EP1907181A1 - Multilayered, transparent articles containing polyesters comprising a cyclobutanediol and a process for their preparation - Google Patents
Multilayered, transparent articles containing polyesters comprising a cyclobutanediol and a process for their preparationInfo
- Publication number
- EP1907181A1 EP1907181A1 EP06749328A EP06749328A EP1907181A1 EP 1907181 A1 EP1907181 A1 EP 1907181A1 EP 06749328 A EP06749328 A EP 06749328A EP 06749328 A EP06749328 A EP 06749328A EP 1907181 A1 EP1907181 A1 EP 1907181A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- residues
- mole percent
- acid
- mole
- cyclohexanedimethanol
- 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.)
- Withdrawn
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 290
- 238000000034 method Methods 0.000 title claims abstract description 208
- 230000008569 process Effects 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title abstract description 20
- NBBUYPNTAABDEY-UHFFFAOYSA-N cyclobutane-1,1-diol Chemical compound OC1(O)CCC1 NBBUYPNTAABDEY-UHFFFAOYSA-N 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 518
- 229920002647 polyamide Polymers 0.000 claims abstract description 199
- 239000004952 Polyamide Substances 0.000 claims abstract description 198
- 229910052751 metal Inorganic materials 0.000 claims abstract description 83
- 239000002184 metal Substances 0.000 claims abstract description 83
- FQXGHZNSUOHCLO-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-cyclobutanediol Chemical compound CC1(C)C(O)C(C)(C)C1O FQXGHZNSUOHCLO-UHFFFAOYSA-N 0.000 claims abstract description 68
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 442
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 226
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 216
- 150000002009 diols Chemical group 0.000 claims description 201
- -1 polytetramethylene Polymers 0.000 claims description 138
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 109
- 229920000515 polycarbonate Polymers 0.000 claims description 103
- 239000004417 polycarbonate Substances 0.000 claims description 102
- 125000004432 carbon atom Chemical group C* 0.000 claims description 72
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 68
- 125000003118 aryl group Chemical group 0.000 claims description 68
- 125000001931 aliphatic group Chemical group 0.000 claims description 65
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 61
- 239000002253 acid Substances 0.000 claims description 58
- 238000002834 transmittance Methods 0.000 claims description 58
- 229920001778 nylon Polymers 0.000 claims description 48
- 239000004677 Nylon Substances 0.000 claims description 46
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 46
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 39
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 38
- 229910017052 cobalt Inorganic materials 0.000 claims description 35
- 239000010941 cobalt Substances 0.000 claims description 35
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 35
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 34
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 33
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 33
- 239000001361 adipic acid Substances 0.000 claims description 32
- 235000011037 adipic acid Nutrition 0.000 claims description 32
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 32
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 31
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 238000001125 extrusion Methods 0.000 claims description 25
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 24
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 24
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 24
- 229920002292 Nylon 6 Polymers 0.000 claims description 23
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 22
- 125000004427 diamine group Chemical group 0.000 claims description 20
- 230000000737 periodic effect Effects 0.000 claims description 19
- 239000006085 branching agent Substances 0.000 claims description 16
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 16
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 14
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 13
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 13
- 229940035437 1,3-propanediol Drugs 0.000 claims description 13
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 13
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 13
- 238000007056 transamidation reaction Methods 0.000 claims description 13
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 13
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 12
- 238000001746 injection moulding Methods 0.000 claims description 12
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 12
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 12
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 11
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 11
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 239000000600 sorbitol Substances 0.000 claims description 11
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 11
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 claims description 10
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 10
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 10
- 238000000071 blow moulding Methods 0.000 claims description 10
- 238000007664 blowing Methods 0.000 claims description 10
- 239000011975 tartaric acid Substances 0.000 claims description 10
- 235000002906 tartaric acid Nutrition 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 9
- 238000010101 extrusion blow moulding Methods 0.000 claims description 9
- 238000000748 compression moulding Methods 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000003490 calendering Methods 0.000 claims description 7
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 7
- 238000003856 thermoforming Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 4
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 4
- 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 claims description 4
- SBBQDUFLZGOASY-OWOJBTEDSA-N 4-[(e)-2-(4-carboxyphenyl)ethenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1\C=C\C1=CC=C(C(O)=O)C=C1 SBBQDUFLZGOASY-OWOJBTEDSA-N 0.000 claims description 4
- 229920001007 Nylon 4 Polymers 0.000 claims description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 4
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 claims description 4
- 229960004063 propylene glycol Drugs 0.000 claims description 4
- 235000013772 propylene glycol Nutrition 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000299 Nylon 12 Polymers 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 229940093476 ethylene glycol Drugs 0.000 claims description 3
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 230000004888 barrier function Effects 0.000 abstract description 57
- 239000003054 catalyst Substances 0.000 abstract description 15
- 238000010348 incorporation Methods 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 description 131
- 239000010410 layer Substances 0.000 description 129
- 239000010408 film Substances 0.000 description 97
- 238000002156 mixing Methods 0.000 description 53
- 229920001169 thermoplastic Polymers 0.000 description 51
- 229920001230 polyarylate Polymers 0.000 description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 35
- 239000001301 oxygen Substances 0.000 description 35
- 229910052760 oxygen Inorganic materials 0.000 description 35
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 34
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 34
- 239000000463 material Substances 0.000 description 26
- 150000002148 esters Chemical class 0.000 description 24
- 150000004985 diamines Chemical class 0.000 description 21
- 230000005540 biological transmission Effects 0.000 description 19
- 239000002245 particle Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- 229920001634 Copolyester Polymers 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 16
- 150000002334 glycols Chemical class 0.000 description 15
- 150000003951 lactams Chemical class 0.000 description 15
- 239000000155 melt Substances 0.000 description 15
- 230000002000 scavenging effect Effects 0.000 description 15
- 150000002989 phenols Chemical class 0.000 description 13
- 238000006068 polycondensation reaction Methods 0.000 description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 description 12
- 239000005020 polyethylene terephthalate Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 229940106691 bisphenol a Drugs 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- 230000035699 permeability Effects 0.000 description 11
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
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- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
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- 239000002356 single layer Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 8
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
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- 239000000243 solution Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
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- 150000001408 amides Chemical class 0.000 description 5
- 235000001014 amino acid Nutrition 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- OGNSCSPNOLGXSM-UHFFFAOYSA-N (+/-)-DABA Natural products NCCC(N)C(O)=O OGNSCSPNOLGXSM-UHFFFAOYSA-N 0.000 description 4
- 239000004953 Aliphatic polyamide Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 4
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 4
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 4
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 201000010549 croup Diseases 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004990 dihydroxyalkyl group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- WSFMFXQNYPNYGG-UHFFFAOYSA-M dimethyl-octadecyl-(3-trimethoxysilylpropyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCC[Si](OC)(OC)OC WSFMFXQNYPNYGG-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
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- 230000032050 esterification Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical class CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- QMYWABFEOZMOIL-UHFFFAOYSA-N heptanediamide Chemical compound NC(=O)CCCCCC(N)=O QMYWABFEOZMOIL-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- GFMIDCCZJUXASS-UHFFFAOYSA-N hexane-1,1,6-triol Chemical compound OCCCCCC(O)O GFMIDCCZJUXASS-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical class CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229920005621 immiscible polymer blend Polymers 0.000 description 1
- 238000010103 injection stretch blow moulding Methods 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229920005623 miscible polymer blend Polymers 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- ZDPHROOEEOARMN-UHFFFAOYSA-N n-hendecanoic acid Natural products CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 235000010603 pastilles Nutrition 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical class CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920012287 polyphenylene sulfone Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000276 sauconite Inorganic materials 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 229910001467 sodium calcium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005891 transamination reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
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- 239000002759 woven fabric Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
- B29B17/0042—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting for shaping parts, e.g. multilayered parts with at least one layer containing regenerated plastic
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0861—Other specified values, e.g. values or ranges
- B29C2949/0862—Crystallinity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
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- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/105—Metal
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- This invention pertains to transparent, multilayered, shaped articles and a process for their preparation. More specifically, the invention pertains to transparent multilayered articles in which at least one layer contains at least one polyester comprising 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and a separate layer which contains copolyamide or homogeneous blend of polyamides. The layers have small differences in the absolute value of their refractive indices. This invention further pertains to a process for the preparation of transparent, multilayered shaped articles in which scrap polymer regrind can be recycled.
- oxygen barriers include polyethylene vinyl alcohol) (“EVOH”), polyvinyl alcohol) (“PVOH”), polyamides (nylons), and blends of these materials.
- EVOH polyethylene vinyl alcohol
- PVH polyvinyl alcohol
- Polyamides polyamides
- Poly(vinylidene chloride), vinyl chloride copolymers, and vinylidene chloride-methyl acrylate copolymers also are useful as moisture and oxygen barriers.
- barrier polymers may be overcome by using a blend of the barrier polymer with another polymer.
- barrier polymers and other thermoplastic polymers are immiscible and are opaque or hazy. Such blends are not satisfactory for applications requiring clarity such as, for example, beverage containers.
- Polyester polymers such as, for example, poly(ethylene terephthalate) (“PET”), are commonly used in packaging applications. PET has a number of properties that make it useful as a packaging material, including acceptable carbon dioxide barrier properties for soft drinks packaged in bottles containing multiple servings. However, improvements in the carbon dioxide barrier of PET are needed for soft drinks packaged in smaller bottles and in its oxygen barrier, which is not well-suited for packaging oxygen sensitive products such as, for example, beer, citrus products, tomato-based products, and aseptically packed meat.
- Polyethylene naphthalate) (“PEN”) is 3-1 0 times more effective as a barrier than PET but is more expensive.
- Multilayer structures can be used to improve the gas barrier characteristics of PET.
- polymers that have excellent oxygen barrier also referred to as “passive barrier” or scavenging properties (also referred to as “active barrier”) may be combined with PET to produce a layered structure consisting of the individual polymers.
- These multilayer structures are expensive to produce.
- Blends of barrier polymers with PET also have been used to improve the oxygen barrier of packages but, as noted above, often have poor transparency and are not suitable for many packaging applications. The poor transparency of blends also makes it difficult to recycle manufacturing scrap from polymer blends into virgin polymer.
- Copolyester films and extrusion blow molded (“EBM”) bottles are often desired for toughness, and are commonly used instead of PET for extrusion blow molding and film applications. These applications often require barrier that is comparable to that of oriented PET. Unfortunately, however, the barrier properties of copolyesters are inferior to oriented PET. Multilayer structures can be produced by coextruding a thin, barrier film into the center of a thicker bulk structure to improve the overall barrier. To be economical, however, EBM and film processes typically require that high levels (up to 80%) of regrind (i.e., flash and trim) are reprocessed.
- regrind i.e., flash and trim
- a polymer blend that provides good passive and/or active barrier properties, is economical, and can be recycled efficiently is needed in the art.
- Such blends should be transparent, contain thermoplastic and barrier polymers that provide a high barrier for oxygen, water, and carbon dioxide, and can be used economically in article forming processes which incorporate a high level of regrind.
- barrier and thermoplastic polymer compositions that can be used to economically produce multilayered articles having high transparency and can tolerate a high level of regrind.
- Polymer compositions having high transparency and high barrier properties can be prepared from a immiscible blend of one or more thermoplastic polymers and a copolyamide or a homogeneous, transamidized blend of at least 2 polyamides in which the difference in refractive index between the polyamide component and thermoplastic polymer component is about 0.006 to about -0.0006.
- the present invention provides a polymer composition, comprising an immiscible blend of: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - RI(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 10% or less.
- the first component comprises a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3- cyclobutanediol, and 1 ,4-cyclohexanedimethanol.
- the invention also provides a polymer composition, comprising an immiscible blend of: (i) a first component comprising at least one polyester which comprises:
- diacid residues comprising about 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms; and
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol; and
- a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 10% or less.
- the first component comprises at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends of these polymers
- the second component comprises a blend of at least 2 polyamides which have been transamidized to produce a homogeneous blend.
- refractive indices of the first and second components can be closely matched by selecting at least 2 polyamides having different levels of aliphatic and aromatic residues and transamidizing these polyamides to form a homogeneous blend.
- homogeneous blends of the thermoplastic polymers and the polymamides can be used to tailor refractive indices of the second component and the first component to within desired ranges such that the difference in refractive indices is about 0.006 to about - 0.0006.
- a homogeneous blend of a polyester and a polycarbonate comprising the residues of bisphenol A can be used as the first component and a transamidized, homogeneous blend of first polyamide comprising the residues of m-xylylenediamine and adipic acid, and a second aliphatic polyamide can be used as the barrier polymer.
- the first and second components form clear, immiscible blends that are suitable for the preparation of high clarity, shaped articles that can be used in many packaging applications.
- Multilayered articles may also be prepared by a variety of processes known in the art.
- the first and second components may be coextruded or coinjected from the melt into separate layers, or the layers may be formed individually and brought together in a subsequent process such as, for example, lamination.
- the second component also can comprise a copolyamide having a ratio of aromatic and aliphatic dicarboxylic acid and diamine residues that can be varied to closely match the refractive indices of the first and second components.
- a polymer composition comprising an immiscible blend of:
- thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof;
- the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 10% or less.
- the first component comprises a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, and 1 ,4-cyclohexanedimethanol.
- diacid residues comprising about 70 to about 1 00 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 1 0 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms; and (b) diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4, 4-tetramethyl-
- Another aspect of our invention is a polymer composition prepared by a process comprising melt blending:
- a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the composition has a percent transmittance of at least 75%, and a haze of 10% or less.
- the first component comprises a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, and 1 ,4-cyclohexanedimethanol.
- the invention therefore, also provides a polymer composition, prepared by a process comprising melt blending:
- a first component comprising at least one polyester which comprises:
- diacid residues comprising about 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms; and
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4, 4-tetramethyl- 1 ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol; and
- a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the composition has a percent transmittance of at least 75%, and a haze of 10% or less.
- compositions of our invention show excellent barrier properties.
- the oxygen barrier properties may be enhanced by incorporating transition metal catalysts such as, for example, cobalt, manganese, iron, ruthenium, copper, nickel, palladium, and platinum into the blends to produce oxygen scavenging compositions.
- transition metal catalysts such as, for example, cobalt, manganese, iron, ruthenium, copper, nickel, palladium, and platinum into the blends to produce oxygen scavenging compositions.
- the invention thus, further provides an oxygen-scavenging composition comprising:
- first component comprising at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof;
- second component comprising a transamidized, homogeneous blend of at least two polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 1 0% or less;
- Typical metal catalysts include, but are not limited to, cobalt, manganese, and iron.
- the first component of the immiscible blend may comprise a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclo- butanediol, and 1 ,4-cyclohexanedimethanol.
- another embodiment of the invention is an oxygen-scavenging composition comprising: (A) an immiscible blend comprising
- a first component comprising at least one polyester which comprises:
- diacid residues comprising about 70 to about 1 00 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms; and (b) diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2, 2,4,4- tetramethyl-l ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol; and (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have
- the blends of the present invention are useful for producing clear, shaped articles having improved barrier properties, melt processability, and excellent mechanical properties, and which can be prepared using a high proportion of regrind to virgin polymer. These shaped articles may have a single layer or multiple layers and have numerous packaging applications. Accordingly, the invention further provides a process for forming a shaped article, comprising:
- a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a copolyamide or a homogeneous, transamidized blend of at least 2 polyamides; wherein the first component (i) and second component (ii) form an immiscible blend, the second component and the first component have a difference in refractive index, RKsecond component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 1 0% or less;
- the instant invention also includes a process for forming a shaped article, comprising:
- diacid residues comprising about 70 to about 1 00 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms;
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4,4- tetramethyl-l ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol;
- a second component comprising a copolyamide or a homogeneous, transamidized blend of at least 2 polyamides; wherein the first component (i) and second component (ii) form an immiscible blend, the second component and the first component have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 10% or less;
- step (F) combining the polymer regrind with the first and second components (i) and (ii) of step (A).
- the shaped article may be produced by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing.
- the shaped articles may have one or more layers comprising an immiscible blend of the first and second components or can have multiple layers in which the first and second components are in separate layers.
- the invention therefore, also provides a multilayered, shaped article, comprising:
- a first layer comprising at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof; and (ii) a second layer comprising a transamidized homogeneous blend of at least two polyamides; wherein the second layer (ii) and the first layer (i) have a difference in refractive index, Rl(second layer) - Ri(first layer), of about 0.006 to about -0.0006, and the shaped article has a percent transmittance of at least 75%, and a haze of 1 0% or less.
- the first layer can comprise a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, and 1 ,4- cyclohexanedimethanol.
- another embodiment of the invention is a multilayered, shaped article, comprising: (i) a first layer comprising at least one polyester which comprises: (a) diacid residues comprising about 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 1 6 carbon atoms; and
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4, 4-tetramethyl- 1 ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol; and
- a second layer comprising a transamidized, homogeneous blend of at least two polyamides; wherein the second layer (ii) and the first layer (i) have a difference in refractive index, Rl(second layer) - Rl(first layer), of about 0.006 to about -0.0006, and the shaped article has a percent transmittance of at least 75%, and a haze of 1 0% or less.
- the invention further provides a process for forming a multilayered shaped article, comprising: (i) heating a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof to a temperature of about Tg + 100 0 C to about Tg + 300 0 C of the first component; (ii) heating a second component comprising a copolyamide or a transamidized, homogeneous blend of at least two polyamides to a temperature of about Tg +10O 0 C to about Tg + 300 0 C of the second component; (iii) forming a shaped article having the first and second components in separate layers;
- step (iv) recovering scrap first and second components; (v) grinding the scrap first and second components to produce a regrind; (vi) optionally, drying the regrind; and (vii) combining the regrind with the first component, second component, or a combination thereof, of steps (i) and (ii); wherein the second component of step (ii) and the first component of step (i) of have a difference in refractive index, Rl(second component) - Rl (first component), of about 0.006 to about -0.0006, and the shaped article has a percent transmittance of at least 75%, and a haze of 10% or less.
- the first component can comprise a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, and 1 ,4- cyclohexanedimethanol.
- another aspect of the invention is a process for forming a multilayered shaped article, comprising: (i) heating a first component to a temperature of about Tg +10O 0 C tO about
- the first component comprising at least one polyester which comprises:
- diacid residues comprising about 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms; and
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4, 4-tetramethyl- 1 ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol; (ii) heating a second component comprising a copolyamide or a transamidized, homogeneous blend of at least two polyamides to a temperature of about Tg + 100 0 C to about Tg + 300 0 C of of the second component; (iii) forming a shaped article having the first and second components in separate layers;
- step (v) grinding the scrap first and second components to produce a regrind; (vi) optionally, drying the regrind; and (vii) combining the regrind with the first component, second component, or a combination thereof, of steps (i) and (ii); wherein the second component of step (ii) and the first component of step (i) of have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the shaped article has a percent transmittance of at least 75%, and a haze of 10% or less.
- the regrind may be incorporated into the first or second layer and may be from about 5 to about 60 weight percent of the article.
- Polymer compositions having high clarity and good barrier properties can be prepared from an immiscible blend of one or more thermoplastic polymers and a transamidized, homogeneous blend of at least two polyamides, in which the difference in refractive index between the blend of polyamides and the thermoplastic polymers is about 0.006 to about -0.0006.
- the immiscible blend has a percent transmittance of at least 75%, and a haze of 10% or less.
- the present invention provides polymer composition, comprising an immiscible blend of: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 10% or less.
- thermoplastic polymers and polyamides may be selected from a wide variety of polymers.
- the first component can comprise a polyester comprising the residues of terephthalic acid, 2,2,4,4 ⁇ tetramethyl-l ,3-cyclobutanediol, and 1 ,4- cyclohexanedimethanol.
- the refractive indices of the second component and the first component can be adjusted to give a difference of about 0.006 to about - 0.0006 by the selection and ratio of the polyamides of the second component or, alternatively, by blending the thermoplastic polymers of the first component to form a homogeneous blend.
- Our novel compositions can be used to manufacture shaped articles having one or more layers such as, for example, sheets, films, tubes, bottles, and profiles.
- the shaped article may be produced by extrusion, calendering, thermoforming, blow-molding, extrusion blow- molding, injection molding, compression molding, casting, drafting, tentering, or blowing.
- Multilayer articles can be prepared in which the immiscible blend is present in one or more layers or the first and second components are in separate layers. Because of the small difference in the refractive indices of the first and second components, shaped articles prepared from the composition of the invention can incorporate substantial quantities of regrind and retain good transparency. The clarity and barrier properties of these shaped articles produced make them particularly useful for packaging applications.
- a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, for example 1 , 2, 3, 4, etc., all fractional numbers between 0 and 10, for example 1 .5, 2.3, 4.57, 6.1 1 13, etc., and the endpoints 0 and 10.
- a range associated with chemical substituent groups such as, for example, "Ci to Cs hydrocarbons”, is intended to specifically include and disclose Ci and Cs hydrocarbons as well as C 2 , C 3 , and C 4 hydrocarbons.
- polyester is intended to include homopolyesters, copolyesters, and terpolyesters.
- polyesters are synthetic polymers prepared by the polycondensation of one or more difunctional and/or multifunctional carboxylic acids with one or more difunctional and/or multifunctional hydroxyl compounds.
- the difunctional carboxylic acid is a dicarboxylic acid or a hydroxycarboxylic acid
- the difunctional hydroxyl compound is a dihydric alcohol such as, for example, glycols and diols.
- the polyesters of the invention can contain branching monomers which may contain 3 or more carboxylic acid groups, hydroxyl groups, or a combination of carboxylic acid and hydroxyl groups. Therefore, the terms “diacid” or “dicarboxylic acid”, as used herein, are intended also to include multifuntional carboxylic acids which may be used as branching monomers such as, for example, trimellitic acid. Similarly, the terms “diol” or “glycol”, as used herein, are intended also to include multifunctional hydroxyl compounds which may be used as branching monomers such, as, for example, pentaerythritol.
- the difunctional or multifunctional carboxylic acid may be an aliphatic or cycloaliphatic dicarboxylic acid such as, for example, adipic acid, or an aromatic dicarboxylic acid such as, for example, terephthalic acid.
- the difunctional hydroxyl compound may be cycloaliphatic diol such as, for example, 1 ,4-cyclohexanedimethanol, a linear or branched aliphatic diol such as, for example, 1 ,4-butanediol, or an aromatic diol such as, for example, hydroquinone.
- the polyesters used in the present invention typically are prepared from dicarboxylic acids and diols which react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues.
- the polyesters derived from dicarboxylic acid and diol residues of the present invention therefore, contain substantially equal molar proportions of acid residues (100 mole percent) and diol residues (100 mole percent) such that the total moles of repeating units is equal to 1 00 mole percent.
- the mole percentages provided in the present disclosure therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units.
- a copolyester containing 30 mole percent terephthalic acid means that the copolyester contains 30 mole percent terephthalic residues out of a total of 100 mole percent acid residues.
- a copolyester containing 30 mole percent 1 ,4-cyclohexanedimethanol means that the copolyester contains 30 mole percent 1 ,4-cyclohexanedimethanol residues out of a total of 100 mole percent diol residues.
- copolyesters of terephthalic acid, ethylene glycol, and 1 ,4-cyclohexandimethanol may be referred to as "PET” when the glycol component is primarily ethylene glycol, "PCT” when the glycol component is primarily 1 ,4-cyclohexanedimethanol, "PETG” when the ratio of ethylene glycol to 1 ,4-cyclohexanedimethanol is greater than 1 and "PCTG” when the ratio of ethylene glycol to 1 ,4-cyclohexanedimethanol ratio is less than 1.
- polyamide is intended to include synthetic polymers prepared by the polycondensation of one or more difunctional carboxylic acids with one or more difunctional amines or by the ring-opening polymerization of a lactam and may include homopolymers and copolymers.
- the difunctional carboxylic acid can be a dicarboxylic acid such as adipic acid or isophthalic acid
- the difunctional amine can be a diamine such as, for example, hexamethylene diamine or m-xylylenediamine.
- copolyamide as used herein, is understood to mean a polyamide comprising at least 2, chemically distinct repeating units.
- MXD6 nylon is not a copolyamide because it contains only a single, chemically distinct repeating unit containing the residues of adipic acid and m-xylylenediamine.
- poly(hexamethylene adipamide-co-isophthalamide) prepared by the condensation of hexamethylenediamine with adipic and isophthalic acid, has two chemically distinct repeating units, that is, a repeating unit containing the residues of hexamethylenediamine and adipic acid, and another repeating unit containing the residues of hexamethylene diamine and isophthalic acid.
- polycarbonate is herein defined as the condensation product of a carbonate source and a diol source, having a carbonate component containing 100 mole percent carbonate units and a diol component containing 100 mole percent diol units, for a total of 200 mole percent monomeric units or 100 mole percent "repeating units".
- the polycarbonate portion of the first component is based upon the polycarbonate of 4,4'-isopropylidenediphenol, commonly known as bisphenol A polycarbonate.
- linear or branched polycarbonates that may be utilized in the present invention may be derived from bisphenol A and can be prepared according to procedures well known in the art such as, for example, as disclosed in U.S. Patent No.'s 3,030,335 and 3,31 7,466.
- Examples of bisphenol A polycarbonates that may be used in the present invention and are available commerically include the materials marketed under the tradenames LEXAN ® , available from the General Electric Company, and MAKROLON ® , available from Bayer, Inc.
- polyarylate as used herein, is understood to mean polyesters prepared by the polycondensation of one or more difunctional aromatic dicarboxylic acids with one or more dihydric phenols.
- typical aromatic dicarboxylic acids are terephthalic and isophthalic acid
- typical aromatic diphenols are bisphenol A and hydroquinone.
- residue as used herein in reference to the polymers of the invention, means any organic structure incorporated into a polymer through a polycondensation or ring opening reaction involving the corresponding monomer.
- replicaating unit as used herein, means shortest sequence of monomer residues that can be found repeatedly in a polymer.
- a repeating unit is an organic structure having dicarboxylic acid residue and a diol residue, or hydroxycarboxylic acid residues bonded through a carbonyloxy group.
- a repeating unit is an organic structure having a dicarboxylic acid and a diamine residue, lactam, or aminoacid residues, bonded through a amide group.
- residues associated within the various polyesters, polyamide, polycarbonates, and polyarylates of the invention can be derived from the parent monomer compound itself or any derivative of the parent compound.
- the dicarboxylic acid and amino acid residues referred to in the polymers of the invention may be derived from a dicarboxylic acid or aminoacid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof.
- dicarboxylic acid or “aminoacid” is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process with a diol to make a high molecular weight polyester, polyamide, polycarbonate, or polyarylate.
- hydroxycarboxylic acid is intended to include aliphatic and cycloaiiphatic hydroxycarboxylic acids as well as monohydroxy-monocarboxylic acids and any derivative thereof, including their associated acid halides, esters, cyclic esters (including dimers such as lactic acid lactides), salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process or ring opening reaction to make a high molecular weight polyester.
- aminoacid is intended to include aliphatic, aromatic, and cycloaiiphatic aminoacids and any derivative thereof, including their associated acid halides, amides, cyclic amides (lactams), salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process or ring opening reaction to make a high molecular weight polyamide.
- diamine is intended to include diamines as well as their associated salts, amides, or any other derivative thereof that are useful for the preparation of polyamides.
- I.V. inherent viscosity
- refractive index refers to refractive index measurements obtained according to standard methods well known in the art.
- the refractive indices reported herein were determined at a wavelength of 633 nm using a Metricon Prism CouplerTM model 2010 refractometer (available from Metricon Inc.) and are reported as the average of the refractive indices measured in 3 orthogonal directions (extrusion or stretch, transverse, and thickness directions).
- difference in refractive index as used herein in the context of the compositions, processes, and shaped articles of the invention always means the value obtained by subtracting the refractive index of the polyester, polycarbonate, or polyarylate- containing component (typically referred to herein as the "first component” or “first layer” in multilayered articles) from the refractive index of the polyamide- or copolyamide-containing component (typically referred to herein as the "second component” or “second layer” in multilayered articles).
- ⁇ RI difference in refractive index
- ⁇ RI Rf (second component or layer) - Rl (first component or layer) It will be evident to persons skilled in the art that the difference in refractive index may be a positive or negative number.
- percent transmittance is synonymous with the term “percent transmission”. The procedure for the determination of refractive index is provided in the Examples.
- haze and percent transmittance is determined by molding or casting the composition into a sheet or film having a thickness of 1 /8 inch or less and measuring the haze and percent transmittance according to the procedures described in the examples.
- the haze and percent transmittance can be determined by cutting out a small (i.e., 1 X 1 cm) section of the article, having a thickness of 1 /8 inch or less, and measuring the haze according the procedure described herein.
- compositions of the present invention comprise a first component comprising one or more thermoplastic polymers selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof.
- thermoplastic polymer as used herein, is intended to have its plain meaning as would be understood by persons having ordinary skill in the art, that is, a polymer that softens when exposed to heat and returns to its original condition when cooled to room temperature.
- the first component may comprise a single thermoplastic polymer or may comprise a blend of 2 or more polymers provided that the blend is a homogeneous blend.
- the term "homogeneous blend”, as used herein, is synonymous with the term “miscible”, and is intended to mean that the blend has a single, homogeneous phase as indicated by a single, composition-dependent Tg.
- a first polymer that is miscible with second polymer may be used to "plasticize" the second polymer as illustrated, for example, in U.S. Patent No. 6,21 1 ,309.
- Homogeneous blends may be formed by simply blending two or polymers or, in the case of condensation polymers such as for example, polyesters or polyamides, by transesterifying or transamidating two or more polymers.
- condensation polymers such as for example, polyesters or polyamides
- transesterifying or transamidating two or more polymers By contrast, the term "immiscible", as used herein, denotes a blend that shows at least 2, randomly mixed, phases and exhibits more than one Tg. Some polymers may be immiscible and yet compatible with each other.
- a further general description of miscible and immiscible polymer blends and the various analytical techniques for their characterization may be found in Polymer Blends Volumes 1 and 2, Edited by D.R. Paul and CB. Bucknall, 2000, John Wiley & Sons, Inc.
- the first component may comprise one or more thermoplastic polymers selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof.
- the first component may comprise a polyester comprising (a) diacid residues, comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanol; neopentyl glycol, diethylene glycol,
- the diacid residues can comprise the residues of one or more dicarboxylic acids selected from terephthalic acid, isophthalic acid, or combinations thereof, and the diol residues comprise the residues of one or more diols selected from 1 ,4-cyclohexanedimethanol, neopentyl glycol, ethylene glycol, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, and combinations thereof.
- the diacid residues may comprise the residues of terephthalic acid and isophthalic acid.
- the diacid residues may comprise from about 60 to about 100 mole percent of the residues terephthalic acid and 0 to about 40 mole percent of the residues isophthalic acid and the diol residues may comprise about 100 mole percent of the residues of 1 ,4-cyclohexanedimethanol.
- dicarboxylic acid content examples include about 80 to about 100 mole percent of the residues of terephthalic acid and 0 to 20 mole percent of the residues isophthalic acid, about 95 to about 100 mole percent of the residues of terephthalic acid, and about 1 00 mole percent of the residues of terephthalic acid.
- polyesters comprising: (a) diacid residues comprising about 80 to about 100 mole percent of the residues of terephthalic acid and diol residues comprising about 50 to about 90 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 10 to about 50 mole percent of the residues of neopentyl glycol; (b) diacid residues comprising 100 mole percent of the residues of terephthalic acid and diol residues comprising about 10 to about 40 mole percent of the residues of 1 ,4-cyclohexanedimethanol and 60 to about 90 mole percent of the residues of ethylene glycol; (c) diacid residues comprising about 100 mole percent terephthalic acid and diol residues comprising about 10 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol, 0 to
- the first component can comprise at least one polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol, and 1 ,4-cyclohexanedimethanol.
- the polyester may comprise (a) diacid residues comprising about 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms; and (b) diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4,4-tetramethyl-l ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol.
- polyesters that may be used in the first component include, but are not limited to, polyesters comprising 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms and any one of the following diol residue compositions: (i) about 5 to about 60 mole percent of the residues of 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and about 40 to about 95 mole percent of the residues of 1 ,4-cyclohexanedimethanol; (ii) about 1 5 to about 40 mole percent of the residues of 2,2,4,4-tetramethyl-l ,3-cyclo- butanediol and about
- the dicarboxylic acid may be selected from terephthalic acid and isophthalic acid, and the diol is selected from 1 ,4-cyclohexanedimethanol and ethylene glycol.
- the dicarboxylic acid is terephthalic acid and the diol is 1 ,4-cyclohexanedimethanol.
- the diacid residues may comprise at least 95 mole percent of the residues of terephthalic acid and the diol residues may comprise about 10 to about 40 mole percent of the residues of 1 ,4-cyclohexanedimethanol, about 1 to about 25 mole percent of the residues of diethylene glycol, and about 35 to about 89 mole percent of the residues of ethylene glycol.
- the polyester may further comprise 0 to about 30 mole percent of one or more residues of a modifying diacid containing 2 to 20 carbon atoms if desired.
- a modifying diacid containing 2 to 20 carbon atoms if desired.
- from 0 to about 30 mole % of other aromatic dicarboxylic acids containing 8 to about 16 carbon atoms, cycloaliphatic dicarboxylic acids containing 8 to about 16 carbon atoms, aliphatic dicarboxylic acids containing about 2 to about 16 carbon atoms, or mixtures thereof may be used.
- modifying aromatic dicarboxylic acids include, but are not limited to, one or more of 4,4'-biphenyldicarboxylic acid, isophthalic acid, 1 ,4- naphthalene- dicarboxylic acid, 1 ,5- naphthalenedicarboxylic acid, 2,6- naphthalene- dicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-oxybenzoic acid, and trans-4,4'-stilbenedicarboxylic acid.
- modifying aliphatic dicarboxylic acids include, but are not limited to, one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
- the diacid component of the polyester may be modified with 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms.
- the polyester can comprise about 1 to about 99 mole percent, based on the total moles of diol residues, of the residues of 1 ,4-cyclohexanedimethanol, about 99 to about 1 mole percent of the residues ethylene glycol.
- Typical mole percentages for the residues of 1 ,4- cyclohexanedimethanol for the polyesters of the invention include from about 1 to about 10 mole percent, from about 1 to about 25 mole percent, from about 1 to about 40 mole percent, 50 mole percent and greater, and 100 mole percent.
- the dicarboxylic acid is 1 ,4- cyclohexanedicarboxylic acid and the diol is 1 ,4-cyclohexanedimethanol.
- the polyester may comprise the residues of 1 ,4-cyclohexanedimethanol units and the neopentyl glycol.
- the polyester may comprise the residues of 1 ,4-cyclohexanedimethanol units and 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol.
- the diol component of the polyester also may be modified from 0 to about 20 mole percent of the residues of at least one modifying diol having from 3 to 16 carbons.
- Other ranges of modifying diol include, but are not limited to, from 0 to about 10 mole percent, and less than 5 mole percent.
- the modifying diol may be selected from one or more of 1 ,2-propanediol, 1 ,3- propanediol, 1 ,4-butanedioI, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,4- cyclohexanedimethanol, p-xylene glycol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol, and 2, 2, 4, 4-tetramethyl-l ,3-cyclobutanediol.
- polyalkylene glycols examples include poly(tetramethylene glycol) (“PTMG”) and poly(ethylene glycol) (“PEG”) having molecular weights up to about 2,000.
- the diol component for example, can be modified with 0 to about 10 mole percent polyethylene glycol or polytetramethylene glycol to enhance elastomeric behavior.
- the diol residues may comprise about 10 to about 99 mole percent of residues of 1 ,4-cyclohexanedimethanol, 0 to about 90 mole percent of residues of ethylene glycol, and about 1 to about 25 mole percent of residues of diethylene glycol.
- the polyester also may contain up to about 5 mole percent, typically from about 0.01 to about 2.0 mole%, or more typically, about 0.01 to about 1 mole percent, based on the total acid or diol residues, of the residues of a polyfunctional branching agent derived from a compound having at least three carboxyl and/or hydroxy groups to form a branched polyester.
- a polyfunctional branching agent derived from a compound having at least three carboxyl and/or hydroxy groups to form a branched polyester.
- examples of such compounds include trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride, glycerol, sorbitol, 1 , 2, 6-hexanetriol, pentaerythritol, tartaric acid, citric acid, trimethylolethane, and trimesic acid, and the like.
- the final composition can be arrived at by blending various resins or by direct reactor copolymerization. The latter is desirable to minimize compositional variability
- polyesters are those containing about 1 00 mole percent terephthalic residues, based on the total diacid residues, and any one of the following diol residue compositions, based on the total diol residues: (0 about 1 to about 5 mole percent of the residues of 1 ,4-cydohexane- dimethanol and about 99 to about 95 mole percent of the residues of ethylene glycol; (ii) about 29 to about 33 mole percent of the residues of 1 ,4-cyclo- hexanedimethanol and about 71 to about 67 mole percent of the residues of ethylene glycol; (iii) about 45 to about 55 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 55 to about 45 mole percent of the residues of ethylene glycol; (iv) about 60 to about 65 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 40 to about
- compositions comprising polyesters formed from terephthalic acid, an ester thereof, or mixtures thereof, 1 ,4- cyclohexanedimethanol and 2,2,4,4-tetramethyl-i ,3-cyclobutanediol with certain monomer compositions, inherent viscosities and/or glass transition temperatures are superior to polyesters known in the art and to polycarbonate with respect to one or more of high impact strengths, hydrolytic stability, toughness, chemical resistance, good color and clarity, long crystallization half- times, low ductile to brittle transition temperatures, lower specific gravity, and thermoformability. These compositions are believed to be similar to polycarbonate in heat resistance and are still processable on the standard industry equipment.
- the Tg of the polyesters useful in the compositions, processes, and shaped articles of the invention can be at least one of the following ranges: 60 to 200°C; 60 to 190 0 C; 60 to 180 0 C; 60 to 170°C; 60 to 160 0 C; 60 to 1 55°C; 60 to 1 50 0 C; 60 to 145°C; 60 to 140°C; 60 to 138°C; 60 to 1 35°C; 60 to 130°C; 60 to 1 25°C; 60 to 1 20 0 C; 60 to 1 1 5°C; 60 to 1 10°C; 60 to 105°C; 60 to 100°C; 60 to 95°C; 60 to 90 0 C; 60 o 85°C; 60 to 80°C; 60 to 75 0 C; 65 to 200°C; 65 to 1 90°C; 65 to 1 80 0 C; 65 to 1 70°C; 65 to l 60°C; 65 to 1 55 0 C; 65 to 1 5O
- the glycol component for the polyesters of the invention include but are not limited to at least one of the following combinations of ranges: 1 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 99 mole % 1 ,4-cyclohexanedimethanol; 1 to 95 mole % 2,2,4,4-tetramethyl-l ,3 ⁇ cyclobutanediol and 5 to 99 mole % 1 ,4-cyclohexanedimethanol; 1 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 99 mole % 1 ,4-cyclohexanedimethanol; 1 to 85 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 1 5 to 99 mole % 1 ,4-cyclohexanedimethanol;
- the glycol component for the polyesters of the invention include but are not limited to at least one of the following combinations of ranges: 0.01 to less than 5 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 95 to 99.99 mole % 1 ,4-cyclohexanedimethanol; 0.01 to 4.5 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 95.5 to 99.99 mole % 1 ,4-cyclohexanedimethanol; 0.01 to 4 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 96 to 99.99 mole % 1 ,4-cyclohexanedimethanol; 0.01 to 3.5 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 96.5 to 99.99 mole
- the glycol component can include but is not limited to at least one of the following combinations of ranges: 5 to 99 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 1 to 95 mole % 1 ,4- cyclohexanedimethanol; 5 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 95 mole % 1 ,4-cyclohexanedimethanol; 5 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 95 mole % 1 ,4-cyclohexanedimethanol; 5 to 85 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 1 5 to 95 mole % 1 ,4-cyclohexanedimethanol; 5 to 80 mole % 2,2,4,4-te
- the glycol component can include but is not limited to at least one of the following combinations of ranges: 5 to less than 50 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and greater than 50 to 95 mole % 1 ,4-cyclohexanedimethanol; 5 to 45 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 55 to 95 mole % 1 ,4-cyclohexane- dimethanol; 5 to 40 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 60 to 95 mole % 1 ,4-cyclohexanedimethanol; 5 to 35 mole % 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol and 65 to 95 mole % 1 ,4-cyclohexanedimethanol;
- the glycol component for the polyesters of invention can include but is not limited to at least one of the following combinations of ranges: 10 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 90 mole % 1 ,4-cyclohexanedimethanol; 10 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 90 mole % 1 ,4-cyclohexanedimethanol; 10 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 90 mole % 1 ,4-cyclohexanedimethanol; 10 to 85 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 1 5 to 90 mole % 1 ,4-cyclohexane-
- the glycol component can include but is not limited to at least one of the following combinations of ranges: 14 to 99 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 1 to 86 mole % 1 ,4- cyclohexanedimethanol; 14 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 86 mole % 1 ,4-cyclohexanedimethanol; 14 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 86 mole % 1 ,4-cyclohexanedimethanol; 14 to 85 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 1 5 to 86 mole % 1 ,4-cyclohexanedimethanol;
- the glycol component of the polyesters of the invention can include but is not limited to at least one of the following combinations of ranges: 1 5 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 85 mole % 1 ,4-cyclohexanedimethanol; 1 5 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 85 mole % 1 ,4-cyclohexanedimethanol; 15 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 85 mole % 1 ,4-cyclohexanedimethanol; 1 5 to 85 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 1 5 to 85 mole % 1 ,4-cyclohexanedimethanol; 1 5 to
- the glycol component for the polyesters of the invention can include but is not limited to at least one of the following combinations of ranges: 20 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 80 mole % 1 ,4-cyclohexanedimethanol; 20 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 80 mole % 1 ,4-cyclohexanedimethanol; 20 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 80 mole % 1 ,4-cyclohexanedimethanol; 20 to 85 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 1 5 to 80 mole % 1 ,4-cyclohexanedimethanol; 20 to 85 mole
- the glycol component for the polyesters of the invention can include but is not limited to at least one of the following combinations of ranges: 25 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 75 mole % 1 ,4-cyclohexanedimethanol; 25 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 75 mole % 1 ,4-cyclohexanedimethanol; 25 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 75 mole % 1 ,4-cyclohexanedimethanol; 25 to 85 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 1 5 to 75 mole % 1 ,4-cyclohexanedimethanol; 25 to 85 mole
- the glycol component for the polyesters of the invention can include but is not limited to at least one of the following combinations of ranges: 30 to 99 mole % 2,2,4,4-tetramethyl-1 ,3- cyclobutanediol and 1 to 70 mole % 1 ,4-cyclohexanedimethanol; 30 to 95 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol and 5 to 70 mole % 1 ,4-cyclohexanedimethanol; 30 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 70 mole % 1 ,4-cyclohexanedimethanol; 30 to 85 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 1 5 to 70 mole % 1 ,4-cyclohexanedimethanol
- the glycol component for the polyesters of the invention can include but is not limited to at least one of the following combinations of ranges: 35 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 65 mole % 1 ,4-cyclohexanedimethanol; 35 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 65 mole % 1 ,4-cyclohexanedimethanol; 35 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 65 mole % 1 ,4-cyclohexanedimethanoi; 35 to 85 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 1 5 to 65 mole % 1 ,4-cyclohexanedimethanol; 35 to 85 mo
- the glycol component for the polyesters of the invention can include but is not limited to at least one of the following combinations of ranges: 40 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 60 mole % 1 ,4-cyclohexanedimethanol; 40 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 60 mole % 1 ,4-cyclohexanedimethanol; 40 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 60 mole % 1 ,4-cyclohexanedimethanol; 40 to 85 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 1 5 to 60 mole % 1 ,4-cyclohexanedimethanol; 40 to 85 mole
- the glycol component for the polyesters of the invention can include but are not limited to at least one of the following combinations of ranges: 45 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 55 mole % 1 ,4-cyclohexanedimethanol; 45 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 55 mole % 1 ,4-cyclohexanedimethanol; 45 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 55 mole % 1 ,4-cyclohexanedimethanol; 45 to 85 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 15 to 55 mole % 1 ,4-cyclohexaned
- the glycol component for the polyesters of the invention can include but is not limited to at least one of the following combinations of ranges: greater than 50 to 99 mole % 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol and 1 to less than 50 mole % 1 ,4- cyclohexanedimethanol; greater than 50 to 95 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 5 to less than 50 mole % 1 ,4-cyclohexanedimethanol; greater than 50 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 1 0 to less than 50 mole % 1 ,4-cyclohexanedimethanol; greater than 50 to 85 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 1 5 to
- the glycol component for the polyesters of the invention can include but is not limited to at least one of the following combinations of ranges: 55 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 45 mole % 1 ,4-cyclohexanedimethanol; 55 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 45 mole % 1 ,4-cyclohexanedimethanol; 55 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 45 mole % 1 ,4-cyclohexanedimethanol; 55 to 85 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 1 5 to 45 mole % 1 ,4-cyclohexanedimethanol; 55 to 85 mole
- the glycol component for the polyesters of the invention can include but is not limited to at least one of the following combinations of ranges: 60 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 40 mole % 1 ,4-cyclohexanedimethanol; 60 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 40 mole % 1 ,4-cyclohexanedimethanol; 60 to 90 mole % 2,2,4,4-tetramethyl ⁇ l ,3-cyclobutanediol and 10 to 40 mole % 1 ,4-cyclohexanedimethanol; 60 to 85 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 1 5 to 40 mole % 1 ,4-cyclohexanedimethanol; 60 to 85 mole
- the glycol component for the polyesters of the invention can include but is not limited to at least one of the following combinations of ranges: 65 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 35 mole % 1 ,4-cyclohexanedimethanol; 65 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 35 mole % 1 ,4-cyclo- hexanedimethanoi; 65 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 35 mole % 1 ,4-cyclohexanedimethanol; 65 to 85 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 1 5 to 35 mole % 1 ,4-cyclo
- the glycol component for the polyesters of the invention can include but is not limited to at least one of the following combinations of ranges: 70 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 30 mole % 1 ,4-cyclohexanedimethanol; 70 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 30 mole % 1 ,4-cyclohexanedimethanol; 70 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 30 mole % 1 ,4-cyclohexanedimethanol; 70 to 85 mole % 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and 1 5 to 30 mole % 1 ,4-cyclohexanedimethanol; 70 to 85 mole
- the glycol component for the polyesters of the invention includes but is not limited to at least one of the following combinations of ranges: 75 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 25 mole % 1 ,4-cyclohexanedimethanol; 75 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 25 mole % 1 ,4-cyclohexanedimethanol; 75 to 90 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol and 10 to 25 mole % 1 ,4-cyclohexanedimethanol; and 75 to 85 mole % 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol and 1 5 to 25 mole % 1 ,4-cyclohexanedimethanol; and 75 to 85 mole %
- the glycol component for the polyesters of the invention can include but is not limited to at least one of the following combinations of ranges: 80 to 99 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 1 to 20 mole % 1 ,4-cyclohexanedimethanol; 80 to 95 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 5 to 20 mole % 1 ,4-cyclohexanedimethanol; 80 to 90 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 10 to 20 mole % 1 ,4-cyclohexanedimethanol.
- the glycol component for the polyesters of the invention can include but is not limited to at least one of the following combinations of ranges 37 to 80 mole % 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and 20 to 63 mole % 1 ,4-cyclohexanedimethanol; 40 to less than 45 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and greater than 55 to 60 mole % 1 ,4-cyclohexanedimethanol; greater than 45 to 55 mole % 2,2,4,4- tetramethyl-l ,3-cyc!obutanediol and 45 to less than 55 mole % 1 ,4-cyclohexanedimethanol; and 46 to 55 mole % 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and 45 to 54 mole %
- 2,2,4,4-tetramethyl-l ,3-cyclobutanediol is present at 0.01 to less than 5 mole % based on the mole percentages for the diol component equaling 100 mole % and where the presence of CHDM is optional, the glycol component for the polyesters useful the invention include but are not limited to at least of the following combinations of ranges: 0.01 to less than 5 mole % of 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol residues, greater than 0.01 to 95 mole %of ethylene glycol residues, and 0 to 99.98 mole % of 1 , 4-cyclohexanedimethanol; 0.01 to less than 5 mole % of 2,2,4, 4-tetramethyl-l ,3-cyclobutanediol residues, greater than 0.01 to 94.99 mole %of ethylene glycol residues, and 0.01 to 99.98 mole % of 1 , 4-cyclohex
- the glycol component may also contain one of the following ranges of 2,2,4, 4-tetramethyl-l ,3-cyclobutanediol residues: 0.01 to 4.5 mole %; 0.01 to 4 mole %; 0.01 to 3.5 mole %; 0.01 to 3 mole %; 0.01 to 2.5 mole %; 0.01 to 2.0 mole %; 0.01 to 2.5 mole %; 0.01 to 2 mole %; 0.01 to 1.5 mole %; 0.01 to 1.0 mole %; and 0.01 to 0.5 mole %.
- the remainder of the glycol component can be any amount of 1 , 4-cyclohexanedimethanol and/or ethylene glycol so long as the total amount of the glycol component equals 100 mole %.
- the polyesters useful in the polyester compositions of the invention may be made from 1 ,3-propanediol, 1 ,4-butanediol, or mixtures thereof.
- compositions of the invention made from 1 ,3-propanediol, i ,4-butanediol, or mixtures thereof can possess at least one of the Tg ranges described herein, at least one of the inherent viscosity ranges described herein, and/or at least one of the glycol or diacid ranges described herein.
- polyesters made from 1 ,3-propanediol or 1 ,4-butanediol or mixtures thereof may also be made from 1 ,4-cyclohexanedmethanol in at least one of the following amounts: from 0.1 to 99 mole %; 0.1 to 90 mole %; from 0.1 to 80 mole %; from 0.1 to 70 mole %; from 0.1 to 60 mole %; from 0.1 to 50 mole %; from 0.1 to 40 mole %; from 0.1 to 35 mole %; from 0.1 to 30 mole %; from 0.1 to 25 mole %; from 0.1 to 20 mole %; from 0.1 to 1 5 mole %; from 0.1 to 10 mole %; from 0.1 to 5 mole %; from 1 to 99 mole %; from 1 to 90 mole %; from 1 to 80 mole %; from 1 to 70 mole %; from 1 to 60 mole %; from
- mole % from 20 to 70 mole %; from 20 to 60 mole %; from 20 to 50 mole %; from 20 to 40 mole %; from 20 to 35 mole %; from 20 to 30 mole %; and from 20 to 25 mole %.
- the polyesters generally will have inherent viscosity (I. V.) values in the range of about 0.1 dL/g to about 1 .4 dL/g. Additional examples of I.V. ranges include about 0.65 dL/g to about 1 .0 dL/g and about 0.7 dL/g to about 0.85 dL/g. As described previously, inherent viscosity is measured at 25 oC using 0.5 grams of polymer per 100 ml of a solvent comprising 60 weight percent phenol and 40 weight % tetrachloroethane.
- the polyesters useful in the invention may exhibit at least one of the following inherent viscosities as determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.5 g/1 00 ml at 25 0 C: 0.10 to 1 .2 dL/g; 0.10 to 1 .1 dL/g; 0.10 to 1 dL/g; 0.1 0 to less than 1 dL/g; 0.1 0 to 0.98 dL/g; 0.10 to 0.95 dL/g; 0.10 to 0.90 dL/g; 0.10 to 0.85 dL/g; 0.10 to 0.80 dL/g; 0.10 to 0.75 dL/g; 0.10 to less than 0.75 dL/g; 0.10 to 0.72 dL/g; 0.10 to 0.70 dL/g; 0.10 to less than 0.70 dL/g; 0.10 to 0.68 dL/g; 0.10 to less
- the polyesters useful in the invention may exhibit at least one of the following inherent viscosities as determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.5 g/100 ml at 25 0 C: 0.45 to 1 .2 dL/g; 0.45 to 1 .1 dL/g; 0.45 to 1 dL/g; 0.45 to 0.98 dL/g; 0.45 to 0.95 dL/g; 0.45 to 0.90 dL/g; 0.45 to 0.85 dL/g; 0.45 to 0.80 dL/g; 0.45 to 0.75 dL/g; 0.45 to less than 0.75 dL/g; 0.45 to 0.72 dL/g; 0.45 to 0.70 dL/g; 0.45 to less than 0.70 dL/g; 0.45 to 0.68 dL/g; 0.45 to less than 0.68 dL/g; 0.45 to 0.45 to 0.45 to 0.45 to 0.45
- polyesters of the invention containing 2,2,4,4-tetramethyl-
- the molar ratio of cis/trans 2,2,4,4-tetramethyl-l ,3- cyclobutanediol can vary from the pure form of each or mixtures thereof.
- the molar percentages for cis and/or trans 2,2,4,4,- tetramethyl-1 ,3-cyclobutanediol are greater than 50 mole % cis and less than 50 mole % trans; or greater than 55 mole % cis and less than 45 mole % trans; or 30 to 70 mole % cis and 70 to 30 % trans; or 40 to 60 mole % cis and 60 to 40 mole % trans; or 50 to 70 mole % trans and 50 to 30 % cis; or 50 to 70 mole % cis and 50 to 30 % trans; or 60 to 70 mole % cis and 30 to 40 mole % trans; or greater than 70 mole % cis and less than 30 mole % trans; wherein the total sum of the mole percentages for cis- and trans- 2,2,4,4-tetramethyl-l ,3-cyclobutanediol is equal to 1 00 mole percentages for
- compositions of the invention can possess at least one of the inherent viscosity ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that compositions of the invention can possess at least one of the Tg ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that compositions of the invention can possess at least one of the inherent viscosity ranges described herein, at least one of the Tg ranges described herein, and at least one of the monomer ranges for the compositions described herein unless otherwise stated.
- terephthalic acid or an ester thereof such as, for example, dimethyl terephthalate or a mixture of terephthalic acid residues and an ester thereof can make up a portion or all of the dicarboxylic acid component used to form the polyesters useful in the invention.
- terephthalic acid residues can make up a portion or all of the dicarboxylic acid component used to form the present polyester at a concentration of at least 70 mole %, such as at least 80 mole %, at least 90 mole % at least 95 mole %, at least 99 mole %, or even 100 mole %.
- terephthalic acid and “dimethyl terephthalate” are used interchangeably herein.
- dimethyl terephthalate is part or all of the dicarboxylic acid component used to make the polyesters useful in the present invention. In all embodiments, ranges of from 70 to 100 mole %; or 80 to 100 mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100 mole % terephthalic acid and/or dimethyl terephthalate and/or mixtures thereof may be used.
- the dicarboxylic acid component of the polyester useful in the invention can comprise up to 30 mole %, up to 20 mole %, up to 10 mole %, up to 5 mole%, or up to 1 mole % modifying aromatic dicarboxylic acids.
- Yet another embodiment contains 0 mole % modifying aromatic dicarboxylic acids.
- the amount of one or more modifying aromatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, from 0.01 to 30 mole %, 0.01 to 20 mole %, from 0.01 to 10 mole %, from 0.01 to 5 mole % and from 0.01 to 1 mole.
- modifying aromatic dicarboxylic acids that may be used in the present invention include but are not limited to those having up to 20 carbon atoms, and which can be linear, para-oriented, or symmetrical.
- Examples of modifying aromatic dicarboxylic acids which may be used in this invention include, but are not limited to, isophthalic acid, 4,4'- biphenyldicarboxylic acid, 1 ,4-, 1 ,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, and trans-4,4'-stilbenedicarboxylic acid, and esters thereof.
- the modifying aromatic dicarboxylic acid is isophthalic acid.
- the carboxylic acid component of the polyesters useful in the invention can be further modified with up to 10 mole % such as up to 5 mole % or up to 1 mole % of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, such as, for example, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and dodecanedioic dicarboxylic acids. Certain embodiments can also comprise 0.01 or more mole %, such as 0.1 or more mole %, 1 or more mole %, 5 or more mole %, or 10 or more mole % of one or more modifying aliphatic dicarboxylic acids.
- Yet another embodiment contains 0 mole % modifying aliphatic dicarboxylic acids.
- the amount of one or more modifying aliphatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, from 0.01 to 1 0 mole % and from 0.1 to 10 mole %.
- the total mole % of the dicarboxylic acid component is 100 mole %.
- esters of terephthalic acid and the other modifying dicarboxylic acids or their corresponding esters and/or salts may be used instead of the dicarboxylic acids.
- Suitable examples of dicarboxylic acid esters include, but are not limited to, the dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters.
- the esters are chosen from at least one of the following: methyl, ethyl, propyl, isopropyl, and phenyl esters.
- the trans-1 ,4-cyclohexanedimethanol can be present in an amount of 60 to 80 mole %.
- the glycol component of the polyester portion of the polyester composition useful in the invention can contain 25 mole % or less of one or more modifying glycols which are not 2,2,4,4-tetramethyl-l ,3-cyclobutanediol or 1 ,4-cyclohexanedimethanol; in one embodiment, the polyester useful in the invention may contain less than 1 5 mole % or of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 10 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 5 mole % or less of one or more modifying glycols.
- the polyesters useful in the invention can contain 3 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 0 mole % modifying glycols. Certain embodiments can also contain 0.01 or more mole %, such as 0.1 or more mole %, 1 or more mole %, 5 or more mole %, or 10 or more mole % of one or more modifying glycols. Thus, if present, it is contemplated that the amount of one or more modifying glycols can range from any of these preceding endpoint values including, for example, from 0.01 to 1 5 mole % and from 0.1 to 10 mole %.
- Modifying glycols useful in the invention refer to diols other than
- suitable modifying glycols include, but are not limited to, ethylene glycol, 1 ,2-propanediol, 1 ,3- propanediol, neopentyl glycol, 1 ,4-butanediol, 1 ,5-pentanediol, polyethylene glycol, diethylene glycol, polytetramethylene glycol, 1 ,6-hexanediol, p-xylene glycol, or mixtures thereof.
- One embodiment for the modifying glycol is ethylene glycol.
- modifying glycols include, but are not limited to, 1 ,3- propanediol and 1 ,4-butanediol.
- ethylene glycol is excluded as a modifying diol.
- 1 ,3-propanediol and 1 ,4-butanediol are excluded as modifying diols.
- 2, 2- dimethyl-l ,3-propanediol is excluded as a modifying diol.
- polyesters and/or the polycarbonates useful in the polyester compositions of the invention can comprise from 0 to about 1 0 mole percent of one or more residues of a branching monomer, also referred to herein as a branching agent, having 3 or more carboxyl substituents, hydroxyl substituents, or a combination thereof.
- a branching monomer also referred to herein as a branching agent
- mole percent ranges of branching agent that may be present in the polyester or polycarbonates of the invention are from about 0.05 to about 5 mole percent, from about 0.01 to about 1 mole percent, about 0.01 to about 0.7, about 0.01 to about 0.5, and from about 0.1 to about 0.7 mole percent, based on the total moles of diols or diacid residues of the polyester and/or polycarbonate, respectively,
- the branching monomer or agent can be added during the polymerization of the polyester.
- the polyesters of the invention can thus be linear or branched.
- the polycarbonate can also be linear or branched.
- branching monomer or agent may be added prior to and/or during and/or after the polymerization of the polycarbonate.
- branching monomers include, but are not limited to, multifunctional acids or multifunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, glycerol, sorbitol, 1 , 2, 6-hexanetriol, trimethylolethane, and/or trimesic acid and the like.
- multifunctional acids or multifunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, glycerol, sorbitol, 1 , 2, 6-hexanet
- the branching monomer residues can comprise 0.01 to 1 mole percent of one or more residues chosen from at least one of the following: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, I 1 2, 6-hexanetriol, pentaerythritol, trimethylolethane, and/or trimesic acid.
- the branching monomer may be added to the polyester reaction mixture or blended with the polyester in the form of a concentrate as described, for example, in U.S. Patent No.'s 5,654,347 and 5,696,1 76.
- polyesters useful in the present invention Because of the long crystallization half-times (e.g., greater than 5 minutes) at 1 70°C exhibited by certain polyesters useful in the present invention, it can be possible to produce containers injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles and extrusion stretch blow molded.
- the polyesters of the invention can be are "amorphous" or semicrystalline. In one aspect, certain polyesters useful in the invention can have a relatively low crystal unity. Certain polyesters useful in the invention can thus have a substantially amorphous morphology, meaning that the polyesters comprising substantially unordered regions of polymer.
- an "amorphous" polyester can have a crystallization half-time of greater than 5 minutes at 17O 0 C or greater than 10 minutes at 1 7O 0 C or greater than 100 minutes at 1 7O 0 C. In one embodiment, of the invention, the crystallization half-times are greater than 1 ,000 minutes at 1 70 0 C. In another embodiment of the invention, the crystallization half-times of the polyester useful in the invention are greater than 10,000 minutes at 1 70 0 C. The crystallization half time of the polyester, as used herein, may be measured using methods well-known to persons of skill in the art.
- the crystallization half time of the polyester, ti / 2 can be determined by measuring the light transmission of a sample via a laser and photo detector as a function of time on a temperature controlled hot stage. This measurement can be done by exposing the polymers to a temperature, T ma ⁇ , and then cooling it to the desired temperature. The sample can then be held at the desired temperature by a hot stage while transmission measurements were made as a function of time. Initially, the sample can be visually clear with high light transmission, and becomes opaque as the sample crystallizes. The crystallization half-time is the time at which the light transmission is halfway between the initial transmission and the final transmission. Tmax is defined as the temperature required to melt the crystalline domains of the sample (if crystalline domains are present). The sample can be heated to T max to condition the sample prior to crystallization half time measurement. The absolute Tmax temperature is different for each composition. For example PCT can be heated to some temperature greater than 29O 0 C to melt the crystalline domains.
- the polymers of the invention may be crystalline, semicrystalline, or amorphous polymers.
- the term "semicrystalline”, as used herein, means that the polymer contains two phases: an ordered crystalline phase and an unordered amorphous phase.
- Polymers with a semicrystalline morphology exhibit both a crystalline melting temperature (Tm) and a glass transition temperature (Tg) and may be distinguished from “amorphous" polymers, which exhibit only a glass transition temperature.
- the polyesters of the instant invention are readily prepared from the appropriate dicarboxylic acids, esters, anhydrides, or salts, and the appropriate diol or diol mixtures using typical polycondensation reaction conditions.
- the dicarboxylic acid component of the polyesters of the present invention can be derived from dicarboxylic acids, their corresponding esters, or mixtures thereof.
- esters of the dicarboxylic acids useful in the present invention include the dimethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters, and the like.
- terephthalic acid may be used as the starting material.
- dimethyl terephthalate may be used as the starting material.
- polyesters of the present invention are prepared by procedures known to persons skilled in the art. They may be made by continuous, semi- continuous, and batch modes of operation and may utilize a variety of reactor types. Examples of suitable reactor types include, but are not limited to, stirred tank, continuous stirred tank, slurry, tubular, wiped-film, falling film, or extrusion reactors.
- the reaction of the diol and dicarboxylic acid may be carried out using conventional polyester polymerization conditions or by melt phase processes, but those with sufficient crystallinity may be made by melt phase followed by solid phase polycondensation techniques.
- the reaction process may comprise two steps.
- the diol component and the dicarboxylic acid component such as, for example, dimethyl terephthalate
- the reaction process may comprise two steps.
- the diol component and the dicarboxylic acid component such as, for example, dimethyl terephthalate
- elevated temperatures typically, about 1 50 0 C to about 25O 0 C for about 0.5 to about 8 hours at pressures ranging from about 0.0 kPa gauge to about 414 kPa gauge (60 pounds per square inch, "psig").
- the temperature for the ester interchange reaction ranges from about 1 8O 0 C to about 230 0 C for about 1 to about 4 hours while the preferred pressure ranges from about 103 kPa gauge (1 5 psig) to about 276 kPa gauge (40 psig).
- the reaction product is heated under higher temperatures and under reduced pressure to form the polyester with the elimination of diol, which is readily volatilized under these conditions and removed from the system.
- This second step, or polycondensation step is continued under higher vacuum and a temperature which generally ranges from about 23O 0 C to about 35O 0 C, preferably about 25O 0 C to about 31 O 0 C and, most preferably, about 26O 0 C to about 290 0 C for about 0.1 to about 6 hours, or preferably, for about 0.2 to about 2 hours, until a polymer having the desired degree of polymerization, as determined by inherent viscosity, is obtained.
- the polycondensation step may be conducted under reduced pressure which ranges from about 53 kPa (400 torr) to about 0.013 kPa (0.1 torr).
- Stirring or appropriate mixing techniques well known in the art can be used in both stages to ensure adequate heat transfer and surface renewal of the reaction mixture.
- the reaction rates of both stages are increased by appropriate catalysts such as, for example, alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like.
- a three-stage manufacturing procedure similar to that described in U.S. Patent No. 5,290,631 , may also be used, particularly when a mixed monomer feed of acids and esters is employed.
- polyesters are produced by reacting the dicarboxylic acid or a mixture of dicarboxylic acids with the diol component or a mixture of diol components.
- the reaction is conducted at a pressure of from about 7 kPa gauge (1 psig) to about 1 379 kPa gauge (200 psig), preferably less than 689 kPa (100 psig) to produce a low molecular weight polyester product having an average degree of polymerization of from about 1 .4 to about 10.
- the temperatures employed during the direct esterification reaction typically range from about 1 8O 0 C to about 28O 0 C, more preferably ranging from about 22O 0 C to about 27O 0 C.
- This low molecular weight polymer may then be polymerized by a polycondensation reaction.
- thermoplastic polymers of the invention may also comprise a polyarylate.
- Polyarylates are obtained by polymerization of a dihydric phenol and a dicarboxylic acid. Examples of polyarylates that can be used in the compositions, processes, and shaped articles of the instant invention are described in U.S. Patent No.'s 4,598,1 30; 5,034,502; and 4,374,239.
- dihydric phenols that can be used to prepare the polyarylates are bisphenols such as bis(4-hydroxyphenyl)methane; 2,2-bis(4-hydroxyphenyl) propane (“bisphenol-A"); 2,2-bis(4-hydroxy-3-methylphenyl)propane; 4,4-bis(4- hydroxyphenyl)heptane; 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; 2,2- bis(4-hydroxy-3,5-dibromophenyl)propane; dihydric phenol ethers such as, for example, bis(4-hydroxyphenyl)ether; bis(3,5-dichloro-4-hydroxyphenyl)ether;; dihydroxydiphenyls such as, for example, p.p'-dihydroxydiphenyl, 3,3'- dichloro-4, 4'-dihydroxydiphenyl; dihydroxyaryl sulfones such as, for example, bis(4- hydroxyphenyl
- dihydric phenols are also available such as are disclosed, for example, in U.S. Patent No.'s 2,999,835; 3,028,365 and 3,1 53,008. Also suitable are copolymers prepared from the above dihydric phenols copolymerized with halogen-containing dihydric phenols such as 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane and 2,2-bis(3,5-dibromo- 4-hydroxyphenyl)propane.
- halogen-containing dihydric phenols such as 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane and 2,2-bis(3,5-dibromo- 4-hydroxyphenyl)propane.
- dicarboxylic acids include, but are not limited to, aromatic dicarboxylic acids such as phthalic, isophthalic, terephthalic, o-phthalic, o-, m-, and p-phenylenediacetic acids, and polynuclear aromatic acids such as, for example, diphenic acid and 1 ,4-naphthalic acid.
- the polyarylates of the present invention can be prepared by any polyester forming reactions well known in the art such as, for example, interfacial polymerization by mixing a solution of an aromatic dicarboxylic acid dihalide in an organic solvent with an alkaline aqueous solution of a bisphenol under stirring to react these materials; solution polymerization by reacting an aromatic dicarboxylic acid dihalide with a bisphenol in the presence of a deacidifying agent such as pyridine in an organic solvent; molten polymerization by reacting an aromatic dicarboxylic acid diphenyl ester with a bisphenol; molten polymerization by reacting an aromatic dicarboxylic acid, diphenyl carbonate and a bisphenol; molten polymerization by reacting an aromatic dicarboxylic acid with a bisphenol diacetate; and polymerization by reacting an aromatic dicarboxylic acid with a bisphenol diacetate.
- a deacidifying agent such as pyridine
- polyarylates of the invention typically have inherent viscosities of about 0.5 to about 1 .1 dL/gm.
- polyester, polycarbonates, and polyarylates may further comprise one or more of the following: antioxidants, melt strength enhancers, branching agents (e.g., glycerol, trimellitic acid and anhydride), chain extenders, flame retardants, fillers, acid scavengers, dyes, colorants, pigments, antiblocking agents, flow enhancers, impact modifiers, antistatic agents, processing aids, mold release additives, plasticizers, slips, stabilizers, waxes, UV absorbers, optical brighteners, lubricants, pinning additives, foaming agents, antistats, nucleators, and the like.
- branching agents e.g., glycerol, trimellitic acid and anhydride
- chain extenders e.g., flame retardants, fillers, acid scavengers, dyes, colorants, pigments, antiblocking agents, flow enhancers, impact modifiers, antistatic agents, processing aids, mold release additives, plasticizers, slips,
- Colorants may be added to impart a desired neutral hue and/or brightness to the polyester.
- the polyester compositions may comprise 0 to about 30 weight percent of one or more processing aids to alter the surface properties of the composition and/or to enhance flow.
- processing aids include calcium carbonate, talc, clay, mica, zeolites, wollastonite, kaolin, diatomaceous earth, TiO 2 , NH4CI, silica, calcium oxide, sodium sulfate, and calcium phosphate.
- Various pigments or dyes might be used, for example, to make a colored articles.
- An antistat or other coating may also be applied to the surface of the article.
- the second component (ii) of the compositions of the invention comprises a transamidized, homogeneous blend of at least two polyamides.
- the homogeneous blend will comprise from 2 to about 10 different polyamides. in another example, the homogeneous blend can comprise from 2 to 4 polyamides.
- polyamides that display a melting point below about 300 0 C can be used as at least one polyamide.
- polyamides with the melting point less than about 275 0 C and glass transition temperature greater than about 25°C may be used.
- the polyamides have an I. V. between about 0.3 dL/g and about 2.0 dL/g and, preferably at least 0.5 dL/g.
- transamidized is intended to be synonymous with the terms “transamidate” and “transamidation”, and refers to the process of exchanging amido groups between two different polyamides.
- a “transamidized blend” of polyamides is a blend in which the polyamide components have exchanged an amount of amido groups sufficient to cause the blend to become a homogeneous blend.
- Transamidation between two or more polyamides can be accomplished by contacting the polyamides at elevated temperatures, typically from about 270 0 C to about 35O 0 C Other examples of transamidation temperatures are about 28O 0 C to about 35O 0 C and about 29O 0 C to about 34O 0 C. Transamidation between the polyamides is indicated by the presence of a single glass transition temperature (“Tg") for the blend as determined by differential scanning calorimetry ("DSC”) using standard techniques well known to persons skilled in the art such as, for example, described in ASTM Method D3418. The polyamides may be heated together directly at these temperature or in the presence of the thermoplastic polymers of the first component (i).
- Tg single glass transition temperature
- DSC differential scanning calorimetry
- the contacting and, hence, transamidation of the polyamides can take place by melt blending of the first and second components, during extrusion, or other high temperature processing of the polymer composition and its components.
- the polyamides may be heated together in a separate vessel and then melt blended with the first component.
- the first and second polyamides of the second component may be selected from a wide range of polyamides.
- the polyamides can comprise partially aromatic polyamides and aliphatic polyamides having a number average molecular weight of 7,000 or less. Combinations of such polyamides are included also within the scope of the invention.
- Partially aromatic polyamides comprise amide linkages between at least one aromatic ring and at least one nonaromatic species.
- wholly aromatic polyamides generally are liquid crystalline, the blends of such resins having melting points less than 300 0 C can be used for this invention.
- the rapid transamidization (amide-amide interchange) of aliphatic nylon with aromatic or partially aromatic polyamide permits the tailoring of refractive index of the polyamide blend by adjusting the ratios of aliphatic polyamide to aromatic, or partially aromatic, polyamide.
- This technique enables a matching of the refractive index of the homogeneous polyamide blend to the thermoplastic polymer such as, for example, one or more polyesters, of the first component.
- a reference for transamidization can be found in the work by Y. Takeda, et.al., Polymer, 1992 vol. 33, pg. 3394.
- the second component can be a transamidized, homogeneous blend of 2 or more polyamides such as, for example, a first polyamide and a second polyamide which are selected to give a refractive index in the second component such that second and first components have a difference in refractive index (Rl(second component) - RKfirst component)) of about 0.006 to about -0.0006.
- a difference in refractive index Rl(second component) - RKfirst component
- the first and second polyamide have different amounts of aromatic and aliphatic residues.
- the second component (ii) can comprise a homogeneous blend of a first polyamide, comprising aromatic residues, and of a second polyamide comprising aliphatic residues.
- aliphatic as used herein with respect to the diamine and dicarboxylic acid monomers of the polyamides of the present invention, means that carboxyl or amino groups of the monomer are not connected through an aromatic nucleus.
- adipic acid contains no aromatic nucleus in its backbone, i.e., the chain of carbon atoms connecting the carboxylic acid groups; thus, it is "aliphatic".
- aromatic means the dicarboxylic acid or diamine contains an aromatic nucleus in the backbone such as, for example, terephthalic acid or 1 ,4-metaxylylenediamine.
- aromatic polyamides are those polyamids comprising at least 70 mole % of residues comprising diamines such as m- xylylenediamine or a xylylenediamine mixture comprising m-xylylenediamine and up to 30% of p-xylylenedi amine and an aliphatic dicarboxylic acid having 6 to 10 carbon atoms.
- aliphatic therefore, is intended to include both aliphatic and cycloaliphatic structures such as, for example, diamine, diacids, lactams, aminoalcohols.and aminocarboxylic acids, that contain as a backbone a straight or branched chain or cyclic arrangement of the constituent carbon atoms which may be saturated or paraffinic in nature, unsaturated (i.e., containing non-aromatic carbon-carbon double bonds), or acetylenic (i.e., containing carbon-carbon triple bonds).
- diamine diacids
- lactams aminoalcohols.and aminocarboxylic acids
- aminocarboxylic acids that contain as a backbone a straight or branched chain or cyclic arrangement of the constituent carbon atoms which may be saturated or paraffinic in nature, unsaturated (i.e., containing non-aromatic carbon-carbon double bonds), or acetylenic (i.e., containing carbon-carbon triple bonds).
- aliphatic is intended to include linear and branched, chain structures (referred to herein as “aliphatic”) and cyclic structures (referred to herein as “alicyclic” or “cycloaliphatic”).
- aliphatic is not intended to exclude any aromatic substituents that may be attached to the backbone of an aliphatic or cycloaliphatic diol or diacid or hydroxycarboxylic acid.
- the weight percentage ratio of the first and second polyamides present in the transamidized, homogeneous blend typically may range from about 1 :50 to about 50:1 based on the total weight of the second component.
- Other examples of weight percentage ratios are 1 :20 to about 20:1 and about 1 :10 to about 10:1.
- polyamide forming diacids and diamines can be used.
- the polyamides also may contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, pyromellitic dianhydride, or other polyamide forming polyacids and polyamines known in the art.
- partially aromatic polyamides include, but are not limited to: poly(m-xylylene adipamide) (referred to herein as "MXD6" nylon), poly(hexamethylene isophthalamide), poly(hexamethylene adipamide-co- isophthalamide), poly(hexamethylene adipamide-co-terephthalamide), and poly(hexamethylene isophthalamide-co-terephthalamide).
- the partially aromatic polyamide is poly(m-xylylene adipamide).
- the partially aromatic polyamides may have a number average molecular weight of 7000 or less.
- Representative examples of aliphatic polyamides include poly(2-pyrrolidinone) (nylon 4, 6; CAS No.
- polycapramide (nylon 6; CAS No. 1 8,1 1 1 -0), poly(2-piperidone) (nylon 5, CAS No. 24938-57-6); poly(7-aminoheptanoic acid) (nylon 7; CAS No. 25035-01 -2); poly(nonanamide) (nylon 9; CAS No. 25748-72-5); polyO 1 -aminoundecanoic acid) (nylon 1 1 ; CAS No. 25035-04-5); polyO 2-aminolauric acid) (nylon 1 2, CAS No.
- poly(ethyleneadipamide) (nylon 2,6); polytetramethylene- adipamide (nylon 4,6; CAS No. 50327-22-5); polyhexamethylene-adipamide (nylon 6,6; CAS No. 42,91 7-1 ), (nylon 6,9; CAS No. 1 8,806-9) poly- (hexamethylene-sebacamide) (nylon 6,1 0; CAS No. 9008-66-6), poly(hexamethylene-undecanamide) (nylon 6, 1 1 ) poly (hexamethylene- dodecamide) (nylon 6,12; CAS No.
- poly(octamethylene- adipamide) (nylon 8,6); adipic acid-decamethylenediamine copolymer (nylon 10,6; CAS No. 26123-27-3); polydecamethylene- dodecamide (nylon 10, 12); poly(dodecamethylene-adipamide) (nylon 12,6); and poly(dodecamethylene- sebacamide) (nylon 12,8).
- the second component (U) can comprise a homogeneous blend comprising a first polyamide comprising the residues of m ⁇ xylylenediamine and adipic acid, and a second polyamide comprising the residues of at least one aliphatic or cycloaliphatic monomer selected from adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioc acid, dodecanedioc acid, caprolactam, butyrolactam, 1 1 -aminoundecanedioc acid, and hexamethylene diamine.
- the first polyamide for example, can comprise MXD6 nylon, which is commerically available from Mitsubishi Corporation.
- the second polyamide can comprise at least one polyamide selected from from nylon 4; nylon 6; nylon 9; nylon 1 1 ; nylon 12; nylon 6,6; nylon 5,10; nylon 6,12; nylon 6,1 1 ; nylon 10,12; and combinations thereof.
- the second polyamide can comprise nylon 6, nylon 6,6, or blends thereof.
- the second component also may comprise a single copolyamide in which the composition of monomer residues is chosen to give a refractive index that closely matches the refractive index of the first component.
- the invention provides a polymer composition, comprising an immiscible blend of: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and
- a second component comprising a copolyamide; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 10% or less.
- the first component can comprise a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, and 1 ,4-cyclohexanedimethanoL
- a polymer composition comprising an immiscible blend of: (i) a first component comprising at least one polyester which comprises:
- diacid residues comprising about 70 to about 1 00 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms;
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol; and
- a second component comprising a copolyamide; wherein the second component (ii) and the first component (i) have a difference in refractive index, RKsecond component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 10% or less.
- the copolyamide can comprise the residues of m-xylylenediamine, p-xylylenediamine, or a combination thereof; and the residues of at least one monomer selected from terephthalic acid, isophthalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioc acid, dodecanedioc acid, caprolactam, butyrolactam, 1 1 -amino-undecanedioc acid, and 1 ,6-hexamethylenediamine.
- the copolyamide can comprise about 1 5 to about 100 mole percent of the residues of m-xylylenediamine, based on a total diamine residue content of 100 mole%, and about 1 5 to about 85 mole percent of the residues adipic acid and about 85 to about 1 5 mole percent of the residues of one or more aliphatic or cycloaliphatic dicarboxylic acids selected from pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, and 1 ,4-cyclohexanedicarboxylic acid, based on a total diacid residue content of 100 mole%.
- copolyamides that can be used as in composition of the invention, either alone or as part of a homogeneous blend with another polyamide, include, but are not limited to, copolyamides comprising from about 1 5 to about 100 mole percent of the residues of m- xylylenediamine, based on a total diamine residue content of 100 mole%, and the residues of adipic acid.
- Typical amounts of adipic acid residues which may be present in these copolyamides, based on the total moles of diacid residues, are about 5 to about 85 mole percent, about 20 to about 80 mole percent, and about 25 to about 75 mole percent.
- the remainder of the dicarboxylic acid residues can comprise residues from one or more aliphatic dicarboxylic acids having from 7-1 2 carbon atoms, such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, or 1 ,4-cyclohexane- dicarboxylic acid.
- the polyamide acid also may comprise residues from isophthalic acid and terephthalic acid.
- the copolyamides of the invention also may comprise other diamines or lactam residues in addition to m-xylylenediamine residues.
- the copolyamide can comprise at least 1 5 mole percent, or at least about 20 mole percent of the residues of m-xylylenediamine with the remainder of the diamines residues comprising the residues of one or more aliphatic or aromatic diamines.
- the copolyamide may comprise about 80 mole percent or about 85 mole %, of the residues of 1 ,6-hexamethylene diamine, based on the total moles of diamine residues.
- the copolyamide may comprise the residues of a lactam, such as caprolactam, or lactams based on gamma-amino-butyric acid or 1 1 -amino-undecanoic acid, in an amount from about 10 mole percent to about 90 mole percent, or from about 10 mole percent to about 70 mole percent based on the total moles of repeating units.
- the copolyamides of the invention can comprise from about 1 5 mole percent to about 85 mole percent, about 20 to about 80 mole percent, or about 25 to about 75 mole percent of the residues from m-xylylenediamine, based on the total moles of diamine residues with the remainder of the diamine residues content comprising residues from one or more diamines, such as aliphatic diamines, and especially 1 ,6-hexamethylene diamine.
- the diamine residues may further comprise minor amounts of the residues of other diamines, for example p-xylylenediamine, or a cyclic aliphatic diamine such as, for example, one or more of: 1 ,3-cyclohexanebis(methylamine) or 1 ,4- cyclohexanebis(methylamine).
- other diamines for example p-xylylenediamine
- a cyclic aliphatic diamine such as, for example, one or more of: 1 ,3-cyclohexanebis(methylamine) or 1 ,4- cyclohexanebis(methylamine).
- the polyamide may optionally include, in place of a portion of the adipic acid, residues from one or more aliphatic or aromatic dicarboxylic acids having from 7-12 carbon atoms, such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, 1 ,4-cyclohexanedicarboxylic acid, or isophthalic acid, which may be present in an amount from about 1 5 mole percent to about 85 mole percent, optionally with minor amounts of terephthalic acid.
- residues from one or more aliphatic or aromatic dicarboxylic acids having from 7-12 carbon atoms such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, 1 ,4-cyclohexanedicarboxylic acid, or isophthalic acid, which may be present in an amount from about 1 5
- the polyamide also may comprise the residues of a lactam, such as caprolactam, or lactams based on gamma-amino-butyric acid or 1 1 -amino-undecanoic acid, in an amount from about 10 mole percent to about 90 mole percent, or about 1 0 mole% to 70 mole percent, based on the total moles repeating units.
- a lactam such as caprolactam
- the copolyamides according to the invention may comprise from about 1 5 mole percent up to about 90 mole percent of residues from adipic acid, with the remaining diacid residues comprising the about 10 to about 85 mole percent of the residues of isophthalic acid, based on the total moles of dicarboxylic acid residues. Additional examples of adipic acid and isophthalic acid residue content include about 20 to 80 mole percent, and about 25 to about 75 mole percent.
- the polyamide may optionally comprise minor amounts of residues from one or more aliphatic dicarboxylic acids having from 7-1 2 carbon atoms, such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, or 1 ,4-cyclohexanedicarboxylic acid, optionally with minor amounts of terephthalic acid.
- the polyamides may comprise m- xylylenediamine residues. Examples of m-xylylenediame residue concentrations include about 1 5 to about 90 mole percent, about 20 to about 85 mole percent, or about 25 to about 80 mole percent.
- the remaining residues can comprise from one or more aliphatic diamines, such as, for example, 1 ,6-hexamethylene diamine, one or more aromatic diamines such as, for example, p-xylylene- diamine.
- the copolyamide also may comprise the residues of a lactam such as, for example, caprolactam, or lactams based on gamma-amino-butyric acid or 1 1 -amino-undecanoic acid, in an amount from about 10 mole percent to about 90 mole percent or about 10 mole percent to about 70 mole percent, based on the total moles of repeating units.
- the copolyamides of the invention may comprise the residues of one or more lactams such as, for example, caprolactam, or lactams based on gamma-amino-butyric acid or 1 1 -amino- undecanoic acid, in an amount from about 10 mole percent to about 90 mole percent, or from about 10 mole percent to about 70 mole percent, or from about 1 5 mole percent to about 60 mole percent, based on the total moles of repeating units.
- lactams such as, for example, caprolactam, or lactams based on gamma-amino-butyric acid or 1 1 -amino- undecanoic acid
- the residues of one or more aliphatic dicarboxylic acids having from 7-12 carbon atoms such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, or 1 ,4-cyclohexanedicarboxylic acid, also may be present in amounts from about 20 mole percent to about 80 mole percent, based on the total moles of repeating units.
- the copolyamide may comprise residues from isophthalic acid or terephthalic acid.
- the copolyamides can comprise from about 1 5 mole percent to about 85 mole percent of the residues from m-xylylenediamine, based on the total moles of diamine residues.
- m- xylylenediamine content are about 20 to about 80 mole percent and about 25 to about 75 mole percent.
- the remainder of the diamine residues may comprise the residues of one or more diamines aliphatic diamines such as, for example, 1 ,6-hexamethylene diamine.
- the diamine residues may further comprise minor amounts of the residues of other diamines, for example p-xylylenediamine, or a cyclic aliphatic diamine such as, for example, one or more of: 1 ,3-cyclohexanebis(methylamine) or 1 ,4-cyclohexanebis(methylamine).
- minor amounts of one or more of: p-xylylenediamine, 1 ,3- cyclohexanebis(methylamine), or 1 ,4-cyclohexanebis(methylamine) may be used.
- Another embodiment of the invention is polymer composition, consisting essentially of an immiscible blend of: (i) a first component consisting essentially of at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component consisting essentially of a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 1 0% or less.
- a first component consisting essentially of at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof
- a second component consisting essentially of a homogeneous, transamidized blend of at least 2 polyamide
- the first component consists essentially of a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, and 1 ,4- cyclohexanedimethanol.
- the invention also provides a polymer composition, consisting essentially of an immiscible blend of: (i) a first component consisting essentially of at least one polyester which comprises:
- diacid residues comprising about 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms; and
- diol residues consisting essentially of about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4,4-tetramethyl-l ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol; and
- a second component consisting essentially of a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 10% or less.
- compositions which are immiscible blends that is, having at least 2, composition-dependent Tg's as measured by DSC, and which have first component containing a polyester, polycarbonate, polyarylate, or homogeneous blends thereof and a second component containing a homogeneous, transamidized blend of at least 2 polyamides.
- the composition is understood to exclude any elements that would substantially alter the essential properties of the composition to which the phrase refers.
- compositions may include other components that do not alter the refractive index of the components, %haze of the immiscible blend, the %transmittance, or the miscibility of the immiscible blend.
- a compatibilizer which may alter the miscibility and refractive index of the composition, would be excluded from this embodiment.
- a second component containing a copolyamide prepared by copolymerization of the component monomers would be excluded because such a copolyamide would be considered to have different properties than a homogeneous, transamidized blend of at least 2 polyamides, even if the mole percentage of the monomer residues are equivalent.
- the polyamides used in the present invention typically are prepared from dicarboxylic acids and diamines, which react in substantially equal proportions, or by the ring-opening polymerization of lactams, and are incorporated into the polyamide polymer as their corresponding residues.
- the polyamides derived from dicarboxylic acid and diamine residues of the present invention therefore, contain substantially equal molar proportions of acid residues (100 mole percent) and diamine residues (100 mole percent) such that the total moles of repeating units is equal to 100 mole percent.
- the mole percentages provided in the present disclosure therefore, may be based on the total moles of acid residues, the total moles of diamine residues, or the total moles of repeating units.
- a polyamide or copolyamide containing 30 mole percent terephthalic acid means that the copolyamide contains 30 mole percent terephthalic residues out of a total of 1 00 mole percent acid residues. Thus, there are 30 moles of terephthalic residues among every 100 moles of acid residues.
- a copolyamide containing 30 mole percent m-xylylenediamine means that the copolyester contains 30 mole percent m- xylylenediamine residues out of a total of 100 mole percent diamine residues. Thus, there are 30 moles of m-xylylenediamine residues among every 100 moles of diamine residues.
- the polyamides are generally prepared by melt phase polymerization from a diacid-diamine complex which may be prepared either In situ or in a separate step. In either method, the diacid and diamine are used as starting materials. Alternatively, an ester form of the diacid may be used, preferably the dimethyl ester. If the ester is used, the reaction must be carried out at a relatively low temperature, generally 80 to 120 0 C, until the ester is converted to an amide. The mixture is then heated to the polymerization temperature.
- caprolactam either caprolactam or 6- aminocaproic acid can be used as a starting material and the polymerization may be catalyzed by the addition of adipic acid/hexamethylene diamine salt which results in a nylon 6/66 copolymer.
- the diacid-diamine complex is used, the mixture is heated to melting and stirred until equilibration.
- the molecular weight is controlled by the diacid-diamine ratio. An excess of diamine produces a higher concentration of terminal amino groups.
- the second component and first component of the immiscible blend typically have refractive indices which differ by about 0.006 to about -0.0006, that is, the RKsecond component) - Rl(first component) is about 0.006 to about -0.0006.
- differences in the absolute value of the refractive indices are about 0.005 to about -0.0006, about 0.004 to about -0.0006, about 0.003 to about -0.0006, about 0.005 to about -0.0005, and about 0.004 to about -0.0005.
- the difference in refractive indices which may be acceptable depends on the blend composition, particle diameter, refractive index, wavelength, and particle structure as described by Biangardi et a!., Die Angew. Makromole. Chemie, 1 83, 221 (1 990).
- the immiscible blend of the instant invention has excellent clarity and has a % transmittance of at least 75%, as determined by ASTM Method Dl 003, and a haze of 1 0% or less. According to this method, the %haze value is calculated from the %transmittance value. Other examples of % transmittance are at least 77%, at least 80%, and at least 85%. Additional examples of haze values which may be exhibited by the blends of the invention are 9% or less, 7% or less, 5% or less, and 3% or less.
- haze is determined by molding or casting the composition into a sheet or film having a thickness of 1 /8 inch or less and measuring the haze according to the procedure described in the examples.
- the haze can be determined by cutting out a small (i.e., 1 X 1 cm) section of the article, having a thickness of 1 /8 inch or less, and measuring the haze according the procedure given in the examples.
- the first component also may comprise homogeneous blend of one or more polymers.
- the first component may comprise a homogeneous blend of a first polyester with one or more polymers chosen from a polycarbonate, a second polyester, and a polyarylate.
- the polyester may be any polyester as described herein.
- the first component may comprise a homogeneous blend of a polyester and a polycarbonate comprising the residues of bisphenol A.
- the polycarbonate may comprise about 90 to 100 mole percent, based on the total moles of diol residues, of the residues bisphenol A, and from 0 to about 10 mole percent of the residues of one or more modifying aliphatic diols or dihydric phenols having from 2 to 16 carbons.
- Representative examples include bis(4-hydroxyphenyl)methane; 2,2-bis(4-hydroxyphenyl) propane ("bisphenol-A"); 2,2-bis(4-hydroxy-3-methylphenyl)propane; 4,4-bis(4- hydroxyphenyl)heptane; 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; 2,2- bis(4-hydroxy ⁇ 3,5-dibromophenyl)propane; dihydric phenol ethers such as, for example, bis(4-hydroxyphenyl)ether; bis(3,5-dichloro-4-hydroxyphenyl)ether;; dihydroxydiphenyls such as, for example, p,p'-dihydroxydiphenyl, 3,3'- dichloro-4, 4'-dihydroxydiphenyl; dihydroxyaryl sulfones such as, for example, bis(4- hydroxyphenyl)sulfone; bis(3,5-dimethyl-4-hydroxyphenyl
- dihydric phenols are also available such as are disclosed, for example, in U.S. Patent No. 1 S 2,999,835; 3,028,365 and 3,1 53,008.
- copolymers prepared from the above dihydric phenols copolymerized with halogen-containing dihydric phenols such as 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane and 2,2-bis(3,5-dibromo- 4-hydroxyphenyl)propane.
- dicarboxylic acids include, but are not limited to, aromatic dicarboxylic acids such as phthalic, isophthalic, terephthalic, o-phthalic, o-, m-, and p-phenylenediacetic acids, and polynuclear aromatic acids such as, for example, diphenic acid and 1 ,4-naphthalic acid.
- aliphatic diols include ethylene glycol, propanediols, butanediols, pentanediols, hexandiols, heptanediols, octanediols, neopentyl glycol, aryl-alkyl glycols such as styrene glycol, xylylene glycols, dihydroxy alkyl ethers of dihydric phenols such as the dihydroxy ethyl ether of bisphenol-A, and the like.
- aliphatic diols are higher molecular weight aliphatic dihydroxy compounds such as, for example, polyethylene glycols, polystyrene glycols, polypropylene glycols, polybutylene glycols, polythioglycols, poly-arylalkyl ether glycols and copolymer polyether glycols. Additional representative examples of dihydric phenols and aliphatic diols are described in U.S. Patent No.'s 3,030,335 and 3,31 7,466.
- the polycarbonate may further comprise the residues of one or more branching agents such as, for example, tetraphenolic compounds, tri-(4-hydroxyphenyl) ethane, pentaerythritol triacrylate and other compounds as disclosed in U.S. Patent No.'s 6,160,082; 6,022,941 ; 5,262,51 1 ; 4,474,999; and 4,286,083.
- branching agents such as, for example, tetraphenolic compounds, tri-(4-hydroxyphenyl) ethane, pentaerythritol triacrylate and other compounds as disclosed in U.S. Patent No.'s 6,160,082; 6,022,941 ; 5,262,51 1 ; 4,474,999; and 4,286,083.
- branching agents are mentioned herein below.
- the polycarbonate comprises at least 95 mole percent, based on the total moles of diol residues, of the residues of bisphenol A.
- the inherent viscosity of the polycarbonate portion of the blends according to the present invention is preferably at least about 0.3 dL/g, more preferably at least 0.5 dL/g.
- the melt flow of the polycarbonate portion of the blends according to the present invention is preferably between 1 and 20, and more preferably between 2 and 1 8, as measured according to ASTM Method Dl 238 at a temperature of 300 0 C and using a weight of 1.2 kg.
- Processes for the preparation of polycarbonates are well known in the art.
- the linear or branched polycarbonates that can be used in the invention and disclosed herein are not limited to or bound by the polycarbonate type or its production method.
- a dihydric phenol such as bisphenol A
- phosgene is reacted with phosgene with the use of optional mono-functional compounds as chain terminators and tri-functional or higher functional compounds as branching or crosslinking agents.
- Monofunctional, difunctional, and trifunctional reactive acyl halides also can used in the preparation of polycarbonates as terminating compounds (mono-functional), comonomers (di-functional), or branching agents (tri-functional or higher).
- the polycarbonate portion of the present blend can be prepared in the melt, in solution, or by interfacial polymerization techniques well known in the art. Suitable methods include the steps of reacting a carbonate source with a diol at a temperature of about O 0 C to 31 5 0 C at a pressure of about 0.1 to 760 mm Hg for a time sufficient to form a polycarbonate.
- Commercially available polycarbonates that can be used in the present invention are normally made by reacting an aromatic diol with a carbonate source such as, for example, phosgene, dibutyl carbonate, or diphenyl carbonate, to incorporate 100 mole percent of carbonate units, along with 100 mole percent diol units into the polycarbonate.
- a carbonate source such as, for example, phosgene, dibutyl carbonate, or diphenyl carbonate
- Blends of the of polyesters and polycarbonates can be made by methods which include the steps of blending the polycarbonate and polyester portions at a temperature of about 25 0 C to 35O 0 C for a time sufficient to form a clear blend composition.
- Suitable conventional blending techniques include the melt method and the solution-prepared method.
- Other suitable blending techniques include dry blending and/or extrusion.
- the compositions of the present invention including the immiscible and homogeneous blends contained therein, may be prepared by any method known in the art and are useful as thermoplastic molding compositions and for formation of films and single and multilayered articles.
- homogeneous polyesters blends may be prepared by transesterification of the polyester components.
- homogeneous blends of polyamides may be prepared by transamination of the polyamide components.
- the melt blending method includes blending the polymers at a temperature sufficient to melt the first component and second component portions, and thereafter cooling the blend to a temperature sufficient to produce a clear blend.
- melt as used herein includes, but is not limited to, merely softening the polymers. Examples of melt mixing methods generally known in the polymers art are described in Mixing and Compounding of Polymers (I. Manas-Zloczower & Z. Tadmor eds., Carl Hanser Verlag publisher, N.Y. 1994).
- the solution-prepared method includes dissolving the appropriate weight/weight ratio of the first component and second component in a suitable organic solvent such as methylene chloride or a 70/30 mixture of methylene chloride and hexafluoroisopropanol, mixing the solution, and separating the blend composition from solution by precipitation of the blend or by evaporation of the solvent.
- a suitable organic solvent such as methylene chloride or a 70/30 mixture of methylene chloride and hexafluoroisopropanol
- the melt blending method is the preferred method for producing the blend compositions of the present invention.
- the melt blending method is more economical and safer than the solution method, which requires the use of volatile solvents.
- the melt blending method also is more effective in providing clear blends. Any of the clear blends of the present invention that can be prepared by. solution blending also can be prepared by the melt method. Some of the blends of the present invention, however, can be prepared by the melt method, but not by the solution-prepared method. Any blending process which provides clear blends of the present invention is suitable. One of ordinary skill in the art will be able to determine appropriate blending methods for producing the clear blends of the present invention.
- first and second components of the composition may be compounded in the melt, for example, by using a single screw or twin screw extruder. They may also be prepared by blending in solution. Additional components such as stabilizers, flame retardants, colorants, lubricants, release agents, impact modifiers, and the like may also be incorporated into the formulation.
- the compositions can be produced via a melt extrusion compounding of the first component and the second component with any other composition components such as, for example, metal catalysts, dyes, toners, fillers, and the like.
- the composition may be formed by dry blending solid particles or pellets of each of thermoplastic polymers and the polyamide components and then melt blending the mixture in a suitable mixing means such as an extruder, a roll mixer, or the like.
- a suitable mixing means such as an extruder, a roll mixer, or the like.
- these temperatures range from about 270 0 C to about 35O 0 C.
- Other examples of transamidation temperatures are about 280°C to about 35O 0 C and about 29O 0 C to about 34O 0 C.
- Blending is conducted for a period of time that will yield a well dispersed, immiscible blend. Such may easily be determined by those skilled in the art. If desired, the composition may be cooled and cut into pellets for further processing, it may be extruded into films, sheets, profiles, and other shaped elements, injection or compression molded to form various shaped articles, or it may be formed into films and optionally uniaxially or biaxially stretched by means well known in the art. [0127]
- the amounts of the first and second components in the immiscible blend may vary widely.
- the immiscible blend of our novel composition may comprise about 5 to about 99 weight percent of the first component and about 95 to about 1 weight percent of the second component, based on the total weight of the composition.
- weight percentages of the first and second components include about 50 to about 99 weight percent of the first component and about 50 to about 1 weight percent of the second component, about 60 to about 99 weight percent of the first component and about 40 to about 1 weight percent of the second component, and about 70 to about 99 weight percent of the first component and about 30 to about 1 weight percent of the second component.
- Our invention also provides a composition prepared by a process comprising melt blending: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the composition has a percent transmittance of at least 75%, and a haze of 10% or less.
- a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof
- a second component comprising a homogeneous, transamidized blend of at least 2 polyamides
- the first component comprises a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, and 1 ,4-cyclohexanedimethanol.
- the invention therefore, also provides a polymer composition, prepared by a process comprising melt blending:
- a first component comprising at least one polyester which comprises:
- diacid residues comprising about 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms; and
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4- cyclohexanedimethanol; and
- composition (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the composition has a percent transmittance of at least 75%, and a haze of 10% or less.
- the composition includes the various embodiments of the polyesters, polycarbonates, polyarylates, homogeneous blends, and polyamides as described above and any combination thereof.
- the second component of the composition can comprise a homogeneous, transamidized blend of at least 2 polyamides in which transamidation may be accomplished by contacting the polyamides at elevated temperatures, typically from about 270 0 C to about 350 0 C.
- elevated temperatures typically from about 270 0 C to about 350 0 C.
- Other examples of transamidation temperatures are about 280°C to about 35O 0 C and about 290 0 C to about 340°C.
- the homogeneous blend of component (ii) can comprise a first polyamide, comprising aromatic residues, and a second .polyamide comprising aliphatic residues, as described previously.
- typical polyamides that can be used as the second polyamide include, but are not limited to, nylon 4; nylon 6; nylon 9; nylon 1 1 ; nylon 1 2; nylon 6,6; nylon 5, 1 0; nylon 6, 1 2; nylon 6,1 1 ; nylon 1 0, 1 2; and combinations thereof.
- the first component can comprise a homogeneous blend of a polyester and a polycarbonate comprising the residues of bisphenol A.
- Another aspect of the instant invention is a method for the preparation of a transparent polymer blend, comprising:
- thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof;
- the first component comprises a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclo- butanediol, and 1 ,4-cyclohexanedimethanol.
- our invention also provides a method for the preparation of a transparent polymer blend, comprising:
- diacid residues comprising about 70 to about 1 00 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 1 0 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 1 6 carbon atoms;
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol; and
- Our methods include the various embodiments of the polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, and polyamides as described previously and any combination thereof.
- Our method comprises selecting the first component which may be a polyester, polycarbonate, polyarylate or homogeneous blend thereof.
- the refractive index of the first component may be determined using methods well known to persons skilled in the art.
- the second component which may comprise as single copolyamide or a transamidized, homogeneous blend of at least two polyamides, is tailored to closely match the refractive index of the first component by selecting the appropriate mixture of aromatic and aliphatic monomers in the case of a copolyamide, or by selecting a mixture of polyamides containing the desired mixture of aromatic and aliphatic residues if a homogeneous blend of polyamides is used.
- the choice of the proper ratio of monomers or of polyamides can be determined, for example, by trial and error, or, in another example, by plotting the refractive index of various polyamides or copolyamides containing varying amounts of aromatic residues and aliphatic residues, and selecting the molar ratio of aromaticaliphatic residues or the weight percentage ratio of polyamides that will give the targeted refractive index.
- the first and second components may be melt blended.
- the second component comprises a transamidized, homogeneous blend of at least 2 polyamides, it is desirable to carry out the melt blending step at a temperature effective for the transmidation process. Typical transamidation temperature ranges are as described previously.
- thermoplastic polymers also may be selected to match the refractive index of the second component.
- another aspect of the invention is a method for the preparation of a transparent polymer blend, comprising: (A) selecting a second component comprising
- the invention also includes a method for the preparation of a transparent polymer blend, comprising:
- diacid residues comprising about 70 to about 1 00 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms;
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4, 4-tetramethyl- 1 ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol; and wherein the polyester is selected to produce a first component refractive index that satisfies the following formula:
- the above methods also include any combination of the various embodiments of the polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides described previously.
- the blending of thermoplastic polymers to obtain a second component and first component that have a difference in refractive index of about 0.006 to about -0.0006 may be illustrated with particular reference to polycarbonate/polyester blends.
- the complete miscibility of a polycarbonate of bisphenol A and PCTG permits the tailoring of refractive index (Rl) of the polycarbonate/PCTG blend, by adjusting the polycarbonate/PCTG ratio.
- the refractive index of the first component of the present invention may be matched to within about 0.006 to about -0.0006 of that of the second component comprising a copolyamide or a homogeneous, transamidized blend of polyamides.
- a polymer may be determined to be a suitable modifying polymer of the homogeneous polyester/polycarbonate blends described hereinabove if a clear blend is formed by: 1 ) blending the modifying polymer with a pre-existing blend containing the polycarbonate and polyester portions, or 2) blending the modifying polymer with the polycarbonate portion prior to the introduction of the polyester portion, or 3) blending the modifying polymer with the polyester portion prior to the introduction of the polycarbonate portion, or 4) mixing the modifying polymer, polycarbonate portion and polyester portion all together prior to blending.
- the clear blends of the present invention can still be modified by the incorporation of modifying polymers to produce performance blends, which may not necessarily be clear.
- polyamides such as nylon 6,6 from DuPont, poly(ether-imides) such as ULTEM poly(ether-imide) from General Electric, polyphenylene oxides such as poly(2,6 ⁇ dimethylphenylene oxide) or polyCphenylene oxide)/polystyrene blends such as the NORYL resins from General Electric, polyesters, polyphenylene sulfides, polyphenylene sulfide/sulfones, poly(ester-carbonates) such as LEXAN 3250 poly(ester- carbonate) (General Electric), polycarbonates other than LEXAN polycarbonate from General Electric, polyarylates such as ARDEL DI OO polyarylate (Amoco), polysulfones, polysulfone ethers, poly(ether-ketones) or aromatic dihydroxy compounds can be used as blend modifiers
- the copolyamide or homogeneous blend of polyamides of the composition of the invention can function as a barrier polymer and, as such, improve the barrier properties of the overall composition.
- barrier polymer means a polymer having one or more of the following properties: (1 ) a water permeability of 2 gm-mils/100 sq in/24 hr or less, as measured by ASTM Method No.
- the barrier properties may be enhanced by incorporating a metal catalyst to produce an oxygen-scavenging composition which catalyzes the reaction of oxygen with one or more polyamides in the composition.
- Our invention therefore, further provides an oxygen-scavenging composition comprising: (A) an immiscible blend comprising
- first component comprising at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof;
- second component comprising a transamidized, homogeneous blend of at least two polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - RKfirst component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 10% or less; and
- B at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic
- the first component of the immiscible blend may comprise a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclo- butanediol, and 1 ,4-cyclohexanedimethanoI.
- another embodiment of the invention is an oxygen-scavenging composition comprising: (A) an immiscible blend comprising
- a first component comprising at least one polyester which comprises:
- diacid residues comprising about 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms; and
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4,4- tetramethyl-l ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol;
- a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - RKfirst component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 1 0% or less; and (B) at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic
- the oxygen-scavenging compositions of the invention also may include a single copolyamide as described hereinabove for the other embodiments of the invention.
- the invention also provides an oxygen-scavenging composition comprising:
- thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof;
- a second component comprising a copolyamide; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - RKfirst component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 10% or less; and
- (B) at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements.
- the first component of the immiscible blend may comprise a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol, and 1 ,4-cyclohexanedimethanol.
- another embodiment of the invention is an oxygen-scavenging composition comprising:
- a first component comprising at least one polyester which comprises:
- diacid residues comprising about 70 to about 1 00 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 1 0 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 1 6 carbon atoms;
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol;
- a second component comprising a copolyamide; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 1 0% or less; and
- oxygen scavenging compositions include any combination of the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, and polyamides described hereinabove.
- another embodiment of the instant invention is an oxygen-scavenging composition consisting essentially of:
- first component consisting essentially of at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof;
- second component consisting essentially of a copolyamide or a transamidized, homogeneous blend of at least two polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 10% or less; and
- the invention provides an oxygen-scavenging composition consisting essentially of : (A) an immiscible blend comprising - I l l -
- a first component consisting essentially of at least one polyester which comprises:
- diacid residues consisting essentially of about 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 1 6 carbon atoms;
- diol residues consisting essentially of about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4,4-tetramethyl-l ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4- cyclohexanedimethanol; and
- a second component consisting essentially of a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 10% or less; and (B) at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic
- the composition is understood to exclude any elements that would substantially alter the essential properties of the composition to which the phrase refers, such as, for example, the refractive index of the components, %haze of the immiscible blend, the %transmittance, the miscibility of the first and second components, or the oxygen-scavenging propertions of the composition.
- the addition an oxygen-scavenging component other than a copolyamide or a transmidized blend of polyamides such as, for example, a diene, polyether, or any easily oxidizable organic compound other than the components as listed in the claims would be excluded.
- the oxygen-scavenging compositions of the invention can include one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements as set forth in the 1984 revision of the Periodic Table by the lnternation Union of Pure and Applied Chemistry .
- Typical oxidation catalysts include transition metal catalysts which can readily interconvert between at least two oxidation states. Examples of metals which can be used include copper, nickel, cobalt, iron, manganese, and combinations thereof. Any amount of catalyst which is effective in catalyzing oxygen scavenging may be used but, typically, the metal will be used in amounts from about 5 ppm to about 1 ,000 ppm.
- metal concentration examples include, about 50 ppm to about 750 ppm, about 5 to about 600 ppm, about 10 to about 500 ppm, about 50 ppm to about 500 ppm, and about 50 to about 300 ppm based on the total weight of the oxygen-scavenging composition.
- the metal typically may be used as the elemental metal itself, as a metal complex containing organic ligands, as an oxide, or as a metal salt.
- metal salts examples include, but are not limited to, chloride, acetate, acetylacetonate, stearate, palmitate, 2- ethylhexanoate, neodecanoate, octanoate, or naphthenate, and mixtures thereof.
- the metal salt may also be an ionomer, in which case a polymeric counterion is employed. Such ionomers are well known in the art.
- the metal catalyst is cobalt or a compound containing cobalt such as, for example, a cobalt salt.
- the cobalt may be in the +2 or +3 oxidation state.
- metal catalysts are rhodium in the + 2 oxidation state and copper in the +2 oxidation state.
- the metals may be added in salt form, conveniently as carboxylate salts such as, for example, cobalt octanoate, cobalt acetate, or cobalt neodecanoate.
- carboxylate salts such as, for example, cobalt octanoate, cobalt acetate, or cobalt neodecanoate.
- the reported amounts are based on the weight of the polymer blends and measured on the metal, not its compound weight as added to the composition.
- cobalt as the metal typical amounts are at least 50 ppm, or at least 60 ppm, or at least 75 ppm, or at least 100 ppm, or at least 125 ppm.
- the catalyst can be added neat or in a carrier (such as a liquid or wax) to an extruder or other device for making an article, or it can be added in a concentrate with a polyamide polymer, in a concentrate with a polyester polymer, or in a concentrate with the immiscible blend.
- the carrier may either be reactive or non-reactive with the first and second component and either volatile or non-volatile carrier liquids may be employed.
- the metal catalyst may be added at a variety of points and by way of a variety of blending protocols during the preparation of the oxygen scavenging composition.
- a particularly useful approach is to bring the polyamide and transition metal together late in the preparation of the final blend composition, even as late as in the final melt step before forming the article, so that the oxygen scavenging activity of the polyamide is not prematurely initiated.
- the first component of the oxygen-scavenging composition can comprise a polyester having any combination of monomer residues as described previously.
- the polyester can comprise (a) diacid residues comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanoI; neopentyl glycol, diethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, and, 2,2,4,4-tetramethyl-l ,3-cyclo
- polyesters comprising: (i) about 80 to about
- polyesters are those comprising about 70 to about 1 00 mole percent, based on the total diacid residues, of the residues of terephthalic acid; and any one of the following diol residue compositions, based on the total diol residues: (i) about 5 to about 60 mole percent of the residues of 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and about 40 to about 95 mole percent of the residues of 1 ,4-cyclohexanedimethanol; (ii) about 1 5 to about 40 mole percent of the residues of 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and about 60 to about 85 mole percent of the residues of 1 ,4-cyclohexanedimethanol; (iii) about 20 to about 30 mole percent of the residues of 2,2,4,4- tetramethyl-l ,3-cyclobutanediol and about 70 to about
- the polyester may also further comprise about 0.1 to about 1 mole%, based on the total diacid residues, of the residues of at least one branching agent selected from trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride, glycerol, sorbitol, 1 , 2, 6-hexanetriol, pentaerythritol, tartaric acid, citric acid, trimethylolethane, and trimesic acid as described hereinabove.
- branching agent selected from trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride, glycerol, sorbitol, 1 , 2, 6-hexanetriol, pentaerythritol, tartaric acid, citric acid, trimethylolethane, and trimesic acid as described hereinabove.
- polyesters are those containing about 1 00 mole percent terephthalic residues, based on the total diacid residues, and any one of the following diol residue compositions, based on the total diol residues: (i) about 1 to about 5 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 99 to about 95 mole percent of the residues of ethylene glycol; (ii) about 29 to about 33 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 71 to about 67 mole percent of the residues of ethylene glycol; (iii) about 45 to about 55 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 55 to about 45 mole percent of the residues of ethylene glycol; (iv) about 60 to about 65 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 40 to about 35 mo
- the first component may also comprise a homogeneous blend of at least one polyester and at least one polycarbonate.
- the polycarbonates that can be used in these homogeneous blends have been described previously.
- the transamidized, homogeneous blend or the copolyamide can comprise any polyamide as described previously such as for example, various nylons. It is advantageous, however, that the copolyamide or homogeneous blend of polyamides of the oxygen-scavenging composition comprise the residues of m-xylylenediamine, p-xylylenediamine, or a combination thereof.
- the second component may comprise a homogeneous blend of a first polyamide comprising the residues of m-xylylenediamine and adipic acid, and a second polyamide comprising nylon 6, nylon 6,6, or blends thereof.
- this homogeneous blend may be combined in an immiscible blend with a first component comprising a homogeneous blend of the polyester and a polycarbonate comprising the residues of bisphenol A. It is desirable also for optimum oxygen scavenging properties that the copolyamide or homogeneous blend of polyamides contain 20 mmoles/kg or less of free amino groups. The concentration of free amino groups can be determined using techniques well known to persons having ordinary skill in the art such as, for example, by titration.
- the oxygen scavenging composition comprises a copolyamide of m-xylylenediamine adipate.
- a modified m- xylylenediamine adipate in which some of the adipic acid residues, or some of the m-xylylenediamine residues, or some of both, are replaced with other residues, can give an oxygen-scavenging composition with improved oxygen- scavenging properties when compared with compositions containing only the m-xylylenediamine adipate homopolymer.
- Other polyamide barrier polymers, as described herein, may also be used as part of the oxygen scavenging composition.
- compositions of the present invention described hereinabove may be used to fabricate shaped articles such as, for example, sheets, films, tubes, preforms, bottles, or profiles. Such articles may be formed by any means well known to persons skilled in the art such as, for example, by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing.
- the compositions of the present invention may be fabricated into shaped articles such as, for example, films, by any technique known in the art. Formation of films can be achieved by melt extrusion, as described, for example, in U.S. Patent No.
- films may be produced by the well known cast film, blown film and extrusion coating techniques, the latter including extrusion onto a substrate.
- a substrate may also include a tie-layer.
- Films produced by melt casting or blowing can be thermally bonded or sealed to a substrate using an adhesive.
- the compositions may be fabricated into monolayer or multilayer films by any technique known in the art.
- monolayer, or multilayer films may be produced by the well known cast film, blown film and extrusion coating techniques, the latter including extrusion onto a substrate.
- Representative substrates include films, sheets, and woven and nonwoven fabrics.
- Monolayer, or multilayer films produced by melt casting or blowing can be thermally bonded or sealed to a substrate using an adhesive.
- the composition may be formed into a film using a conventional blown film apparatus.
- the film forming apparatus may be one which is referred to in the art as a "blown film” apparatus and includes a circular die head for bubble blown film through which the composition is forced and formed into a film "bubble". The "bubble" is ultimately collapsed and formed into a film.
- compositions also may be used to form shaped articles through extrusion blow molding and injection stretch-blow molding.
- An injection molding process softens the copolyamide or homogeneous polyamide blend in a heated cylinder, injecting it while molten under high pressure into a closed mold, cooling the mold to induce solidification, and ejecting the molded preform from the mold.
- Molding compositions are well suited for the production of preforms and subsequent reheat stretch-blow molding of these preforms into the final bottle shapes having the desired properties.
- the injection molded preform is heated to suitable orientation temperature in the 100 0 C to 1 5O 0 C range and then stretch-blow molded.
- the latter process consists of first stretching the hot preform in the axial direction by mechanical means such as by pushing with a core rod insert followed by blowing high pressure air (up to 500 psi) to stretch in the hoop direction. In this manner, a biaxially oriented blown bottle is made. Typical blow-up ratios range from 5/1 to 1 5/1 .
- the excellent transparency and low haze of the compositions of the invention enable the preparation of transparent, shaped articles with the incorporation of substantial amounts of scrap polymer or "regrind".
- the term "regrind”, as used herein, is understood to have its commonly accepted meaning in art, that is, scrap polymer that recovered from an article forming process and ground into smaller particles.
- regrind is sold as scrap for incorporation into shaped articles in which the transparency of the article is immaterial to its application.
- shaped articles such as, for example, bottles and films used in packaging applications
- low haze and high transparency are desirable features.
- the manufacture of these articles, in particular, multilayered articles inherently produces large quantities of scrap polymer which frequently cannot be returned to the article-forming process because of the formation of unacceptable levels of haze.
- low haze, transparent, shaped articles may be produced from the compositions of the invention with the inclusion of regrind.
- Another aspect of our invention is a process for forming a shaped article, comprising:
- a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a copolyamide or a homogeneous, transamidized blend of at least 2 polyamides; wherein the first component (i) and second component (ii) form an immiscible blend, the second component and the first component have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 1 0% or less;
- step (F) combining the polymer regrind with the first and second components (i) and (ii) of step (A).
- the first component can comprise a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, and 1 ,4-cyclohexanedimethanol.
- the instant invention also includes a process for forming a shaped article, comprising: (A) melt blending
- a first component comprising at least one polyester which comprises:
- diacid residues comprising about 70 to about 1 00 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 1 0 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 1 6 carbon atoms;
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4,4- tetramethyl-l ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol; and (ii) a second component comprising a copolyamide or a homogeneous, transamidized blend of at least 2 polyamides; wherein the first component (i) and second component (ii) form an immiscible blend, the second component and the first component have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the immiscible blend has a percent transmittance of at least 75%, and a haze of 1 0% or less;
- step (F) combining the polymer regrind with the first and second components (i) and (ii) of step (A).
- the above process includes the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides, oxygen-scavenging compositions, and any combination thereof described hereinabove.
- the immiscible blend formed from the first and second components may further comprise at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic Table of the Elements.
- metals include, but are not limited to, copper, nickel, cobalt, iron, manganese, and combinations thereof.
- the metal is present in amounts of about 5 to about 600 parts per million by weight of the metal, based on the total weight of the shaped article.
- the preferred metal is cobalt.
- the shaped article of our inventive process may be formed by any methods known in the art and described hereinabove.
- the shaped article may be formed by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing.
- any shaped article representative articles that may be produced are sheets, films, preforms, tubes, and bottles. These articles may have a single layer or contain from 2 to about 7 layers.
- the regrind may be incorporated into one or more of these layers which typically may comprise from about 50 to 100 weight percent regrind based on the weight of the one or more layers.
- Other examples of regrind levels that can be present in the shaped article are 5 to about 95 weight percent, about 10 to about 60 weight percent, about 1 5 to about 50 weight, and about 20 to about 30 weight percent, based on the total weight of the one or more layers.
- the shaped article may comprise multiple layers in which one or more of the layers comprise the first and second component as an immiscible blend or in which the first component and the second component are present in separate layers.
- a multilayered, shaped article comprising:
- a first layer comprising at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof; and (ii) a second layer comprising a transamidized homogeneous blend of at least two polyamides; wherein the second layer (M) and the first layer (i) have a difference in refractive index, Rl(second layer) - Rl(first layer), of about 0.006 to about -0.0006, and the shaped article has a percent transmittance of at least 75%, and a haze of 1 0% or less.
- the first layer can comprise a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, and 1 ,4- cyclohexanedimethanol.
- a multilayered, shaped article comprising: (i) a first layer comprising at least one polyester which comprises:
- diacid residues comprising about 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms; and
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4, 4-tetramethyl- 1 ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol; and
- a second layer comprising a transamidized, homogeneous blend of at least two polyamides; wherein the second layer (ii) and the first layer (i) have a difference in refractive index, RKsecond layer) - Rl(first layer), of about 0.006 to about -0.0006, and the shaped article has a percent transmittance of at least 75%, and a haze of 1 0% or less.
- the shaped article may include the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides, oxygen-scavenging compositions, shaped articles, and any combination thereof described hereinabove.
- the multilayered shaped article may be produced by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing. Because of the close match between the refractive indices of the first and second layers, the multilayered article may further comprise a regrind comprising a mixture of the first and second layers, which may be incorporated into first layer, second layer, or a combination of the first and second layer. Typically, the regrind is about 5 weight percent to about 60 weight percent of the multilayered article, based on the total weight of the article. Other examples of weight percentages of regrind in the shaped article are about 10 weight percent to about 40 weight percent and about 20 weight percent to about 30 weight percent of the total weight of the article.
- the multilayered article can have from 2 to about 7 layers depending on its intended application.
- the shaped article may be a sheet, film, tube, bottle, or preform.
- Complex layered structures are possible also.
- the shaped article can have a layered structure represented by ABA, ABABA, ABCBA, or ACBCA in which layer A comprises the first layer (i), layer B comprises the second layer (ii), and layer C comprises a regrind comprising a mixture of scrap first and second layers (i) and (ii), polyester or polycarbonate obtained from post consumer recycle, or a combination thereof.
- layer B and layer C have a difference in refractive index, RKIayer B) - R(layer C), of about 0.006 to about -0.0006 to maintain the transparency of the article and the ability to incorporate regrind.
- layer A can comprise the second layer (ii)
- layer B comprises the first layer (i)
- layer C comprises a a mixture of scrap first and second layers (i) and (ii), polyester or polycarbonate obtained from post consumer recycle, or a combination thereof.
- the second layer (ii) of our novel multilayered article can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements.
- metals include copper, nickel, cobalt, iron, manganese, and combinations thereof.
- the metal is present in amounts of about 10 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article.
- Other examples of metal concentrations are about 5 ppm to about 600 ppm, and 10 ppm to about 750 ppm, based on the total weight of the shaped article.
- the preferred metal is cobalt.
- the multilayered, shaped article of the invention can further comprise at least one additional layer comprising about 50 to about 100 weight percent of regrind, based on the total weight of the layer.
- the additional layer containing the regrind can further comprise at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic Table of the Elements.
- metals include copper, nickel, cobalt, iron, manganese, and combinations thereof.
- the metal is present in amounts of about 10 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article.
- Other examples of metal concentrations are about 5 ppm to about 600 ppm, and 10 ppm to about 750 ppm, based on the total weight of the shaped article.
- the multilayered, shaped article may comprise the various embodiments of the shaped articles, thermoplastic polymers, polyamides, immiscible blends, homogeneous blends, and oxygen scavenging compositions as described earlier.
- the at least one thermoplastic polymer may comprise a linear or branched polyester comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanol; neopentyl glycol, diethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, and, 2,2,4,4-tetramethyl-l
- polyesters are those comprising about 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms; and any one of the following diol residue compositions, based on the total diol residues: (i) about 5 to about 60 mole percent of the residues of 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and about 40 to about 95 mole percent of the residues of 1 ,4-cyclohexanedimethanol; (ii) about 1 5 to about 40 mole percent of the residues of 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and about 60 to about 85 mole percent
- the polyester may also further comprise about 0.1 to 1 mole%, based on the total diacid residues, of the residues of at least one branching agent selected from trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride, glycerol, sorbitol, 1 , 2, 6-hexanetriol, pentaerythritol, tartaric acid, citric acid, trimethylolethane, and trimesic acid as described hereinabove.
- the thermoplastic polymer may comprise a branched polyester.
- the thermoplastic polymer further comprise a homogeneous blend of the polyester and a polycarbonate comprising the residues of bisphenol A.
- the multilayered, shaped articles of the present invention may be prepared by any method known to persons of ordinary skill in the art.
- the shaped articles can be formed by any conventional technique for forming films, including lamination, extrusion lamination, coinjection, stretch- blow molding and coextrusion blowmolding, and may be illustrated with particular reference to a typical method for making multilayer film by coextrusion.
- the first and second components, as well as any optional layers are fed into infeed hoppers of the extruders of like number, each extruder handling the material for one or more of the layers.
- the first and second components each will be heated to a temperature of about Tg + 100 0 C to about Tg + 300 0 C before and during extrusion, wherein Tg is the glass transition temperature of the first or second component as measured by differential scanning calorimetry.
- Tg is the glass transition temperature of the first or second component as measured by differential scanning calorimetry.
- the melted streams from the individual extruders are fed into a single manifold co-extrusion die. While in the die, the layers are juxtaposed and combined, then emerge from the die as a single multiple layer film of polymeric material. After exiting the die, the film is cast onto a first controlled temperature casting roll, passes around the first roll, and then onto a second controlled temperature roll, which is normally cooler than the first roll.
- the film forming apparatus may be one which is referred to in the art as a blown film apparatus and includes a multi-manifold circular die head for bubble blown film through which the film composition is forced and formed into a film bubble which may ultimately be collapsed and formed into a film.
- Processes of coextrusion to form film and sheet laminates are generally known.
- the individual layers may first be formed into sheets and then laminated together under heat and pressure with or without intermediate adhesive layers.
- compositions of the invention also enable the preparation of multilayered, transparent, shaped articles with the incorporation of substantial amounts of scrap polymer or "regrind".
- Our invention therefore, also provides a process for forming a multilayered, shaped article, comprising:
- thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof to a temperature of about Tg +100 0 C to about Tg + 300 0 C of the first component;
- heating a second component comprising a copolyamide or a transamidized, homogeneous blend of at least two polyamides to a temperature of about Tg +10O 0 C to about Tg + 300 0 C of the second component;
- step (iv) recovering scrap first and second components; (v) grinding the scrap first and second components to produce a regrind; (vi) optionally, drying the regrind; and (vii) combining the regrind with the first component, second component, or a combination thereof, of steps (i) and (ii); wherein the second component of step (ii) and the first component of step (i) of have a difference in refractive index, RKsecond component) - Rl(first component), of about 0.006 to about -0.0006, and the shaped article has a percent transmittance of at least 75%, and a haze of 10% or less.
- the first component can comprise a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, and 1 ,4- cyclohexanedimethanol.
- another aspect of the invention is a process for forming a multilayered shaped article, comprising: (i) heating a first component to a temperature of about Tg + 1 00 0 C to about
- the first component comprising at least one polyester which comprises:
- diacid residues comprising about 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 1 6 carbon atoms;
- diol residues comprising about 1 to about 99 mole percent, based on the total diol residues, of the residues of 2,2,4, 4-tetramethyl- 1 ,3-cyclobutanediol; and about 1 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol;
- steps (vii) and (vii) combining the regrind with the first component, second component, or a combination thereof, of steps (i) and (ii); wherein the second component of step (ii) and the first component of step (i) of have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the shaped article has a percent transmittance of at least 75%, and a haze of 10% or less.
- the above processes may include the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides, oxygen-scavenging compositions, shaped articles, article-forming processes, and any combination thereof described hereinabove.
- the regrind will typically comprise a mixture of the first and second components of steps (i) and (ii) that are produced as scrap during the article-forming process, but any polymer material can be used as long as its refractive index differs from the that second component by about 0.006 to about -0.0006.
- the regrind material of the process can be combined with the first component of step (i), the second component of step (ii) or a combination of the first and second components.
- the regrind may be incorporated into the first or second layer and can be from about 5 weight percent to about 60 weight percent of the shaped article, based on the total weight of the shaped article.
- Other representative examples of regrind content for the shaped artice of the process of the invention are about 10 weight percent to about 40 weight percent of the shaped article and about 20 weight percent to about 30 weight percent of the shaped article.
- the multilayered article of our process can have from 2 to about 7 layers depending on its intended application.
- the multilayered, shaped article may be a sheet, film, tube, bottle, or preform.
- Complex layered structures are possible also.
- the shaped article can have a layered structure represented by ABA, ABABA, ABCBA, or ACBCA in which layer A comprises the first component of step (i), layer B comprises the second component of step (ii), and layer C comprises a regrind comprising a mixture of scrap first and second components from steps (i) and (ii), polyester or polycarbonate obtained from post consumer recycle, or a combination thereof.
- layer B and layer C have a difference in refractive index, Rl(layer B) - R(layer C) 1 of about 0.006 to about -0.0006 to maintain the transparency of the article and the ability to incorporate regrind.
- layer A can comprise the second component of step (ii)
- layer B comprises the first component of step (i)
- layer C comprises a a mixture of scrap first and second components of steps (i) and (ii), polyester or polycarbonate obtained from post consumer recycle, or a combination thereof.
- the second component of step (ii) of our novel multilayered article can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements.
- metals which can be used include copper, nickel, cobalt, iron, manganese, and combinations thereof.
- the metal is present in amounts of about 10 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article.
- Other examples of metal concentrations are about 5 ppm to about 600 ppm, and 10 ppm to about 750 ppm, based on the total weight of the shaped article.
- the preferred metal is cobalt. When metals are present, is advantageous to adjust the diacid-diamine ratio to produce the concentration of terminal amine groups to 20 mmole/kg or less.
- step (iii) of the process of the invention can further comprise forming at least one additional layer comprising about 50 to about 100 weight percent of regrind, based on the total weight of the layer.
- the additional layer containing the regrind can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements. Examples of metals include copper, nickel, cobalt, iron, manganese, and combinations thereof. Typically, the metal is present in amounts of about 10 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article.
- the multilayered, shaped article may comprise the various embodiments of the shaped articles, thermoplastic polymers, polyamides, immiscible blends, homogeneous blends, and oxygen scavenging compositions as described earlier.
- the at least one thermoplastic polymer may comprise a polyester comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanol; neopentyl glycol, diethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, and, 2,2,4,4-tetramethyl-l ,3-cyclo
- polyesters are those comprising about 70 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid; 0 to about 30 mole percent of the residues of at least one modifying aromatic dicarboxylic acid having up to 20 carbon atoms; and 0 to about 10 mole percent of the residues of at least one modifying aliphatic dicarboxylic acid having up to 16 carbon atoms; and any one of the following diol residue compositions, based on the total diol residues: (i) about 5 to about 60 mole percent of the residues of 2,2,4,4-tetramethyl-l ,3- cyclobutanediol and about 40 to about 95 mole percent of the residues of 1 ,4- cyclohexanedimethanol; (ii) about 1 5 to about 40 mole percent of the residues of 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and about 60 to about
- the polyester may also further comprise about 0.1 to 1 mole%, based on the total diacid residues, of the residues of at least one branching agent selected from trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride, glycerol, sorbitol, 1 , 2, 6- hexanetriol, pentaerythritol, tartaric acid, citric acid, trimethylolethane, and trimesic acid as described hereinabove.
- branching agent selected from trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride, glycerol, sorbitol, 1 , 2, 6- hexanetriol, pentaerythritol, tartaric acid, citric acid, trimethylolethane, and trimesic acid as described hereinabove.
- the thermoplastic polymer may comprise a branched polyester.
- the thermoplastic polymer further comprise a homogeneous blend of the polyester and a polycarbonate comprising the residues of bisphenol A.
- Another embodiment of our invention further is a process for forming a multilayered shaped article, comprising:
- A heating a first component comprising (i) at least one polyester comprising: (a) diacid residues comprising at least about 95 mole percent, based on the total diacid residues, of the residues of terephthalic acid; and (b) diol residues comprising at least 95 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol and 1 ,4-cyclohexanedimethanol; (ii) at least one polycarbonate comprising the residues of bisphenol A; or (iii) a homogeneous blend thereof to a temperature of about Tg +100 0 C to about Tg + 300°C of the first component;
- the first component can comprise a polyester comprising the residues of terephthalic acid, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol, and 1 ,4- cyclohexanedimethanol.
- another embodiment of the invention is a process for forming a multilayered shaped article, comprising:
- the first component comprising at least one polyester which comprises: (a) diacid residues comprising about 95 to about 1 00 mole percent, based on the total diacid residues, of the residues of terephthalic acid; and (b) diol residues comprising about 1 5 to about 40 mole percent, based on the total diol residues, of the residues of 2,2,4,4-tetramethyl-l ,3-cyclobutanediol; and about 60 to about 85 mole percent of the residues of 1 ,4-cyclohexane- dimethanol; wherein the polyester has. an inherent viscosity of about 0.55 to about 0.75 dL/g;
- step (G) combining the regrind with the first component, second component, or a combination thereof, of steps (A) and (B); wherein the second component of step (B) and the first component of step (B) have a difference in refractive index, Rl(second component) - RKfirst component), of about 0.006 to about -0.0006, and the shaped article has a percent transmittance of at least 75%, and a haze of 10% or less.
- the above processs may include the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides, oxygen-scavenging compositions, shaped articles, article-forming processes, and any combination thereof described hereinabove.
- the regrind may comprise a mixture of the first and second components (i) and (ii) and can be combined with the first component (i), second component (ii), or a combination thereof.
- the regrind can be from about 5 weight percent to about 60 weight percent of the shaped article, based on the total weight of the shaped article.
- Other representative examples of regrind content for the shaped artice of the process of the invention are about 10 weight percent to about 40 weight percent of the shaped article and about 20 weight percent to about 30 weight percent of the shaped article.
- the polyester of the process can comprises diacid residues comprising at least about 95 mole percent of the residues of terephthalic acid and can have a range of diol compositions.
- the polyester can comprise diol residues comprising about 1 to about 5 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 99 to about 95 mole percent of the residues of ethylene glycol.
- diol compositions for the polyester of our process include, but are not limited to: (i) diol residues comprising about 29 to about 33 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 71 to about 67 mole percent of the residues of ethylene glycol; (b) diol residues comprising about 45 to about 55 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 55 to about 45 mole percent of the residues of ethylene glycol; (iii) residues comprising about 60 to about 65 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 40 to about 35 mole percent of the residues of ethylene glycol; (i)
- polyesters are those comprising diacid residues comprising about 95 to about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid, and any one of the following diol residue compositions, based on the total diol residues: (i) about 5 to about 60 mole percent of the residues of 2,2,4,4-tetramethyl-l ,3-cyclo- butanediol and about 40 to about 95 mole percent of the residues of 1 ,4- cyclohexanedimethanol; (ii) about 1 5 to about 40 mole percent of the residues of 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and about 60 to about 85 mole percent of the residues of 1 ,4-cyclohexanedimethanol; (iii) about 20 to about 30 mole percent of the residues of 2,2,4,4-tetramethyl-l ,3-cyclobutanedio
- the polyester may further comprise about 0.01 to 1 mole%, based on the total diacid residues, of the residues at least one branching agent selected from trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride, glycerol, sorbitol, 1 , 2, 6- hexanetriol, pentaerythritol, tartaric acid, citric acid, trimethylolethane, and trimesic acid.
- branching agent selected from trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride, glycerol, sorbitol, 1 , 2, 6- hexanetriol, pentaerythritol, tartaric acid, citric acid, trimethylolethane, and trimesic acid.
- thermoplastic polymer may further comprise a homogeneous blend of the polyester and a polycarbonate comprising the residues of bisphenol A.
- a homogeneous blend of the polyester and a polycarbonate comprising the residues of bisphenol A.
- Each of the polyester and polycarbonate may be linear or branched.
- the second component of step (ii) of our novel process can further comprise at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic Table of the Elements.
- metals which can be used include copper, nickel, cobalt, iron, manganese, and combinations thereof.
- the metal is present in amounts of about 10 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article.
- Other examples of metal concentrations are about 5 ppm to about 600 ppm, and 10 ppm to about 750 ppm, based on the total weight of the shaped article.
- the preferred metal is cobalt. When metals are present, is advantageous to adjust the diacid-diamine ratio to produce the concentration of terminal amine groups to 20 mmole/kg or less.
- step (C) of the process of the invention can further comprise forming at least one additional layer comprising about 50 to about 100 weight percent regrind, based on the total weight of the layer.
- the additional layer containing the regrind can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements.
- metals include copper, nickel, cobalt, iron, manganese, and combinations thereof.
- the metal is present in amounts of about 10 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article.
- Other examples of metal concentrations are about 5 ppm to about 600 ppm, and 10 ppm to about 750 ppm, based on the total weight of the shaped article.
- the preferred metal is cobalt.
- the shaped articles of the invention may be further oriented by stretching which may improve the barrier properties of the article.
- it may be desirable to incorporate other conventional additives or modifying polymers with the polymeric compositions of the present invention.
- additives or modifying polymers for example, there may be added antioxidants, heat and light stabilizers, dyes, antistatic agents, lubricants, preservatives, processing aids, slip agents, antiblocking agents, pigments, flame retardants, blowing agents, and the like. More than one additive may be used.
- the additive may be present in any desired amount, but typically are not present at more than about 20 weight percent, preferably not more than 10 weight percent, of the total weight of the shaped article.
- the polymer compositions, oxygen-scavenging compositions, and shaped articles prepared therefrom also may comprise up to about 30 weight percent, preferably less than about 20 weight percent, of certain platelet particles derived from at least one layered silicate material to improve their barrier properties.
- the platelet particles can be modified with at least one ammonium compound.
- the amount of platelet particles may be determined by measuring the residual ash of the polymer-platelet particle compositions when treated in accordance with ASTM D5630-94.
- the gas barrier improvement typically increases with increasing concentration of platelet particles in the composite.
- compositions having at least about 0.5 weight percent of the platelet particles are preferred because they display desirable improvements in gas permeability.
- Generally layered silicate materials are a dense agglomeration of platelet particles which are closely stacked together like cards.
- the platelet particles of the present invention typically have a thickness of less than about 2 nm and a diameter in the range of about 1 0 to about 5000 nm.
- measurements refer only to the platelet particle and not to the ammonium compounds or any additional dispersing aids and treatment compounds which might be used.
- Suitable platelet particles are derived from layered silicate materials that are typically free flowing powders having a cation exchange capacity between about 0.3 and about 3 meq/g and preferably between about 0.8 and about 1.5 meq/g.
- suitable layered silicate materials include mica-type layered phyllosilicates, including clays, smectite clays, sodium montmorillonite, sodium hectorite, bentonites, nontronite, beidelite, volonsloite, saponite, sauconite, magadite, kenyaite, synthetic sodium hectorites, and the like. Clays of this nature are available from various companies including Southern Clay Products and Nanocor, Inc.
- the most preferred platelet particles are derived from sodium bentonite or sodium montmorillonite. Such clays are readily available in the U.S., known as Wyoming type montmorillonite, and other parts of the world, including the Kunipia clays available from Kunimine Industries, Inc.
- the layered silicate materials are typically treated to improve dispersion into the polymer composition.
- Many useful clay treatments are known in the art, and these treatments may also be used before, after, or during incorporation of the layered silicate materials into the composites of this invention without deviating from the scope of this invention.
- Examples of useful treatments include, but are not limited to treatments with silane compounds, expanding agents, polymers and oligomers, dispersing aids, organic cation salts, and their combinations.
- Examples of useful treatment with silane compounds include those treatments disclosed in International Publication No. WO 93/1 1 190.
- Examples of useful silane compounds includes (3-glycidoxypropyl)trimethoxysilane, 2- methoxy (polyethyleneoxy)propyl heptamethyl trisiloxane, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride and the like.
- Examples of useful treatment with expanding agents include oligomeric polymers well known in the art. Representative polymers and oligomers for treating clays include those disclosed in U.S. Patent No.'s 5,552,469 and 5,578,672. Many dispersing aids are known, covering a wide range of materials including water, alcohols, ketones, aldehydes, chlorinated solvents, hydrocarbon solvents, aromatic solvents, and the like or combinations thereof.
- Cenera/ The invention is further illustrated by the following examples.
- the glass transition temperatures (Tg's) of the polyesters, polyamides, and blends were determined by ASTM Method D341 8 using a TA Instruments 2920 differential scanning calorimeter (DSC) at a scan rate of 20°C/min.
- Heat Deflection Temperature was determined by ASTM Method D648, and Notched Izod Impact Strength was performed according to ASTM Method D256.
- Flexural properties were determined according to ASTM Method D790.
- the tensile properties of the blends were determined according to ASTM Method D638 at 23°C.
- the inherent viscosity of the polyesters was determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/1 00 mL at 25 0 C.
- the diol content of the polyester portion of these blends was determined by proton nuclear magnetic resonance spectroscopy ( 1 H NMR).
- the miscibility of the blends was determined by differential scanning calorimetry of pressed films and molded objects.
- haze and percent transmittance was determined by forming the composition into a sheet, film, or plaque having a thickness of 1 /8 inch or less and measuring the haze and percent transmittance according to the above procedure.
- haze and percent transmittance was determined by cutting out a small (i.e., 1 X 1 cm) section of the article, having a thickness of 1 /8 inch or less, and measuring the haze and percent transmittance according the procedure described above.
- Refractive index was measured at 633 nm with a Metricon Prism CouplerTM model 2010 refractometer (available from Metricon Inc.) and is reported as the average of the refractive indices measured in 3 orthogonal directions (extrusion or stretch, transverse, and thickness directions).
- Oriented films were produced on a TM Long film stretcher (named for the producer) which uniaxially or biaxially stretches samples of pressed, blown, or extruded film. The operation of the film stretcher was based upon the movement of two drawbars at right angles to each other upon hydraulically driven rods. There was a fixed draw bar opposed to each moving draw bar.
- Oxygen permeabilities of films were determined using Ox-T ran Oxygen Permeation instruments manufactured by MOCON, Inc. Minneapolis, MN. Oxygen permeabilities were calculated from the known area of the films in the test, thickness of the film, partial pressure differential of oxygen across the film, and the measured steady state transmission rate. In the case of samples which exhibit active oxygen scavenging, the measured flux is not truly at steady state, since the transmission rate can slowly change as the efficiency of the oxygen scavenging reaction changes with time. However, in these instances, the oxygen transmission can often be considered to be at pseudo-steady state during the duration of permeation measurement. In the active oxygen scavenger samples included in the examples which follow, little to no change in scavenger efficiency was evident during the course of the measurements and permeabilities were calculated from the measured pseudo-steady state transmission rates.
- Comparative Examples 1-12 The copolyesters listed in Table 1 , with the exception of polyester G, were prepared from terephthalic acid, ethylene glycol, and 1 ,4-cyclohexanedimethanol (CHDM). The amount of CHDM in the polyesters is shown in Table 1.
- Example F contains 1 00% CHDM (0% ethylene glycol) but 26 mole% of the acid portion is isophthalic acid instead of terephthalic acid.
- Polyester G was prepared as follows: 21.24 Ib (49.71 gram- mol) dimethyl terephthalate, 12.61 Ib (39.77 gram-mol) 1 ,4- cyclohexanedimethanol, and 6.30 Ib (1 9.88 gram-mol) 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The cis/trans ratio of the 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol was approximately 50/50.
- the cis/trans ratio of the 1 ,4-cyclohexanedimethanol was approximately 30/70.
- the reaction was carried out under a nitrogen gas purge in an 1 8-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 25O 0 C and the pressure was increased to 20 psig. The reaction mixture was held for 2 hours at 250 0 C and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. The temperature of the reaction mixture was then increased to 27O 0 C and the pressure was decreased to 90 mm of Hg.
- the agitator speed was decreased to 1 5 RPM
- the reaction mixture temperature was increased to 290°C
- the pressure was decreased to ⁇ 1 mm of Hg.
- the reaction mixture was held at 290°C and at a pressure of ⁇ 1 mm of Hg for 1 2 minutes.
- the pressure of the pressure vessel was then increased to 1 atmosphere using nitrogen gas.
- the molten polymer was then extruded from the pressure vessel.
- the cooled, extruded polymer was ground to pass a 6-mm screen.
- the polymer had an inherent viscosity of 0.590 dL/g and a Tg of 1 06 0 C.
- copolyesters and MXD6 6121 polyamide (containing 100 mole% m-xylylene and 1 00 mole% adipic acid, available from Mitsubishi Corporation) were dried overnight at 7O 0 C.
- MXD6 6121 polyamide containing 100 mole% m-xylylene and 1 00 mole% adipic acid, available from Mitsubishi Corporation
- Each of these copolyesters were bag blended with a MXD6 at 1 , 3, and 5 wt% and fed to a Sterling 1 .5 inch single screw extruder at 90 rpm under the following temperature settings (degrees C) to form a blend:
- Nylon 6 (availabe as Zytel ® 7335F from DuPont) and MXD6 (grade 6121 ) were dried at 120 0 C for 48 hours and bag blended in various ratios. Polyamide bag blends were then fed to a Sterling 1 .5 inch single screw extruder at 90 rpm under the following conditions ( 0 C) to form a homogeneous, transamidized blends as indicated by the presence of a single, composition dependent Tg value for each blend. The Tg values are shown in Table 3.
- Example 40 In this prophetic example, a synthetic route to a polyamide with the appropriate refractive index is employed instead of blending two polyamides as in the above Examples 13-24. Any method known in the art can be used to produce these directly synthetic polyamides.
- the polyamides are generally prepared by melt phase polymerization from a diacid-diamine complex which may be prepared either in situ or in a separate step. In either method, the diacid and diamine are used as starting materials. Alternatively, an ester form of the diacid may be used, preferably the dimethyl ester. If the ester is used, the reaction must be carried out at a relatively low temperature, generally 80 to 12O 0 C, until the ester is converted to an amide.
- the polyamide synthesized is poly(m-xylylene pimelamide) which is synthesized from the diamine m-xylylenediamine and the diacid pimelic acid.
- This polyamide is then blended with 90 wt% of the copolyester A in Table 1 , in accordance with methods disclosed in Examples 25-39.
- the difference in refractive index between these the copolyester A and poly(m-xylylene pimelamide) is predicted to be 0.0034 and is predicted to be transparent.
- the resulting blend is predicted to have a haze value of less 10% and a transmittance of greater than 75%.
- Examples 42, 47-49, and 56 and Comparative Examples 41, 43-46, and 50-55 Monolayer Films of blends and Oxygen-Scavenging Compositions: Several- MXD6/N6 transamidized blends were prepared in the manner discussed above for examples 13-24 and are given in Table 5. The refractive index values listed in Table 5 were measured on 1 5mil films of these transamidized blends in the manner discussed above for examples 1 3-24. Three wt% or 5 wt% of either these transamidized MXD6/N6 preblends or MXD6 were bag blended with several of the copolyesters from Table 1 as per Table 6.
- a concentrate containing cobalt neodecanoate was added to two of the films.
- This concentrate was prepared as follows. Separate feeds of polyester type C and cobalt neodecanoate, in the form of a pastille and supplied as Cobalt Ten-CemTM 22.5% (available from OMG Corp.) were fed into a 57mm twin-screw extruder and melt blended at barrel set points of approximately 235 0 C. Molten polymer exited the extruder in the form of approximate 0.08" diameter strands which were water quenched and cut into approximate 0.125" length pellets.
- the ratio (by weight) of polyester to polyamide to concentrate was 93:5 to 5 to 1 .5 and the concentration of cobalt metal in the concentrate was such that this ratio resulted in about 140 to 1 50 ppm cobalt in the final blended film.
- the samples which contained cobalt exhibited excellent oxygen scavenging capacity. These samples, which were mounted on the Ox-T ran permeation instrument 1 week after extrusion, had average apparent permeabilities under these conditions of less than 0.1 5 cc(STP)*miI/ 100 in 2 /day/atm for over 6 months. Table 6 - 30 mil Monolayer Film Results
- Multilayer films were prepared by coextruding two 1 5 mil layers of polyester C around a 4 mil thick layer of either MXD6 or transamidized MXD6/30wt% N6 blend 11 X". This is referred to as an "ABA" structure where the "A" layers are the outer layers and the "B” layer is the interior layer. A Killian 1 " extruder was used to extrude the outer layers from polyester C at a temperature of 265 0 C.
- a 0.75" Killian extruder was used to extrude the inner layers at a temperature of 285 0 C for the MXD6, and 275°C for the transamidized MXD6/30wt% Nylon 6 blend "X"
- these multilayer films were then ground up and dry blended with additional polyester C pellets at a 50/50 ratio.
- This dry blend was then dried at 7O 0 C and extruded on a Killian 1 " extruder at a temperature of 240 0 C into 20 mil films. Haze values are shown in Table 7.
- the coextruded films all have haze values less then 2%. However, when these films are reground and blended with neat polyester "C", the film containing the C/MXD6 regrind blend the values increase above 1 0%.
- the film containing the "C/X" regrind remains clear.
- multilayer films were prepared by co-extruding two 1 5 mil layers of polyester C around a 5 mil thick layer of either MXD6 or transamidized MXD6/50wt% N6 blend "Z".
- This is referred to as an "ABA" structure where the "A” layers are the outer layers and the "B” layer is the interior layer.
- a Killian 1 " extruder was used to extrude the outer layers from polyester G at a temperature of 285 0 C.
- a 0.75" Killian extruder was used to extrude the inner layers of either MXD6 or the transamidized MXD6/5Owt% Nylon 6 blend "Z" at a temperature of 285 0 C.
- these multilayer films were then ground up and dry blended with additional polyester G pellets at a 50/50 ratio. This dry blend was then dried at 1 00 0 C and extruded on a Killian 1 " extruder at a temperature of 280 0 C into 20 mil films. Haze values are shown in Table 7. The coextruded films all have haze values less then 2.5%. However, when these films are reground and blended with neat polyester "G", the film containing the G/MXD6 regrind blend the values increase above 10%. The film containing the "G/Z" regrind remains clear.
- Example 64 and Comparative Examples 63 - Adhesion of multilayer films ABA films were prepared by co-extruding two 1 5 mil layers of polyester C around a 4 mil thick layer of either MXD6 or transamidized MXD6/30wt% N6 blend "X".
- the Nylon 6 used in the transamidized blend in this example was Zytel 7301 .
- a Killian 1 " extruder was used to extrude the outer polyester C layers at a temperature of 265 0 C.
- a 0.75" Killian extruder was used to extrude the inner layers at the temperatures indicated in Table 8.
- the transamidized MXD6/30wt% N6 blend "X" shows superior adhesion over MXD6 to polyester C.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyamides (AREA)
- Packages (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Wrappers (AREA)
Abstract
Description
Claims
Applications Claiming Priority (15)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US69156705P | 2005-06-17 | 2005-06-17 | |
US73145405P | 2005-10-28 | 2005-10-28 | |
US73138905P | 2005-10-28 | 2005-10-28 | |
US73905805P | 2005-11-22 | 2005-11-22 | |
US73886905P | 2005-11-22 | 2005-11-22 | |
US75069305P | 2005-12-15 | 2005-12-15 | |
US75069205P | 2005-12-15 | 2005-12-15 | |
US75068205P | 2005-12-15 | 2005-12-15 | |
US75054705P | 2005-12-15 | 2005-12-15 | |
US11/363,374 US7964258B2 (en) | 2005-03-02 | 2006-02-27 | Transparent, oxygen-scavenging compositions and articles prepared therefrom |
US11/363,418 US20060199871A1 (en) | 2005-03-02 | 2006-02-27 | Multilayered, transparent articles and a process for their preparation |
US11/363,417 US7955533B2 (en) | 2005-03-02 | 2006-02-27 | Process for the preparation of transparent shaped articles |
US11/363,481 US7786252B2 (en) | 2005-03-02 | 2006-02-27 | Preparation of transparent multilayered articles |
US11/363,375 US7968164B2 (en) | 2005-03-02 | 2006-02-27 | Transparent polymer blends and articles prepared therefrom |
PCT/US2006/012660 WO2006137961A1 (en) | 2005-06-17 | 2006-03-30 | Multilayered, transparent articles containing polyesters comprising a cyclobutanediol and a process for their preparation |
Publications (1)
Publication Number | Publication Date |
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EP1907181A1 true EP1907181A1 (en) | 2008-04-09 |
Family
ID=36658746
Family Applications (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20060749018 Active EP1891158B1 (en) | 2005-06-17 | 2006-03-30 | Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
EP20060740072 Active EP1913085B1 (en) | 2005-06-17 | 2006-03-30 | Transparent oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
EP20060749031 Active EP1901871B1 (en) | 2005-06-17 | 2006-03-30 | Preparation of transparent, multilayered articles containing polyesters comprising a cyclobutanediol and homogeneneous polyamide blends |
EP06749328A Withdrawn EP1907181A1 (en) | 2005-06-17 | 2006-03-30 | Multilayered, transparent articles containing polyesters comprising a cyclobutanediol and a process for their preparation |
EP20060740279 Active EP1910466B1 (en) | 2005-06-17 | 2006-03-30 | Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol |
Family Applications Before (3)
Application Number | Title | Priority Date | Filing Date |
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EP20060749018 Active EP1891158B1 (en) | 2005-06-17 | 2006-03-30 | Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
EP20060740072 Active EP1913085B1 (en) | 2005-06-17 | 2006-03-30 | Transparent oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
EP20060749031 Active EP1901871B1 (en) | 2005-06-17 | 2006-03-30 | Preparation of transparent, multilayered articles containing polyesters comprising a cyclobutanediol and homogeneneous polyamide blends |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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EP20060740279 Active EP1910466B1 (en) | 2005-06-17 | 2006-03-30 | Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol |
Country Status (6)
Country | Link |
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EP (5) | EP1891158B1 (en) |
JP (5) | JP2008546562A (en) |
KR (1) | KR20080021013A (en) |
AT (4) | ATE411361T1 (en) |
HK (4) | HK1115404A1 (en) |
WO (5) | WO2007001534A1 (en) |
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US9598533B2 (en) | 2005-11-22 | 2017-03-21 | Eastman Chemical Company | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
US9169388B2 (en) | 2006-03-28 | 2015-10-27 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof |
CN101711374B (en) | 2007-03-08 | 2011-11-02 | 澳加光学有限公司 | Eyeglasses and eyeglass frames comprising glycol modified copolyesters |
WO2010101562A1 (en) * | 2009-03-02 | 2010-09-10 | Eastman Chemical Company | Molded articles made from blends of polyesters and bisphenol a polycarbonates |
JP4902717B2 (en) * | 2009-10-05 | 2012-03-21 | 住友化学株式会社 | Manufacturing method of laminated resin plate |
US20120305575A1 (en) * | 2011-06-01 | 2012-12-06 | Eastman Chemical Company | High strength bottle |
US20130217830A1 (en) | 2012-02-16 | 2013-08-22 | Eastman Chemical Company | Clear Semi-Crystalline Articles with Improved Heat Resistance |
EP2907851B1 (en) * | 2012-10-15 | 2017-05-03 | Asahi Kasei Kabushiki Kaisha | Thermoplastic resin composition and molded product thereof |
EP3318501B1 (en) * | 2015-07-02 | 2020-05-20 | Toyo Seikan Group Holdings, Ltd. | Cup-type multilayered container |
JP6642042B2 (en) * | 2016-01-27 | 2020-02-05 | 三菱ケミカル株式会社 | Heat-shrinkable tube and electronic component or battery covered with the tube |
US11390416B2 (en) | 2016-12-08 | 2022-07-19 | Amcor Rigid Packaging Usa, Llc | Multi-layer barrier for a container |
US10070516B1 (en) | 2017-06-14 | 2018-09-04 | Eastman Chemical Company | Multilayer stretchable films for flexible printed circuits and methods of making |
JP2019167460A (en) * | 2018-03-23 | 2019-10-03 | プランティック・テクノロジーズ・リミテッド | Resin composition |
EP3921139A4 (en) | 2019-02-05 | 2022-12-21 | Eastman Chemical Company | Reduced haze compositions for coatings |
EP3990281A1 (en) * | 2019-06-26 | 2022-05-04 | Eastman Chemical Company | Multilayer polymeric cushion films for foldable displays |
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US3313777A (en) * | 1959-12-18 | 1967-04-11 | Eastman Kodak Co | Linear polyesters and polyester-amides from 2, 2, 4, 4-tetraalkyl-1, 3-cyclobutanediols |
US6288161B1 (en) * | 1990-01-31 | 2001-09-11 | Pechiney Emballage Flexible Europe | Barrier compositions and articles made therefrom |
JP3725915B2 (en) * | 1995-02-14 | 2005-12-14 | 共同印刷株式会社 | Polymer alloy of copolymerized polyester resin and polycarbonate resin, and packaging material and packaging container comprising the same |
JP3153437B2 (en) * | 1995-05-11 | 2001-04-09 | 電気化学工業株式会社 | Polyester-based multilayer sheet, container, and method for producing the same |
US5942585A (en) * | 1996-12-28 | 1999-08-24 | Eastman Chemical Company | Polycarbonate and polyester blends |
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US5989663A (en) * | 1996-12-30 | 1999-11-23 | Eastman Chemical Company | Blow-molding polyesters from terephthalic acid, 2, 2, 4, 4-tetramethyl-1,3-cyclobutanediol, and ethylene glycol |
EP0964893A1 (en) * | 1997-03-05 | 1999-12-22 | Eastman Chemical Company | Naphthalenedicarboxylate containing polyester/polyamide blend having improved flavor retaining property |
JP4495264B2 (en) * | 1998-04-24 | 2010-06-30 | 株式会社クレハ | Heat shrinkable multilayer film |
CN1505661A (en) * | 1999-07-30 | 2004-06-16 | 伊斯曼化学公司 | Polyester-polyamide blends with reduced gas permeability and low haze |
EP1239008B1 (en) * | 2001-03-05 | 2004-04-14 | Mitsubishi Gas Chemical Company, Inc. | Polyester-based resin composition and shaped articles |
AU784042B2 (en) * | 2001-05-24 | 2006-01-19 | Mitsubishi Gas Chemical Company, Inc. | Polyester based resin composition and molded product therefrom |
JP2002348482A (en) * | 2001-05-25 | 2002-12-04 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
US7037576B2 (en) * | 2002-02-06 | 2006-05-02 | Eastman Chemical Company | Polyester or copolyester/polyolefin laminate structures and methods of making the same |
CN1550326B (en) * | 2003-05-06 | 2010-08-25 | 三菱瓦斯化学株式会社 | Multilayer container |
JP2005008809A (en) * | 2003-06-20 | 2005-01-13 | Mitsubishi Gas Chem Co Inc | Method for producing recycled polyester resin composition |
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-
2006
- 2006-03-30 AT AT06740072T patent/ATE411361T1/en not_active IP Right Cessation
- 2006-03-30 EP EP20060749018 patent/EP1891158B1/en active Active
- 2006-03-30 AT AT06749018T patent/ATE411359T1/en not_active IP Right Cessation
- 2006-03-30 AT AT06749031T patent/ATE413938T1/en not_active IP Right Cessation
- 2006-03-30 WO PCT/US2006/011693 patent/WO2007001534A1/en active Application Filing
- 2006-03-30 JP JP2008516864A patent/JP2008546562A/en not_active Withdrawn
- 2006-03-30 WO PCT/US2006/012074 patent/WO2007001574A1/en active Application Filing
- 2006-03-30 WO PCT/US2006/012660 patent/WO2006137961A1/en active Application Filing
- 2006-03-30 JP JP2008516843A patent/JP2008543610A/en active Pending
- 2006-03-30 JP JP2008516828A patent/JP2008546864A/en not_active Withdrawn
- 2006-03-30 WO PCT/US2006/011928 patent/WO2007001561A1/en active Application Filing
- 2006-03-30 EP EP20060740072 patent/EP1913085B1/en active Active
- 2006-03-30 JP JP2008516856A patent/JP2008544036A/en not_active Withdrawn
- 2006-03-30 EP EP20060749031 patent/EP1901871B1/en active Active
- 2006-03-30 AT AT06740279T patent/ATE411360T1/en not_active IP Right Cessation
- 2006-03-30 EP EP06749328A patent/EP1907181A1/en not_active Withdrawn
- 2006-03-30 JP JP2008516834A patent/JP2008544021A/en not_active Withdrawn
- 2006-03-30 EP EP20060740279 patent/EP1910466B1/en active Active
- 2006-03-30 WO PCT/US2006/011909 patent/WO2007001551A1/en active Application Filing
- 2006-03-30 KR KR20077028785A patent/KR20080021013A/en not_active Application Discontinuation
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2008
- 2008-05-14 HK HK08105338A patent/HK1115404A1/en not_active IP Right Cessation
- 2008-05-14 HK HK08105342A patent/HK1115405A1/en not_active IP Right Cessation
- 2008-06-19 HK HK08106816A patent/HK1116815A1/en not_active IP Right Cessation
- 2008-06-19 HK HK08106818A patent/HK1116727A1/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
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See references of WO2006137961A1 * |
Also Published As
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HK1116815A1 (en) | 2009-01-02 |
EP1910466A1 (en) | 2008-04-16 |
HK1116727A1 (en) | 2009-01-02 |
JP2008544036A (en) | 2008-12-04 |
ATE411361T1 (en) | 2008-10-15 |
JP2008546562A (en) | 2008-12-25 |
WO2007001551A1 (en) | 2007-01-04 |
EP1901871B1 (en) | 2008-11-12 |
KR20080021013A (en) | 2008-03-06 |
WO2006137961A1 (en) | 2006-12-28 |
WO2006137961A8 (en) | 2008-01-24 |
WO2007001574A1 (en) | 2007-01-04 |
JP2008546864A (en) | 2008-12-25 |
EP1901871A1 (en) | 2008-03-26 |
JP2008543610A (en) | 2008-12-04 |
EP1913085B1 (en) | 2008-10-15 |
EP1910466B1 (en) | 2008-10-15 |
JP2008544021A (en) | 2008-12-04 |
WO2007001551A8 (en) | 2007-03-01 |
WO2007001561A1 (en) | 2007-01-04 |
ATE411359T1 (en) | 2008-10-15 |
ATE411360T1 (en) | 2008-10-15 |
EP1913085A1 (en) | 2008-04-23 |
HK1115404A1 (en) | 2008-11-28 |
WO2007001534A1 (en) | 2007-01-04 |
EP1891158B1 (en) | 2008-10-15 |
ATE413938T1 (en) | 2008-11-15 |
HK1115405A1 (en) | 2008-11-28 |
EP1891158A1 (en) | 2008-02-27 |
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