r al e ~D
o O
~ ~ ~ C ~ , U ,;
o ~ ~, ~ J O a) t~ 0'10~ a) J- +
E~ O ~ E ~
0 1: U~ OE~ , ~ S .~
~ 0 ~ o ~ ~
Crl ~ o w ~ 0 X x ~ C ~ I
U~ C O C ~ O ~\
3~2~
--4fi--As apparent from Table V, fiber-reinforced thermoplastic molding compositions were obtained having extremely high tensile modulus, flexural modulus, heat deflection temperatures, impact resistance, and the like, and yet, the surface was extremely smooth. Inasmuch as the surface is essentially urethane-rich, it is readily paintable without being pr.imed. ..
Examples 9, lo, 11 a.nd 12 TPU/unmodified PET/qlass vs.
lo TPU/modified PET/~lass vs. modified PTU/PET/qlass A composite of thermoplastic polyurethane, polyethylene terephthalate, and glass fiber, in the percentages indicated in Table VI, was made on a pilot scale Werner-Pfleiderer compounding twin screw e.xtruder. The polyurethane was made from a polyester intermediate utilizing MDI and 1,4-butane diol and sold by The BFGoodrich Company as Estane~ 581~2 polyurethane. The TPU was characterized by its low viscosity of 38 poise, measured on a 20/1, L/D
capillary rheometer at 400-500 sec~l shear rate and 250C. For the mTPU used in Comparative Examples lO(a) and 12(a), the polyurethane was modified with Traytuf ~5/200/28 polyethylene terephthalate having a molecular we.ight (Mn) of 9200 and an inherent viscosity of 0.37 as produced by Shell Oil. The polyethylene terephthalate in Examples 9 and 11 was unmodified PET sold by The Goodyear Tire and Rubber Company as TRAYTUF~ 5900C resin. The unmodified PET
was characterized by its hiyh viscosity of 2000 poise, mea~ured on a 20/1, L/D capillary rheometer at 100 sec~1 shear rate and 260C. The PET in Exampl.es 10 and 12 was modi~ied PET, that i5, a random mixed linear copolyester f ormed by the reaction of ethylene glycol, terephthalic acid, 205% (based on total acid) ~5 isophthalic acid and 1-4% (based upon total glycol) diethylene glycol, sold as TRAYTUF~ 6254C resin by The 3l-~2 ., Goodyear Tire and Rubber Company. The modified PET
was characterized by its high viscosity of 2,200 poise, measured on a 20/1, L/D capillary rheometer at 400-500 sec~l shear rate and 270C. The glass was 1/8-inch chopped "E" glass. 0.1-0.3% of carbon black as colorant.
Prior to compounding the TPU and PET were dried for 6 hours at 100C. Then the TPU and PET were mixed on a Werner-Pfleiderer compounding twin-screw extruder, adding granules of thesei materials at the rear extruder port. Downstream, after these ma~erials were mixed and heated to about 240C, glass was added.
Mixing and compounding was continued in the extruder and at 260~C, this composite blend was extruded through a spaghetti die, cooled in air, and chopped into pellets.
The pellets were dried 6 hours at 105C.
The injection molding was carried out in a physical property mold. The mold temperature was set at 45C.
The melt temperature achieved was 250~C.
Physical data are set forth in Table VI.
r ~ 2 4 ~
-50- .
U: _ , _ _ ~ ~
c ~ = ~ E Z~ 1~ ~ 8 ~ .. , ~
~ . . ~ _. . ~
E E E ~ 8 8 ¢ ~ L~ D ~ E ~:^ o o ~ ~ ~ ~ ,~;~
~ ~ __ . - I
~1 D _ ~; E o E, N ~ _.. _.. __ U~ l ~ o ~ l O G l L. ~ 52 C _ ~ _, ~3 ~ 1`~ ' ,, ~ _ __ _ ~
~ ~ ~ ~eo ~ ~ t`'~ '' r~ "';'`
U~ _ ___ _ -- ~..._._ tr: I ~
~ l ~ Q~ 1~ CL
. ~ ~Z~
~. 13 ll2~1 ~
Example 13 The ratio of viscosity of M-PET to TPU was determined for shear rates considered standard for high shear compounding and injection molding. The results are summarized below in Table VII.
- - 2 ~ 3 L~l 2 l~ ~
C ~ , I ~E~
H W ~ OD t`~ ~D
U~ ~ ,1 ~1 ,~
~ U~ ~
~: H
E~ .,,'~
H P~ ~ r c~
:~' ~
~:1 0 H U~
~ ~ 8~
^~ ~ ~1 m o OD 1 U~
~ ,, ~1 .
u ~n ~ o o o ~ U$
~ :~ 3 ~
Examples 14-21 Composite of modified thermoplastic polyurethane, polyethylene terephthalate (modified and unmodified) with and without glass fiber, in the percentages indicated in Tables VIII-XI were made on a pilot scale Werner-Pfleiderer compounding twin screw extruder.
The polyurethane was made from a polyes~er intermediate utilizing MDI and 1,4 butane diol sold by The B.F.Goodrich Co. as ESTANE0 58142 polyurethane.
The TPU is characterized by its low viscosity of 38 poise, measured on a 20/1, C/D capillary rheometer at 400-500 sec 1 shear rate and 250C.
The polyurethane ESTANE~ 58142 polyurethane was modified with TRAYTUF 85/200/~8 polyethylene kerephthalate having a molecular weight (Mn) of 9200, and an inherent viscosity of .37 as produced by the Shell Oil Co.
The polyethylene terephthalate (PET) in the examples was unmodified PET sold by the Shell Oil Co.
as TRAYTUF~ 5900C resin. The unmodified PET was characterized by its high viscosity of 2000 poise, measured on a 20/1 L/D capillary rheometer at 100 sec 1 shear rate and 260C. The random mixed linear copolyester formed by the reaction of ethylene glycol, terephthalic acid, 2056 (based on total acid) isophthalic acid and 1-~% (based upon total glycol) diethylene glycol, sold as TRAYTUF~ 625~C resin by Shell Oil Co. The modified PET was characterized by its high viscosity of 2,200 poise, measured on a 20/1, I./D capillary rheomeker at ~00-500 secl shear rate and 270C. The glass, if added, was 1/8-inch chopped l'E"
ylass. 0.1-0.3% of carbon black was colorant.
Prior to compounding, the TPU and PET were dried for 6 hours at 100C. Then the TPU and PET were mixed on a Werner~Pfleiderer compounding twin-screw extruder, adding granules of these materials at the ~ 3~2~
rear extruder port. Downstream, after these materials were mixed and heated to about 240~C, glass was added. ,~
Mixing and compounding was continued in the extruder and at 260OC, this composi-te blend was extruded through a spaghetti die, cooled in air, and chopped into pellets.
The pellets were dried 6 hours at 105C.
The injection molding was carried out in a physical property mold. The mold temperature was set at 450C.
The melt temperature achieved was 250C~
Physical data are set forth in Tables VIII-XI.
~3~2~
~ r-_ _ ~- = 0~ ~ _ O ~
3 ~ ~ ~_ ~--xl ~ E ~, ~ ~3, _ ~ o . ~33~
= ~
In o u~ o M
~3~2~
_~ -56- ` `
1~ ~T~
~ ~I E ~ 8 ~' o ~ ~ v~ ~ ~^
~ _ x ~ L _ _ _ 9 _~ ' '~ _ L _ _ ~~ ~i ~t _, e o ~- -57- ~ ~3~4 ~ _ . = _ .
~ ~ E ¦ 8 ~ ~ 1` R ~j? ~ ~
~_ -~ _ ___ _l , ~,:
~e " ~ ~ r~ x o t_ ~ o ~3 l E
X ~ E ~ _ _ --~ = ~g~ ~ ~ I
~ ~ ~ ._. _ . .. .___ _ E De i ~ _ _ ....... __ É~ É7 ~: E ' ~ _ A.
1~
U7 o ~ o 2 ~ 4 4 : - 5 8 -_ . _ __ _ ~E 18~ æ ~r~ ~ v~ ~ 0~
~7 C~ I
C~ _ _ U~ I
I
E ~ e I ~} ~ ~o v~ ~3 o 1-E l ~ ;. _ _ _ ,_ ~ _ I
x~ ~ ~1 ~ c ~e I ~ o~ O x ~ ~ ~0 O
.~ E
.~, I
.,.__ _ __ o Xl~ I ~ ~ o~ ~ ~ æ`
~ ~1 ~, I
. - - ~ - - - . .
Ln o Ln C) L 3 L~
;
While in accordance with the Patent Statutes, the best mode and preferred embodiment has been set forth, the scope of the invention is not limited thereto, but rather by the scope of the attached claims.
Claims (27)
1. A thermoplastic molding composition having improved processability, comprising:
a fiber-reinforced blend containing a thermoplastic copolyester with a modified polyurethane component wherein, the modified polyurethane component is a polyurethane modified by an aromatic polyester. Wherein the amount of said thermoplastic copolyester is from about 10 percent to about 90 percent by weightand wherein the amount of said modified polyurethane component is from about 90 percent to about 10 percent by weight based upon the total weight of said thermoplastic copolyester and said modified polyurethane component, and wherein the amount of said fibers is from about 5 percent to about 60 percent by weight based upon the total weight of said thermoplastic copolyester, said modified polyurethane component and said fibers.
a fiber-reinforced blend containing a thermoplastic copolyester with a modified polyurethane component wherein, the modified polyurethane component is a polyurethane modified by an aromatic polyester. Wherein the amount of said thermoplastic copolyester is from about 10 percent to about 90 percent by weightand wherein the amount of said modified polyurethane component is from about 90 percent to about 10 percent by weight based upon the total weight of said thermoplastic copolyester and said modified polyurethane component, and wherein the amount of said fibers is from about 5 percent to about 60 percent by weight based upon the total weight of said thermoplastic copolyester, said modified polyurethane component and said fibers.
2. A thermoplastic molding composition according to Claim 1 wherein said at least one other glycol and/or dicarboxylic acid of said copolyester are an alkane diol or a polyether glycol and/or an aromatic dicarboxylic acid.
3. A thermoplastic molding composition according to Claim 1 wherein said at least one other glycol and/or dicarboxylic acid of said copolyester is diethylene glycol and/or isophthalic acid.
4. A thermoplastic molding composition according to Claim 3 wherein said isophthalic acid is present in an amount of from about 2-5% of the total weight of acid in the copolyester and said diethylene glycol is present in an amount of from about 1-4% of the total weight of glycol in the copolyester.
5. A thermoplastic molding composition according to Claim 1, wherein said fibers are glass fibers.
6. A thermoplastic molding composition according to Claim 5, wherein said thermoplastic copolyester has a viscosity at said high shear at a processing temperature which is different than said modified polyurethane component and wherein the viscosity ratio of said high viscosity component to said relatively low viscosity component is from about 1.5 to about 200 during molding.
7. A thermoplastic molding composition according to Claim 1, wherein said aromatic polyester is polyethylene terephthalate.
8. A thermoplastic molding composition according to Claim 1, wherein said modified polyurethane is modified from about 2 to about 20 mole percent of an aromatic polyester.
9. A thermoplastic molded article formed from the composition claimed in Claim 1.
10. A process for molding a thermoplastic molded article, comprising the steps of:
a) blending under high shear reinforcing fibers with from about 10 percent to about 90 percent by weight of a thermoplastic copolyester and from about 90 percent to about 10 percent by weight of a modified polyurethane component based upon the total weight of said thermoplastic copolyester and saidpolyurethane component, wherein said modified polyurethane component is modified by an aromatic polyester, the amount of said fibers in said blend beingfrom about 5 percent to about 60 percent by weight based upon the total weight of said thermoplastic copolyester, said polyurethane component and said fibers, and b) forming an article having a smooth surface layer essentially free of said fibers; wherei said copolyester is formed by the reaction of ethylene glycol, terephthalic acid and at least one other glycol an/or dicarboxylic acid.
a) blending under high shear reinforcing fibers with from about 10 percent to about 90 percent by weight of a thermoplastic copolyester and from about 90 percent to about 10 percent by weight of a modified polyurethane component based upon the total weight of said thermoplastic copolyester and saidpolyurethane component, wherein said modified polyurethane component is modified by an aromatic polyester, the amount of said fibers in said blend beingfrom about 5 percent to about 60 percent by weight based upon the total weight of said thermoplastic copolyester, said polyurethane component and said fibers, and b) forming an article having a smooth surface layer essentially free of said fibers; wherei said copolyester is formed by the reaction of ethylene glycol, terephthalic acid and at least one other glycol an/or dicarboxylic acid.
11. The process according to Claim 10, wherein said high shear is a shear rate of at least 100 reciprocal seconds.
12. A process according to Claim 10, wherein said thermoplastic copolyester and said polyurethane component have a different viscosity in the presence of said high shear at a processing temperature, and wherein the viscosity ratio of said high viscosity component to said relatively low viscosity component is from about 5 to about 50.
13. The process according to Claim 10, wherein said at least one other glycol and/or dicarboxylic acid of said copolyester are an alkane diol or a polyether glycol and/or a aromatic dicarboxylic acid.
14. The process according to Claim 10, wherein said at least one other glycol and/or dicarboxylic acid of said copolyester is diethylene glycol and/or isophthalic acid.
15. A thermoplastic molding composition, comprising:
a fiber-reinforced blend containing a thermoplastic copolyester with at least one immiscible thermoplastic polymer component, said blend containing an effective amount of said fibers to improve physical properties thereof and beingprepared in the presence of at least moderate shear, said thermoplastic copolyester formed by the reaction of ethylene glycol, terephthalic acid and at least one other glycol and/or dicarboxylic acid, and said immiscible thermoplastic polymer component being selected from thermoplastic polyurethane, polyester-ether polymers block styrenic copolymers, polyether block amide, or ethylene propylenediene, said blend having a smooth surface essentially free of fibers when moldedat high shear.
a fiber-reinforced blend containing a thermoplastic copolyester with at least one immiscible thermoplastic polymer component, said blend containing an effective amount of said fibers to improve physical properties thereof and beingprepared in the presence of at least moderate shear, said thermoplastic copolyester formed by the reaction of ethylene glycol, terephthalic acid and at least one other glycol and/or dicarboxylic acid, and said immiscible thermoplastic polymer component being selected from thermoplastic polyurethane, polyester-ether polymers block styrenic copolymers, polyether block amide, or ethylene propylenediene, said blend having a smooth surface essentially free of fibers when moldedat high shear.
16. A thermoplastic molding composition according to Claim 15, wherein said at least one other glycol and/or dicarboxylic acid of said copolyester are an alkane diol for a polyether glycol and/or an aromatic dicarboxylic acid.
17. A thermoplastic molding composition according to Claim 15, wherein said at least one other glycol and/or dicarboxylic acid of said copolyester is diethylene glycol and/or isophthalic acid.
18. A thermoplastic molding composition according to Claim 15, wherein the immiscible thermoplastic polymer is polyurethane.
19. A thermoplastic molding composition according to Claim 15, wherein the amount of said thermoplastic copolyester is from about 10 percent toabout 90 percent by weight and wherein the amount of said at least one immiscible thermoplastic polymer component is from about 90 percent to about 10 percent by weight based upon the total weight of said thermoplastic copolyester and said at least one immiscible thermoplastic polymer component, and wherein the amount of said fibers is from about 5 percent to about 60 percent by weight based upon the total weight of said thermoplastic copolyester, said atleast one immiscible thermoplastic polymer component and said fibers.
20. A thermoplastic molding composition according to Claim 15, wherein said fibers are glass fibers.
21. A thermoplastic molding composition according to Claim 15, wherein said thermoplastic copolyester has a viscosity at said high shear at a processing temperature which is different than said at least one immiscible thermoplastic polymer component is from about 1.5 to about 200 during molding.
22. A thermoplastic molded article, formed using the composition of Claim 15.
23. A process for molding a thermoplastic molded article, comprising the steps of:
a) blending under high shear reinforcing fibers with from about 10 percent to about 90 percent by weight of thermoplastic copolyester and from about 90 percent to about 10 percent by weight of at least one immiscible thermoplastic polymer component based upon the total weight of said thermoplastic copolyester and said immiscible thermoplastic polymer component, said immiscible thermoplastic polymer component being polyurethane, polyester-ether polymers block styrenic copolymer, polyether block amide or ethylene propylene diene, the amount of said fibers in said blend being from about 5 percent to about 60 percent by weight based upon the total weight of said thermoplastic copolyester, said immiscible thermoplastic polymer component and said fibers, and b) forming an article having a smooth surface layer essentially free of said fibers; wherein said copolyester is formed by the reaction of ethylene glycol, terephthalic acid and at least one other glycol and/or dicarboxylic acid.
a) blending under high shear reinforcing fibers with from about 10 percent to about 90 percent by weight of thermoplastic copolyester and from about 90 percent to about 10 percent by weight of at least one immiscible thermoplastic polymer component based upon the total weight of said thermoplastic copolyester and said immiscible thermoplastic polymer component, said immiscible thermoplastic polymer component being polyurethane, polyester-ether polymers block styrenic copolymer, polyether block amide or ethylene propylene diene, the amount of said fibers in said blend being from about 5 percent to about 60 percent by weight based upon the total weight of said thermoplastic copolyester, said immiscible thermoplastic polymer component and said fibers, and b) forming an article having a smooth surface layer essentially free of said fibers; wherein said copolyester is formed by the reaction of ethylene glycol, terephthalic acid and at least one other glycol and/or dicarboxylic acid.
24. The process according to Claim 23, wherein said high shear is a shear rate of at least 100 reciprocal seconds.
25. A process according to Claim 23, wherein said immiscible thermoplastic polymer component is polyurethane and wherein said fibers are glass fibers.
26. A process according to Claim 23, wherein said thermoplastic copolyester and said immiscible thermoplastic polymer component have a different viscosity in the presence of said high sear at a processing temperature, and wherein the viscosity ratio of said high viscosity component to said relatively low viscosity component is from about 5 to about 50.
27. The process according to Claim 25, wherein said at least one other glycol and/or dicarboxylic acid of said copolyester are an alkane diol or a polyether glycol and/or a aromatic dicarboxylic acid.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/847,529 US5258445A (en) | 1990-03-08 | 1992-03-06 | Fiber-reinforced thermoplastic molding compositions using a copolyester |
US08/145,948 US5519094A (en) | 1992-03-06 | 1993-10-29 | Fiber-reinforced thermoplastic molding compositions using a modified thermoplastic polyurethane |
US08/145,948 | 1993-10-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2134244A1 true CA2134244A1 (en) | 1995-04-30 |
Family
ID=26843430
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2134244 Abandoned CA2134244A1 (en) | 1992-03-06 | 1994-10-25 | Fiber-reinforced thermoplastic molding compositions using a modified thermoplastic polyurethane |
Country Status (1)
Country | Link |
---|---|
CA (1) | CA2134244A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113862827A (en) * | 2021-09-06 | 2021-12-31 | 新疆蓝山屯河高端新材料工程技术研究中心有限公司 | Parallel composite elastic fiber, preparation method and application thereof, and composite spinning pack |
CN114262512A (en) * | 2021-12-28 | 2022-04-01 | 苏州聚复高分子材料有限公司 | Extrusion type 3D printing material for rehabilitation equipment |
-
1994
- 1994-10-25 CA CA 2134244 patent/CA2134244A1/en not_active Abandoned
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113862827A (en) * | 2021-09-06 | 2021-12-31 | 新疆蓝山屯河高端新材料工程技术研究中心有限公司 | Parallel composite elastic fiber, preparation method and application thereof, and composite spinning pack |
CN113862827B (en) * | 2021-09-06 | 2024-03-15 | 新疆蓝山屯河高端新材料工程技术研究中心有限公司 | Parallel composite elastic fiber, preparation method and application thereof, and composite spinning assembly |
CN114262512A (en) * | 2021-12-28 | 2022-04-01 | 苏州聚复高分子材料有限公司 | Extrusion type 3D printing material for rehabilitation equipment |
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