IL131170A - A polymer blend containing polyester and anhydrite acid and processes for its preparation - Google Patents
A polymer blend containing polyester and anhydrite acid and processes for its preparationInfo
- Publication number
- IL131170A IL131170A IL13117098A IL13117098A IL131170A IL 131170 A IL131170 A IL 131170A IL 13117098 A IL13117098 A IL 13117098A IL 13117098 A IL13117098 A IL 13117098A IL 131170 A IL131170 A IL 131170A
- Authority
- IL
- Israel
- Prior art keywords
- polyester
- acid anhydride
- polyhydric alcohol
- polymer blend
- pet
- Prior art date
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 118
- 150000008065 acid anhydrides Chemical class 0.000 title claims abstract description 54
- 229920002959 polymer blend Polymers 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 47
- 238000002360 preparation method Methods 0.000 title description 3
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 59
- 239000002243 precursor Substances 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 71
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 71
- 239000003054 catalyst Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 31
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 27
- 229920001577 copolymer Polymers 0.000 claims description 27
- 239000000654 additive Substances 0.000 claims description 23
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 23
- 239000000155 melt Substances 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- -1 polyethylene terephthalate Polymers 0.000 claims description 12
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 8
- 229920001225 polyester resin Polymers 0.000 claims description 8
- 239000004645 polyester resin Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000010168 coupling process Methods 0.000 claims description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 229920013730 reactive polymer Polymers 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 claims description 3
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 claims 2
- 239000012963 UV stabilizer Substances 0.000 claims 2
- 230000003078 antioxidant effect Effects 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 2
- 239000004088 foaming agent Substances 0.000 claims 2
- 239000013538 functional additive Substances 0.000 claims 2
- 229920000106 Liquid crystal polymer Polymers 0.000 claims 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 53
- 229920000642 polymer Polymers 0.000 description 29
- 230000000694 effects Effects 0.000 description 25
- 238000012986 modification Methods 0.000 description 25
- 230000004048 modification Effects 0.000 description 25
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 238000000518 rheometry Methods 0.000 description 13
- 238000012545 processing Methods 0.000 description 12
- 238000007792 addition Methods 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 7
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000000071 blow moulding Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 241000233805 Phoenix Species 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- POLIXZIAIMAECK-UHFFFAOYSA-N 4-[2-(2,6-dioxomorpholin-4-yl)ethyl]morpholine-2,6-dione Chemical compound C1C(=O)OC(=O)CN1CCN1CC(=O)OC(=O)C1 POLIXZIAIMAECK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000006085 branching agent Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 235000014171 carbonated beverage Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- UFOIOXZLTXNHQH-UHFFFAOYSA-N oxolane-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1OC(C(O)=O)C(C(O)=O)C1C(O)=O UFOIOXZLTXNHQH-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- MNUHUVIZSPCLFF-UHFFFAOYSA-N 1-methylhept-6-ene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)CC(C(O)=O)C(C=C)C(O)=O MNUHUVIZSPCLFF-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- VILWHDNLOJCHNJ-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfanylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1SC1=CC=C(C(O)=O)C(C(O)=O)=C1 VILWHDNLOJCHNJ-UHFFFAOYSA-N 0.000 description 1
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 description 1
- GEYAGBVEAJGCFB-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 GEYAGBVEAJGCFB-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical group C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 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 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- HIZCTWCPHWUPFU-UHFFFAOYSA-N Glycerol tribenzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(OC(=O)C=1C=CC=CC=1)COC(=O)C1=CC=CC=C1 HIZCTWCPHWUPFU-UHFFFAOYSA-N 0.000 description 1
- 101000837308 Homo sapiens Testis-expressed protein 30 Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001054 Poly(ethylene‐co‐vinyl acetate) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 102100028631 Testis-expressed protein 30 Human genes 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000012632 extractable Substances 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010103 injection stretch blow moulding Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000013365 molecular weight analysis method Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 229920001713 poly(ethylene-co-vinyl alcohol) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- 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
- C08G63/46—Polyesters chemically modified by esterification
-
- 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
- C08G63/78—Preparation processes
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Medicinal Preparation (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPO4887A AUPO488797A0 (en) | 1997-01-31 | 1997-01-31 | Modified polyesters |
| AUPO6627A AUPO662797A0 (en) | 1997-05-06 | 1997-05-06 | Modified polyesters |
| PCT/AU1998/000051 WO1998033837A1 (en) | 1997-01-31 | 1998-01-30 | Modified polyesters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL131170A0 IL131170A0 (en) | 2001-01-28 |
| IL131170A true IL131170A (en) | 2004-09-27 |
Family
ID=25645354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL13117098A IL131170A (en) | 1997-01-31 | 1998-01-30 | A polymer blend containing polyester and anhydrite acid and processes for its preparation |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US6350822B1 (enExample) |
| EP (1) | EP0956313B1 (enExample) |
| JP (1) | JP2001509197A (enExample) |
| KR (1) | KR100567089B1 (enExample) |
| CN (1) | CN1109056C (enExample) |
| AT (1) | ATE269370T1 (enExample) |
| CA (1) | CA2278800C (enExample) |
| DE (1) | DE69824550T2 (enExample) |
| DK (1) | DK0956313T3 (enExample) |
| ES (1) | ES2223117T3 (enExample) |
| ID (1) | ID22418A (enExample) |
| IL (1) | IL131170A (enExample) |
| MY (1) | MY120019A (enExample) |
| NZ (1) | NZ336961A (enExample) |
| PT (1) | PT956313E (enExample) |
| WO (1) | WO1998033837A1 (enExample) |
Families Citing this family (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AUPP610798A0 (en) * | 1998-09-23 | 1998-10-15 | Swig Pty Ltd | Improved polymers |
| EP1054031B1 (de) * | 1999-05-21 | 2005-08-24 | Ciba SC Holding AG | Molekulargewichtsaufbau und Modifizierung von Polykondensaten |
| WO2003066704A1 (en) * | 2002-02-01 | 2003-08-14 | Johnson Polymer, Llc | Oligomeric chain extenders for processing, post-processing and recycling of condensation polymers, synthesis, compositions and applications |
| KR100531934B1 (ko) * | 2002-06-25 | 2005-11-28 | 주식회사 삼양사 | 필름용 폴리에스테르계 수지 조성물 및 그 제조방법 |
| US20040147678A1 (en) * | 2003-01-29 | 2004-07-29 | Clariant International, Ltd. | Solid concentrate composition for polymeric chain extension |
| KR100553883B1 (ko) * | 2003-02-26 | 2006-02-24 | 삼성전자주식회사 | 저온 정착 토너 |
| EP1641869A2 (en) * | 2003-05-19 | 2006-04-05 | Polymers Australia PTY Limited | Polyester masterbatch composition |
| US20100234501A1 (en) * | 2006-03-01 | 2010-09-16 | Invista North America S.A.R.L. | Polymer composition with enhanced gas barrier, articles and methods |
| MY148587A (en) * | 2006-07-28 | 2013-04-30 | Biograde Hong Kong Pty Ltd | Masterbatch and polymer composition |
| US8080191B2 (en) | 2006-10-20 | 2011-12-20 | Pepsico, Inc. | Extrudable polyethylene terephthalate blend |
| US9095997B2 (en) * | 2007-03-22 | 2015-08-04 | Toyo Seikan Kaisha, Ltd. | Multi-layer polyester container and method of producing the same |
| JP5305610B2 (ja) * | 2007-04-05 | 2013-10-02 | 東洋製罐株式会社 | 耐圧性ポリエステル容器及びその製造方法 |
| FR2919874B1 (fr) * | 2007-08-07 | 2011-02-18 | Setup Performance | Procede de modification des caracteristiques physiques, rheologiques et thermomecaniques d'un polymere thermoplastique polaire |
| FR2919873B1 (fr) * | 2007-08-07 | 2009-11-20 | Setup Performance | Matiere thermoplastique postreticulable apres transformation et articles moules stables a tres haute temperature obtenus apres transformation |
| US8404755B2 (en) | 2008-04-18 | 2013-03-26 | Pepsico, Inc. | Polyester composition and method for preparing articles by extrusion blow molding |
| US8110265B2 (en) | 2008-12-09 | 2012-02-07 | The Coca-Cola Company | Pet container and compositions having enhanced mechanical properties and gas barrier properties |
| US20100143546A1 (en) * | 2008-12-09 | 2010-06-10 | The Coca-Cola Company | Container and composition for enhanced gas barrier properties |
| TW201100622A (en) * | 2009-06-16 | 2011-01-01 | Nien Made Entpr Co Ltd | Curtain manufacture and its manufacturing method |
| EP2683756B1 (en) | 2011-03-10 | 2016-05-11 | Nexam Chemical AB | Compositions for improving polyesters |
| US8623969B2 (en) * | 2011-12-08 | 2014-01-07 | Surfatech Corporation | Terminal silicone capped regiospecific glycerin polyesters |
| US10100159B2 (en) * | 2013-07-12 | 2018-10-16 | Polyone Corporation | Polyester compounds having enhanced hydrophobic surface properties |
| CN104497284B (zh) * | 2015-01-17 | 2016-06-01 | 上海青品新材料科技有限公司 | 改性聚酯及其制备方法 |
| CN106916287A (zh) | 2015-11-04 | 2017-07-04 | 财团法人工业技术研究院 | 聚酯及其制造方法 |
| EP3246349A1 (en) | 2017-05-24 | 2017-11-22 | Nexam Chemical AB | Process for increasing the melt strength of a thermoplastic polymer |
| CA3101912C (en) * | 2018-06-01 | 2023-05-02 | Elantas Pdg Inc. | Continous process for producing polyol modified polyalkenylene terephthalate |
| KR102734010B1 (ko) | 2018-11-21 | 2024-11-25 | 삼성전자주식회사 | 액정 고분자, 복합체 조성물, 성형품, 전지 케이스, 및 전지 |
| US11258184B2 (en) | 2019-08-21 | 2022-02-22 | Ticona Llc | Antenna system including a polymer composition having a low dissipation factor |
| US11637365B2 (en) | 2019-08-21 | 2023-04-25 | Ticona Llc | Polymer composition for use in an antenna system |
| US12294185B2 (en) | 2019-09-10 | 2025-05-06 | Ticona Llc | Electrical connector formed from a polymer composition having a low dielectric constant and dissipation factor |
| US12142820B2 (en) | 2019-09-10 | 2024-11-12 | Ticona Llc | 5G system containing a polymer composition |
| US11555113B2 (en) | 2019-09-10 | 2023-01-17 | Ticona Llc | Liquid crystalline polymer composition |
| US12209164B2 (en) | 2019-09-10 | 2025-01-28 | Ticona Llc | Polymer composition and film for use in 5G applications |
| US11912817B2 (en) | 2019-09-10 | 2024-02-27 | Ticona Llc | Polymer composition for laser direct structuring |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| US11646760B2 (en) | 2019-09-23 | 2023-05-09 | Ticona Llc | RF filter for use at 5G frequencies |
| US11721888B2 (en) | 2019-11-11 | 2023-08-08 | Ticona Llc | Antenna cover including a polymer composition having a low dielectric constant and dissipation factor |
| KR102548758B1 (ko) * | 2020-11-30 | 2023-06-28 | 피아이첨단소재 주식회사 | Lcp 분말을 포함하는 폴리이미드 복합 분말 및 이의 제조방법 |
| DE102020216002A1 (de) | 2020-12-16 | 2022-06-23 | Robert Bosch Gesellschaft mit beschränkter Haftung | Dichtmaterial zur Abdichtung einer Bipolarplatte |
| CN115975354B (zh) * | 2022-12-28 | 2025-04-29 | 金发科技股份有限公司 | 一种pbt复合材料及其制备方法和应用 |
| CN116496476B (zh) * | 2023-04-28 | 2025-04-25 | 苏州何洛清洁能源科技研究院有限公司 | 高抗蠕变性pet聚酯材料的制备方法 |
| CN119753881B (zh) * | 2024-12-30 | 2025-09-26 | 常熟涤纶有限公司 | 一种具有高效阻燃特性的有色阻燃聚酯纤维及其制备方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61124684A (ja) * | 1984-11-16 | 1986-06-12 | 日本合成化学工業株式会社 | 繊維用糊剤 |
| CH678184A5 (enExample) | 1989-03-09 | 1991-08-15 | Tisslan S A | |
| DE69222522T2 (de) | 1991-12-20 | 1998-05-07 | Showa Highpolymer | Verfahren zur herstellung eines hochmolekularen aliphatischen polyesters und folie |
| US5229432A (en) | 1992-11-24 | 1993-07-20 | E. I. Du Pont De Nemours And Company | High melt strength pet polymers for foam applications and methods relating thereto |
| JPH07179736A (ja) * | 1993-12-24 | 1995-07-18 | Kanegafuchi Chem Ind Co Ltd | 高溶融粘弾性発現性樹脂組成物およびそれを用いた芳香族ポリエステル系樹脂発泡体の製造法 |
-
1998
- 1998-01-30 JP JP53238998A patent/JP2001509197A/ja active Pending
- 1998-01-30 ID IDW990789A patent/ID22418A/id unknown
- 1998-01-30 US US09/355,540 patent/US6350822B1/en not_active Expired - Fee Related
- 1998-01-30 EP EP98901250A patent/EP0956313B1/en not_active Expired - Lifetime
- 1998-01-30 CA CA002278800A patent/CA2278800C/en not_active Expired - Fee Related
- 1998-01-30 IL IL13117098A patent/IL131170A/en not_active IP Right Cessation
- 1998-01-30 DK DK98901250T patent/DK0956313T3/da active
- 1998-01-30 AT AT98901250T patent/ATE269370T1/de not_active IP Right Cessation
- 1998-01-30 NZ NZ336961A patent/NZ336961A/xx not_active IP Right Cessation
- 1998-01-30 KR KR1019997006903A patent/KR100567089B1/ko not_active Expired - Fee Related
- 1998-01-30 CN CN98802201A patent/CN1109056C/zh not_active Expired - Fee Related
- 1998-01-30 ES ES98901250T patent/ES2223117T3/es not_active Expired - Lifetime
- 1998-01-30 DE DE69824550T patent/DE69824550T2/de not_active Expired - Fee Related
- 1998-01-30 WO PCT/AU1998/000051 patent/WO1998033837A1/en not_active Ceased
- 1998-01-30 PT PT98901250T patent/PT956313E/pt unknown
- 1998-02-03 MY MYPI98000411A patent/MY120019A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001509197A (ja) | 2001-07-10 |
| KR20000070654A (ko) | 2000-11-25 |
| DE69824550T2 (de) | 2005-08-25 |
| WO1998033837A1 (en) | 1998-08-06 |
| MY120019A (en) | 2005-08-30 |
| PT956313E (pt) | 2004-10-29 |
| CN1109056C (zh) | 2003-05-21 |
| NZ336961A (en) | 2001-02-23 |
| DE69824550D1 (de) | 2004-07-22 |
| EP0956313A1 (en) | 1999-11-17 |
| ES2223117T3 (es) | 2005-02-16 |
| EP0956313A4 (en) | 2001-05-02 |
| CA2278800A1 (en) | 1998-08-06 |
| CN1246129A (zh) | 2000-03-01 |
| CA2278800C (en) | 2007-04-03 |
| ATE269370T1 (de) | 2004-07-15 |
| KR100567089B1 (ko) | 2006-03-31 |
| ID22418A (id) | 1999-10-14 |
| IL131170A0 (en) | 2001-01-28 |
| US6350822B1 (en) | 2002-02-26 |
| EP0956313B1 (en) | 2004-06-16 |
| DK0956313T3 (da) | 2004-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6350822B1 (en) | Modified polyesters | |
| KR102138388B1 (ko) | 내열성이 개선된 투명한 반-결정질 물품 | |
| EP2231744B1 (en) | Extrusion blow molded articles | |
| US5334669A (en) | Process for the production of high molecular weight polyester resins | |
| JPH04505031A (ja) | 高分子量ポリエステル樹脂の連続製造方法 | |
| PT1461379E (pt) | Produção em contínuo de poliéster transparente utilizando resíduo | |
| JP2020023701A (ja) | フラン系ポリエステルとのポリマーブレンド | |
| SK100895A3 (en) | Preparation method of linear copolyesters containing omega-hydroxycarbonic acidic units | |
| US6447711B1 (en) | Polyester resins having improved rheological properties | |
| CN102174201B (zh) | 用于制造高光泽度厚壁制品的改性共聚酯材料及制备方法 | |
| EP1137696B1 (en) | Increasing the melt viscosities of a polyester resin | |
| EP0708792A1 (en) | Preparation of branched polyethylene terephthalate | |
| EP4267651A1 (en) | Improved polyester composition for extrusion blow molded containers | |
| CN102942687A (zh) | 一种阻燃脂肪-芳香族共聚酯及其制备方法 | |
| AU730757C (en) | Modified polyesters | |
| KR100200169B1 (ko) | 폴리에스테르 수지로 제조된 성형물품 | |
| US7834127B2 (en) | Amorphous copolyesters | |
| JP2000230058A (ja) | ポリエステル樹脂の透明物品 | |
| JPH05222169A (ja) | 変性ポリエチレンテレフタレート、その製造方法、押出吹込成形容器の製造方法、及び該方法によって得られる容器 | |
| WO2023114069A1 (en) | Improved polyester composition for extrusion blow molded containers | |
| WO2025188873A1 (en) | Polyester composition for extrusion blow molded containers containing post-consumer polyester and process for its preparation | |
| US20020082381A1 (en) | Polyester molding composition | |
| MXPA96002605A (en) | Polyester resins that have rheological properties improves | |
| JPH01256561A (ja) | 結晶性に優れたガラス繊維強化ポリエステル樹脂組成物 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FF | Patent granted | ||
| KB | Patent renewed | ||
| KB | Patent renewed | ||
| MM9K | Patent not in force due to non-payment of renewal fees |