CN1322021C - 无定形－结晶嵌段共聚物 - Google Patents
无定形－结晶嵌段共聚物 Download PDFInfo
- Publication number
- CN1322021C CN1322021C CNB038090872A CN03809087A CN1322021C CN 1322021 C CN1322021 C CN 1322021C CN B038090872 A CNB038090872 A CN B038090872A CN 03809087 A CN03809087 A CN 03809087A CN 1322021 C CN1322021 C CN 1322021C
- Authority
- CN
- China
- Prior art keywords
- acid
- block copolymers
- biological degradation
- thermoplastic block
- degradation thermoplastic
- 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.)
- Expired - Fee Related
Links
- 229920001400 block copolymer Polymers 0.000 title claims 23
- 239000002253 acid Substances 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 27
- 230000015556 catabolic process Effects 0.000 claims description 26
- 238000006731 degradation reaction Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 239000010408 film Substances 0.000 claims description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 17
- 229920006125 amorphous polymer Polymers 0.000 claims description 16
- 229920002472 Starch Polymers 0.000 claims description 14
- 239000008107 starch Substances 0.000 claims description 14
- 235000019698 starch Nutrition 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 10
- 235000013305 food Nutrition 0.000 claims description 8
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 8
- 241000212978 Amorpha <angiosperm> Species 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000007520 diprotic acids Chemical class 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000003281 allosteric effect Effects 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000229 biodegradable polyester Polymers 0.000 claims description 4
- 239000004622 biodegradable polyester Substances 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 claims description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 4
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 4
- -1 hydroxyalkyl methacrylate Chemical compound 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical group OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- 238000003856 thermoforming Methods 0.000 claims description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 4
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 235000013361 beverage Nutrition 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 235000013372 meat Nutrition 0.000 claims description 3
- 239000011104 metalized film Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000002362 mulch Substances 0.000 claims description 3
- 239000010815 organic waste Substances 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000000123 paper Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- 230000009257 reactivity Effects 0.000 claims description 3
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 claims description 3
- 229960003656 ricinoleic acid Drugs 0.000 claims description 3
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000013618 yogurt Nutrition 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 2
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 claims description 2
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 claims description 2
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 claims description 2
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 claims description 2
- PNAJBOZYCFSQDJ-UHFFFAOYSA-N 7-hydroxyheptanoic acid Chemical compound OCCCCCCC(O)=O PNAJBOZYCFSQDJ-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-ZXXMMSQZSA-N D-iditol Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-ZXXMMSQZSA-N 0.000 claims description 2
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- UGUYQBMBIJFNRM-OQFOIZHKSA-N [(z)-but-2-en-2-yl]benzene Chemical compound C\C=C(\C)C1=CC=CC=C1 UGUYQBMBIJFNRM-OQFOIZHKSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 2
- 229960005082 etohexadiol Drugs 0.000 claims description 2
- 235000019256 formaldehyde Nutrition 0.000 claims description 2
- 235000012055 fruits and vegetables Nutrition 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229960004232 linoleic acid Drugs 0.000 claims description 2
- 229960004488 linolenic acid Drugs 0.000 claims description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims 22
- 239000004416 thermosoftening plastic Substances 0.000 claims 22
- 150000001875 compounds Chemical class 0.000 claims 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 235000013399 edible fruits Nutrition 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 235000013336 milk Nutrition 0.000 claims 1
- 239000008267 milk Substances 0.000 claims 1
- 210000004080 milk Anatomy 0.000 claims 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 1
- 229920001634 Copolyester Polymers 0.000 abstract description 9
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000002009 diols Chemical class 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 23
- 229940116351 sebacate Drugs 0.000 description 23
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 23
- 239000000047 product Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 229920006126 semicrystalline polymer Polymers 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 238000010096 film blowing Methods 0.000 description 3
- 230000004941 influx Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- OKIDIWHWTIMACU-MNEPGTOVSA-N 12R-HODE Chemical compound CC\C=C/CC[C@@H](O)C\C=C/CCCCCCCC(O)=O OKIDIWHWTIMACU-MNEPGTOVSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XTUPREMODWQUSJ-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;hexane Chemical compound CCCCCC.CC(C)(C)OOC(C)(C)C XTUPREMODWQUSJ-UHFFFAOYSA-N 0.000 description 1
- OONXYOAWMIVMCI-UHFFFAOYSA-N D-Lesquerolinsaeure Natural products CCCCCCC(O)CC=CCCCCCCCCCC(O)=O OONXYOAWMIVMCI-UHFFFAOYSA-N 0.000 description 1
- 241001448434 Pirex Species 0.000 description 1
- XKGDWZQXVZSXAO-ADYSOMBNSA-N Ricinoleic Acid methyl ester Chemical group CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC XKGDWZQXVZSXAO-ADYSOMBNSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001341 hydroxy propyl starch Substances 0.000 description 1
- 235000013828 hydroxypropyl starch Nutrition 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- OONXYOAWMIVMCI-KWRJMZDGSA-N lesquerolic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCCCC(O)=O OONXYOAWMIVMCI-KWRJMZDGSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 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
- C08G63/02—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
-
- 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
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- 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
-
- 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
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/126—Copolymers block
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
- Y10T428/1341—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
本发明描述了从结晶嵌段和无定形嵌段获得的生物降解嵌段共聚酯，其中两种嵌段的重复单元为二羧酸/二元醇类型。该共聚酯的特征为，熔融温度等于起始结晶聚合物温度或比起始结晶聚合物温度低出小于15%，并且具有增加的韧性，这使它们特别可用于生产不同类型的物品。
Description
本发明涉及由结晶嵌段和无定形嵌段组成的生物降解嵌段共聚酯，其中两种嵌段的重复单元为二元羧酸/二元醇类型。该共聚酯的特征为，熔融温度等于起始结晶聚合物的熔融温度或比起始结晶聚合物的熔融温度低出小于15％，并且特征为具有提高的强度，其使它们特别可用于生产不同类型的制品。
二元羧酸/二元醇类型的生物降解聚酯是已知的。例如，WO00/55236公开了二元羧酸/二元醇类型生物降解脂族聚酯的简化的生产方法，然而没有描述由结晶嵌段和无定形嵌段组成的共聚酯的实施例。因此，未解决如下问题：获得具有足够高熔点和，同时，改进的韧性特性的生物降解聚酯，使得它适用于几种实际应用领域。
已令人惊奇地发现，采用本发明的共聚酯恰当地解决了上述问题，该共聚酯特征为成膜性和韧性性能，所述性能允许该共聚酯用于几种实际应用领域，例如食品包装膜。
当聚合物由仅一种类型的重复单元组成时称为均聚物，而当在聚合物链中存在不同类型的重复单元时称为共聚物。在无规共聚物中，重复单元可以按任何顺序存在，而在嵌段共聚物中，相同类型的重复单元沿链分成组。因此，嵌段共聚物是其中重复单元在聚合物主链的长区段中保持分开的共聚物。
本发明的生物降解嵌段共聚物由结晶嵌段和无定形嵌段组成，所述共聚物以至少一种结晶聚合物和至少一种无定形聚合物为原料形成，这两种聚合物中每一种都为二元羧酸/二元醇类型，并且特征为，结晶部分的熔点TmA等于结晶聚合物的熔融温度或比结晶聚合物的熔融温度低出小于15％，并且无定形部分的熔点TmB相关的ΔH小于10J/g。
产生共聚物结晶部分的(二元酸/二元醇类型)结晶聚合物的特征为ΔH＞50J/g，Tm＞60℃和Mn(数均分子量)＞25,000。产生共聚物无定形部分的(二元酸/二元醇类型)无定形聚合物的特征为ΔH≤30J/g和Tg低于0℃，优选低于-10℃。
在根据本发明的共聚物中，无定形聚合物的存在数量为1-70％，基于无定形聚合物+结晶聚合物的总数量，优选5-65％和更优选10-60％。
关于本发明共聚物的无定形和结晶嵌段的组分，二元羧酸的例子包括草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸和十三烷二酸。
二元醇的例子包括1，2-乙二醇、1，2-丙二醇、1，3-丙二醇、1，4-丁二醇、1，6-己二醇、1，7-庚二醇、1，8-辛二醇、1，9-壬二醇、1，10-癸二醇、1，11-十一烷二醇、1，12-十二烷二醇、1，4-环己烷二甲醇、新戊二醇、2-甲基-1，3-丙二醇、双脱水山梨醇、双脱水甘露糖醇、双脱水艾杜糖醇、环己二醇、环己烷甲二醇。
通过使用由于结构对称性或空间位阻而不能结晶的二元酸/二元醇(例如，新戊二醇、1，3-丁二醇、二甘醇)，或通过使用高百分比的不同种共聚单体(如具有高壬二酸含量的癸二酸、壬二酸和丁二醇的共聚物)，可以有利地获得根据本发明意义的二元羧酸/二元醇类型无定形或低结晶度聚酯，具有ΔH小于30J/g。
除二元羧酸和二元醇以外，根据本发明的生物降解共聚酯也可有利地包含作为起始单体的天然或合成来源的不饱和共聚单体。不饱和共聚单体的数量为0.5-45％，基于二元羧酸/二元醇的总和。
合成来源的不饱和酸的例子包括丙二酸、富马酸、醋酸乙烯酯、丙烯酸、甲基丙烯酸、丙烯酸羟烷基酯和甲基丙烯酸羟烷基酯。天然来源的不饱和共聚单体的例子包括衣康酸，单不饱和羟基酸，如蓖麻油酸和14-羟基-二十碳-顺式-11-烯酸：20：1-OH(lesquerolic acid)，和单或多不饱和一元羧酸，如油酸、芥酸、亚油酸、亚麻酸。天然来源的不饱和酸可以以纯物质形式使用或与饱和或不饱和的其它脂肪酸混合使用。特别地，它们可以作为从它们所源自的植物油的皂化或酯交换而获得的共混物形式使用。例如，蓖麻油酸甲酯形式的蓖麻油酸可以采用如下衍生的或多或少为纯物质的形式使用：蓖麻油与甲醇的酯交换反应，并随后脱除甘油(反应副产物)和过量甲醇。
除基础单体以外，根据本发明的共聚物可包括数量在0-30摩尔％范围内的至少一种羧基酸，基于脂族二元羧酸的摩尔数。合适羟基酸的例子包括乙醇酸、羟基丁酸、羟基己酸、羟基戊酸、7-羟基庚酸、8-羟基己酸、9-羟基壬酸和乳酸。
同样有利地，根据本发明的生物降解共聚物可包含作为起始单体的，也最多至50摩尔％的多官能芳族化合物，例如苯二甲酸，特别是对苯二甲酸，双酚A，对苯二酚等，基于二元羧酸/二元醇总和。
另外，根据本发明的共聚物可以与如下物质的共混物形式使用并也以该形式由反应性挤出获得：相同类型共聚物，或其它生物降解聚酯(如聚乳酸、聚-ε-己内酯、聚羟基丁酸酯、聚亚烷基琥珀酸酯)，或聚酯以外的聚合物；它也可作为与如下天然来源的聚合物的共混物形式使用：如淀粉、纤维素、壳聚糖或天然橡胶。淀粉和纤维素可以是改性的，并且其中可以提及，例如取代度为0.2-2.5的淀粉或纤维素酯，羟丙基化淀粉，由脂肪链改性的淀粉。此外，淀粉可以是以变构的或以胶凝化形式使用。
在根据本发明的聚酯的制备方法中，可以有利地采用0.1-30摩尔％数量加入一种或多种多官能分子，基于二元羧酸，以获得支化产物。这些分子的例子包括甘油、季戊四醇、三羟甲基丙烷、新戊二醇、柠檬酸、12-羟基-十八碳-顺式-9，15-烯酸：18：2-OH(densipolic acid)、14-羟基-二十碳-顺式-11，17-烯酸：20：2-OH(auripolic acid)、环氧化豆油和蓖麻油。
以至少两种二元羧酸/二元醇类型的聚合物为原料，其中一种为结晶和另一种为无定形，例如通过在聚合物之间的交换反应(酯交换)获得根据本发明的嵌段共聚物。在此情况下，重要的是合适地调节反应时间，这是由于后者的延长涉及聚合物链之间交换的增加，其可能导致无规共聚物的形成。
也可以由所述至少两种起始聚合物的混合物，通过与有机过氧化物的反应性挤出的聚合后反应而获得根据本发明的嵌段共聚物。
根据本发明的嵌段共聚物适用于许多实际应用领域如膜、注塑产品、挤出涂层、纤维、泡沫材料、热成形产品等。特别地，根据本发明的共聚物适用于如下产品的生产：
-单向或双向的膜，和含有其它聚合物材料的多层膜；
-用于农业用途的膜如地膜；
-用于有机废物收集的袋子和内衬；
-单层或多层食品包装物，如用于奶、酸乳、肉、饮料等的容器；
-采用挤出涂覆技术获得的涂层；
-含有纸、塑料、铝、金属化膜的层的多层层压材料；
-膨胀和半膨胀产品，包括从预膨胀粒子获得的膨胀块；
-膨胀片材和热成形片材和从其获得的用于食品包装的容器；
-一般用于水果和蔬菜的容器；
-采用胶凝化、变构和/或复合淀粉或天然淀粉作为填料的复合材料；
-用于卫生和保健领域的纤维、织物和非织造织物。
实施例
在实施例中，在25℃下，在氯仿中，在0.2g/dl的浓度下测量比浓对数粘度。
采用配有液氮冷却系统的Perkin Elmer DSC 7差示扫描量热仪测量熔融温度Tm和熔融焓ΔHm。采用高纯度标准物(铟)校准该仪器。将约10mg聚合物放入小铝皿中并在20℃/min的速度下(第一次扫描)加热到比熔融温度高出约40℃的温度，然后冷却到-30℃并最后在20℃/min的速度下(第二次扫描)再次达到高于聚合物完全熔融的温度的温度。从第二次扫描的差示热分析图获得Tm和ΔHm，该二次扫描为了具有样品的均匀热历史。熔融温度作为DSC曲线的吸热现象的峰值测定，并从该峰的面积获得焓。由动态机械分析和量热分析检测共聚物的形成。除非另外说明，根据ASTM D-882/88在成膜之后15天测量膜的撕裂强度。
实施例1
半结晶聚合物(聚癸二酸乙二醇酯)
将-5.7kg癸二酸(2.2摩尔)，
-2.0kg乙二醇(32.2摩尔)，
-6g一丁基锡酸(2.9·10-2摩尔)
加入到配有机械搅拌器，氮气流入口，冷凝器，并与真空泵连接的251钢反应器中。
在剧烈搅拌和氮气流下逐渐升高温度到210℃。进行反应直到蒸馏出89％的理论数量的易挥发副产物(900ml)。然后将温度升高到240℃并对系统施加0.5mmHg的压力。反应继续300min。
获得比浓对数粘度为1.11dl/g，Tm＝74.27℃，ΔHm＝72.3J/g和Tg＝-36℃的聚合物。
无定形聚合物(聚癸二酸新戊二醇酯)
向以上反应器中加入
5050g癸二酸(25.0摩尔)，
-2700g新戊二醇(26.0摩尔)，
-8g一丁基锡酸(3.8·10-2摩尔)。
在剧烈搅拌和氮气流下逐渐升高温度到210℃。进行反应直到蒸馏出87％的理论数量的易挥发副产物(780ml)。然后将温度升高到240℃并对系统施加0.2mmHg的压力。反应进行300min。
产物在Tamb(室温)下是无定形聚合物，无定形聚合物在DSC分析中显示没有熔融峰，及比浓对数粘度为1.2dl/g，和Tg为-62℃。嵌段共聚物
在中试反应器中由上述聚癸二酸乙二醇酯和聚癸二酸新戊二醇酯的酯交换反应而获得嵌段共聚物。
将4.8kg聚癸二酸乙二醇酯(60wt％)和3.2kg(40wt％)聚癸二酸新戊二醇酯加入到反应器中并加热到230℃。一旦聚合物熔融，将混合物在240℃下在0.5mmHg的真空下搅拌30分钟。
获得粘度为1.05dl/g，Tm＝65.24℃，ΔHm＝52J/g和单一Tg＝-50℃的产物。
图1显示结晶聚合物(a)和嵌段共聚物(b)的差示热分析图。该图以图解方式突出表明，关于结晶聚合物熔点计，共聚物熔点降低了小于15％。与共聚物无定形部分相关的ΔH是0。
采用这样获得的嵌段共聚物，通过薄膜吹塑聚癸二酸乙二醇酯和嵌段共聚物，而生产厚度为25μm的膜。
撕裂强度(埃尔门多夫(Elmendorf))见下表：
| 实施例1 | 纵向(N/mm) | 横向(N/mm) |
| 聚癸二酸乙二醇酯 | 3 | 20 |
| 嵌段共聚物 | 3 | 47 |
当在1年之后测量埃尔门多夫数值时，嵌段共聚物总是得到相同的数值，而聚癸二酸乙二醇酯在纵向上得到3N/mm，但在横向上得到12N/mm。
对比例1-两种聚合物的溶液共混
将实施例1的6g聚癸二酸乙二醇酯(60％)和4g聚癸二酸新戊二醇酯(40％)在25℃下在搅拌下溶于100ml氯仿中30min。在旋转蒸发器中真空蒸发(18mmHg)主要部分的溶剂。在真空烘箱中在40℃下干燥获得的混合物24小时。以此方式，混合两种产物而没有反应。
获得的产物具有Tm＝72℃并显示在-36℃和-48℃的两个Tg。对比例2-两种聚合物的挤出共混
将实施例1的180g聚癸二酸乙二醇酯(60％)和120g聚癸二酸新戊二醇酯(40％)在具有计量螺杆，在25rpm下全入口进料并具有如下温度分布：25-50-80-90-100℃的Haake Rheocord挤出机中共混。
获得的混合物具有Tm＝72℃并显示在-60℃和-50℃的两个Tg。
实施例1的聚合物，不象在对比例中描述的两种混合物，它具有单一的Tg。因此，它是共聚物而不是共混物。
对比例3-无规共聚物
将
-202g癸二酸(1摩尔)，
-44g乙二醇(0.7摩尔)，
-41g新戊二醇(0.4摩尔)
-0.3g一丁基锡酸
加入到配有机械搅拌器，氮气流入口，冷凝器，并与真空泵连接的1.5升Pirex玻璃反应器中。
乙二醇/新戊二醇比例使得获得60wt％的聚癸二酸乙二醇酯重复单元和40wt％的聚癸二酸新戊二醇酯重复单元。在剧烈搅拌和氮气流下逐渐升高反应器的温度到210℃。进行反应直到蒸馏出90％的理论数量的易挥发副产物(32ml)。然后将温度升高到240℃并对系统施加0.5mmHg的压力。反应继续240min。
产物是比浓对数粘度为1.15dl/g和Tm＝35℃的聚合物。此结果表明，实施例1中所述的共聚物不是无规共聚物。
实施例2
半结晶聚合物(聚癸二酸丁二醇酯)
将-7079g癸二酸(35摩尔)，
-3470g丁二醇(38.6摩尔)，
-10.8g一丁基锡酸(5.2·10-2摩尔)
加入到配有机械搅拌器，氮气流入口，冷凝器，并与真空泵连接的251钢反应器中。
在剧烈搅拌和氮气流下逐渐升高温度到210℃。进行反应直到蒸馏出91％的理论数量的易挥发副产物(1150ml)。然后将温度升高到240℃并对系统施加0.8mmHg的压力。反应继续300min。获得比浓对数粘度为1.11dl/g，Tm＝66℃和ΔHm＝90J/g的聚癸二酸丁二醇酯。
无定形聚合物(聚癸二酸新戊二醇酯)
根据由实施例1公开的内容合成聚癸二酸新戊二醇酯。
嵌段共聚物
在中试反应器中由聚癸二酸丁二醇酯和聚癸二酸新戊二醇酯的酯交换反应而获得嵌段共聚物。
将6.0kg聚癸二酸丁二醇酯(60wt％)和4.0kg(40wt％)聚癸二酸新戊二醇酯加入到反应器中并加热到230℃。一旦聚合物熔融，将混合物在240℃下在0.5mmHg真空下搅拌90min。
获得比浓对数粘度为1.31dl/g，Tm＝62℃和ΔHm＝58J/g的产物。
采用该产物，通过薄膜吹塑聚癸二酸丁二醇酯和嵌段共聚物，生产厚度为30μm的膜。
撕裂强度(埃尔门多夫)见下表：
| 实施例2 | 纵向(N/mm) | 横向(N/mm) |
| 聚癸二酸丁二醇酯 | 4 | 26 |
| 嵌段共聚物 | 5 | 180 |
实施例3
半结晶聚合物(聚癸二酸丁二醇酯)
根据实施例1中公开的内容制备聚癸二酸丁二醇酯。无定形聚合物（聚（癸二酸丁二醇-共-新戊二醇酯）支化的）
向以上所述反应器中加入
-4000g癸二酸(19.8摩尔)，
-878g新戊二醇(8.4摩尔)，
-1200g丁二醇(13.3摩尔)，
-8g一丁基锡酸(3.8·10-2摩尔)。
在剧烈搅拌和氮气流下逐渐升高温度到180℃。进行反应直到蒸馏出85％的理论数量的易挥发副产物。然后将温度升高到240℃并对系统施加0.2mmHg的压力。反应继续360min。产物是比浓对数粘度为1.13dl/g，Tm＝32℃和ΔHm＝30J/g的聚合物。
嵌段共聚物
在中试反应器中由聚癸二酸丁二醇酯和聚癸二酸丁二醇-共-新戊二醇酯的酯交换反应，获得嵌段共聚物。
将6kg聚癸二酸丁二醇酯(60wt％)和4kg(40wt％)聚癸二酸丁二醇-共-新戊二醇酯加入到反应器中并加热到230℃。一旦聚合物熔融，将混合物在240℃下在0.5mmHg的真空下搅拌90min。获得粘度为1.16dl/g，单一熔融Tm＝59℃和ΔHm＝70J/g的产物。
采用该产物，通过薄膜吹塑聚癸二酸丁二醇酯和嵌段共聚物，生产厚度为30μm的膜。撕裂强度(埃尔门多夫)见下表：
| 实施例3 | 纵向(N/mm) | 横向(N/mm) |
| 聚癸二酸丁二醇酯 | 4 | 26 |
| 嵌段共聚物 | 5 | 150 |
实施例4
半结晶聚合物(聚癸二酸丁二醇酯)
向实施例1的反应器中加入
-6000g癸二酸(29.7摩尔)，
-2940g丁二醇(32.7摩尔)，
-9g一丁基锡酸(4.3·10-2摩尔)。
在剧烈搅拌和氮气流下逐渐升高温度到210℃。进行反应直到蒸馏出95％的理论数量的易挥发副产物。然后将温度升高到240℃并对系统施加1mmHg的压力。反应继续120min。获得7kg的具有比浓对数粘度为0.84dl/g的聚合物。在Haake Rheocord中将聚合物成膜。无定形聚合物(聚癸二酸新戊二醇酯)
向实施例1的反应器中加入
-5050kg癸二酸(25.0摩尔)，
-2700g新戊二醇(26.0摩尔)，
-8g一丁基锡酸(3.8·10-2摩尔)。
在剧烈搅拌和氮气流下逐渐升高温度到210℃。进行反应直到蒸馏出87％的理论数量的易挥发副产物(780ml)。然后将温度升高到240℃并对系统施加0.2mmHg的压力。反应进行200min。获得的产物是在室温，Tamb下为无定形的聚合物，该聚合物在DSC分析中显示没有熔融峰，其比浓对数粘度为0.87dl/g。
支化嵌段聚合物
在挤出机中采用0.3pph的2，5-二甲基-2，5-二(叔丁基)过氧己烷(Luperox 101)以如下条件，通过反应240g聚癸二酸丁二醇酯和160g聚癸二酸新戊二醇酯获得无定形结晶共聚物：
-温度分布：23-90-170-170-170℃
-螺杆转速：200rpm，生产量：1.2 kg/h。
获得粘度为1.29dl/g的聚合物。
在Haake Rheocord中成膜的产品得到如下结果：
| 实施例4 | 纵向(N/mm) | 横向(N/mm) |
| 聚癸二酸丁二醇酯 | 3 | 20 |
| 嵌段共聚物 | 10 | 30 |
Claims (31)
1.一种由结晶嵌段和无定形嵌段组成的生物降解热塑性嵌段共聚物，所述共聚物从至少一种结晶聚合物和至少一种无定形聚合物获得，这两种聚合物中每一种都为二元羧酸/二元醇类型，并且特征为，结晶部分的熔点TmA等于结晶聚合物的熔融温度或比结晶聚合物的熔融温度低出小于15％，并且无定形部分的熔点TmB相关的ΔH小于10J/g。
2.根据权利要求1的生物降解热塑性嵌段共聚物，其中形成共聚物结晶部分的二元酸/二元醇类型结晶聚合物的特征为ΔH＞50J/g，Tm＞60℃和Mn＞25,000，并且形成共聚物无定形部分的二元酸/二元醇类型无定形聚合物的特征为ΔH≤30J/g，和Tg低于0℃。
3.根据权利要求2的生物降解热塑性嵌段共聚物，其中形成共聚物无定形部分的二元酸/二元醇类型无定形聚合物的Tg低于-10℃。
4.根据权利要求1或2的生物降解热塑性嵌段共聚物，其中无定形聚合物的数量为1-70％，基于无定形+结晶聚合物的总数量。
5.根据权利要求4的生物降解热塑性嵌段共聚物，其中无定形聚合物的数量为5-65％。
6.根据权利要求5的生物降解热塑性嵌段共聚物，其中无定形聚合物的数量为10-60％。
7.根据权利要求1或2的生物降解热塑性嵌段共聚物，其中二元羧酸选自草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸和十三烷二酸及其混合物。
8.根据权利要求1或2的生物降解热塑性嵌段共聚物，其中所述二元醇选自1，2-乙二醇、1，2-丙二醇、1，3-丙二醇、1，4-丁二醇、1，6-己二醇、1，7-庚二醇、1，8-辛二醇、1，9-壬二醇、1，1 0-癸二醇、1，11-十一烷二醇、1，12-十二烷二醇、1，4-环己烷二甲醇、新戊二醇、2-甲基-1，3-丙二醇、双脱水山梨醇、双脱水甘露糖醇、双脱水艾杜糖醇、环己二醇、环己烷甲二醇及其混合物。
9.根据权利要求1或2的生物降解热塑性嵌段共聚物，其包含数量为0.5-45％的天然或合成来源的不饱和共聚单体，基于二元羧酸/二元醇数量的总和。
10.根据权利要求9的生物降解热塑性嵌段共聚物，其中合成来源不饱和共聚单体选自丙二酸、富马酸、醋酸乙烯酯、丙烯酸、甲基丙烯酸、丙烯酸羟烷基酯和甲基丙烯酸羟烷基酯，且天然来源不饱和共聚单体选自衣康酸，单不饱和羟基酸，和单或多不饱和一元羧酸。
11.根据权利要求10的生物降解热塑性嵌段共聚物，其中所述单不饱和羟基酸是蓖麻油酸或14-羟基-二十碳-顺式-11-烯酸。
12.根据权利要求10的生物降解热塑性嵌段共聚物，其中所述单或多不饱和一元羧酸是油酸、芥酸、亚油酸或亚麻酸。
13.根据权利要求1或2的生物降解热塑性嵌段共聚物，其包含数量在0-30摩尔％范围内的至少一种羟基酸，基于脂族二元羧酸的摩尔数，该羟基酸选自乙醇酸、羟基丁酸、羟基己酸、羟基戊酸、7-羟基庚酸、8-羟基己酸、9-羟基壬酸和乳酸及其混合物。
14.根据权利要求1或2的生物降解热塑性嵌段共聚物，其包含最多至50摩尔％的芳族多官能化合物，基于二元羧酸/二元醇的总摩尔数。
15.根据权利要求14的生物降解热塑性嵌段共聚物，其中所述芳族多官能化合物是苯二甲酸，双酚A，或对苯二酚。
16.根据权利要求15的生物降解热塑性嵌段共聚物，其中所述苯二甲酸是对苯二甲酸。
17.根据权利要求1或2的生物降解热塑性嵌段共聚物，其包含数量为0.1-3摩尔％的一种或多种多官能分子，基于二元羧酸，该分子选自甘油、季戊四醇、三羟甲基丙烷、新戊二醇、柠檬酸、12-羟基-十八碳-顺式-9，15-烯酸、14-羟基-二十碳-顺式-11，17-烯酸、环氧化豆油和蓖麻油。
18.根据权利要求1或2的生物降解热塑性嵌段共聚物，其以与如下物质的共混物形式使用并也以该形式由反应性挤出获得：相同类型共聚物，或其它生物降解聚酯，或聚酯以外的聚合物。
19.根据权利要求1或2的生物降解热塑性嵌段共聚物，与天然来源的聚合物的共混物形式使用。
20.根据权利要求19的生物降解热塑性嵌段共聚物，其中所述天然来源的聚合物是淀粉、纤维素、壳聚糖、天然橡胶、改性淀粉和纤维素或以变构和胶凝化形式的淀粉。
21.根据权利要求1-20中任一项的生物降解热塑性嵌段共聚物用于生产如下产品的用途：
-单向或双向的膜，和含有其它聚合物材料的多层膜；
-用于农业用途的膜；
-用于有机废物收集的袋子和内衬；
-单层或多层食品包装物；
-采用挤出涂覆技术获得的涂层；
-含有纸、塑料、铝、金属化膜的层的多层层压材料；
-膨胀和半膨胀产品，包括从预膨胀粒子获得的膨胀块；
-膨胀片材和热成形片材和从其获得的用于食品包装的容器；
-一般用于水果和蔬菜的容器；
-采用胶凝化、变构和/或复合淀粉或天然淀粉作为填料的复合材料；
-用于卫生和保健领域的纤维、织物和非织造织物。
22.根据权利要求21的用途，其中所述用于农业用途的膜是地膜。
23.根据权利要求21的用途，其中所述单层或多层食品包装物是用于奶、酸乳、肉、饮料的容器。
24.从权利要求1-20中任一项的生物降解热塑性嵌段共聚物获得的成形制品。
25.根据权利要求24的成形制品，其中该制品选自单向膜、双向膜、含有其它聚合物材料的多层膜、地膜、由挤出涂覆技术获得的涂层。
26.根据权利要求24的成形制品，其中该制品选自用于有机废物收集的袋子或内衬。
27.根据权利要求24的成形制品，其中该制品是选自奶容器、酸乳容器、肉容器、饮料容器、水果容器、蔬菜容器的单层或多层食品容器。
28.根据权利要求24的成形制品，其中该制品是包括选自如下材料的层的多层层压材料：纸、塑料、铝、金属化膜。
29.根据权利要求24的成形制品，其中该制品选自半膨胀产品、膨胀产品、由预膨胀粒子形成的膨胀块、膨胀片材、热成形片材、由膨胀片材或热成形片材制成的食品用容器。
30.根据权利要求24的成形制品，其中该制品选自采用胶凝化，变构和/或复合淀粉或天然淀粉作为填料的复合材料。
31.根据权利要求24的成形制品，其中该制品选自用于卫生和保健领域的纤维、织物或非织造织物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2002MI000864A ITMI20020864A1 (it) | 2002-04-22 | 2002-04-22 | Copolimeri a blocchi amorfo-cristallini |
| ITMI2002A000864 | 2002-04-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1646595A CN1646595A (zh) | 2005-07-27 |
| CN1322021C true CN1322021C (zh) | 2007-06-20 |
Family
ID=11449759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038090872A Expired - Fee Related CN1322021C (zh) | 2002-04-22 | 2003-04-22 | 无定形－结晶嵌段共聚物 |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US7169860B2 (zh) |
| EP (1) | EP1497352B1 (zh) |
| JP (1) | JP2005523355A (zh) |
| CN (1) | CN1322021C (zh) |
| AT (1) | ATE300567T1 (zh) |
| AU (1) | AU2003240455A1 (zh) |
| CA (1) | CA2480539C (zh) |
| DE (1) | DE60301144T2 (zh) |
| ES (1) | ES2246477T3 (zh) |
| IT (1) | ITMI20020864A1 (zh) |
| TW (1) | TWI259190B (zh) |
| WO (1) | WO2003089491A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102597105A (zh) * | 2009-11-05 | 2012-07-18 | 诺瓦蒙特股份公司 | 生物可降解聚酯与至少一种天然来源的聚合物的混合物 |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6806346B2 (en) * | 2002-07-12 | 2004-10-19 | E. I. Du Pont De Nemours And Company | Copolymerization of cyclic ester oligomers |
| US7888405B2 (en) * | 2004-01-30 | 2011-02-15 | E. I. Du Pont De Nemours And Company | Aliphatic-aromatic polyesters, and articles made therefrom |
| ITMI20050452A1 (it) * | 2005-03-18 | 2006-09-19 | Novamont Spa | Poliestere biodegradabile alifatico-aromatico |
| US20070082982A1 (en) * | 2005-10-11 | 2007-04-12 | The Procter & Gamble Company | Water stable compositions and articles comprising starch and methods of making the same |
| US8729176B2 (en) | 2006-09-06 | 2014-05-20 | Keio University | Polyricinoleate composition and process for producing the same |
| ITMI20061844A1 (it) * | 2006-09-27 | 2008-03-28 | Novamont Spa | Composizioni biodegradabili a base di amido nanoparticellare |
| US7772362B2 (en) * | 2007-07-16 | 2010-08-10 | Texas State University | Treatment method for imparting self-healing and shape memory properties to certain CBDO copolymers |
| KR101168601B1 (ko) * | 2007-10-18 | 2012-07-30 | 베.에.테. 오토모티브 시스템스 아게 | 전기 전도성 장치 |
| TWM336741U (en) * | 2007-12-11 | 2008-07-21 | J & C Prosperity Int L Co Ltd | Laminated structure of food container |
| EP2098552A1 (en) * | 2008-03-06 | 2009-09-09 | Hexion Specialty Chemicals Research Belgium S.A. | Thermosetting polyester resin modified with semi-crystalline polyester for powder coatings |
| EP3360927B1 (en) | 2009-06-26 | 2020-09-09 | CJ CheilJedang Corporation | Pha compositions comprising pbs and pbsa and method for producing the compositions |
| EP2470363A4 (en) * | 2009-10-02 | 2013-02-27 | Toray Plastics America Inc | BIODEGRADABLE COMPOSITE BARRIER FILM |
| DE202011102425U1 (de) | 2010-07-15 | 2011-11-08 | W.E.T. Automotive Systems Ag | Elektrische Leitung |
| JP2012107156A (ja) * | 2010-11-19 | 2012-06-07 | Sanyo Chem Ind Ltd | 樹脂粒子およびその製造方法 |
| CN103059310B (zh) * | 2011-10-21 | 2015-04-29 | 中国科学院化学研究所 | 一种含有双键的可生物降解聚酯多嵌段共聚物及其制备方法 |
| US9353258B2 (en) | 2012-06-05 | 2016-05-31 | Metabolix, Inc. | Low glass transition polyhydroxyalkanoates for modification of biodegradable polymers |
| EP3377579A1 (en) | 2015-11-17 | 2018-09-26 | CJ Cheiljedang Corporation | Polymer blends with controllable biodegradation rates |
| CN111647146B (zh) * | 2020-05-12 | 2021-09-21 | 江南大学 | 一种低温3d打印生物降解材料、制备方法及其应用 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3968183A (en) * | 1973-06-30 | 1976-07-06 | Toyo Boseki Kabushiki Kaisha | Film excellent in slip characteristics and its production |
| US4070417A (en) * | 1974-12-19 | 1978-01-24 | Toyobo Co., Ltd. | Stretched polyester film from a polymer blend |
| JP2000218694A (ja) * | 1999-01-28 | 2000-08-08 | Toyobo Co Ltd | 熱収縮性ポリエステル系フィルム |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4208360A1 (de) * | 1992-03-16 | 1993-09-23 | Bayer Ag | Kompostierbare thermoplastische blockcopolyester fuer verpackungsmaterialien |
| JP3411168B2 (ja) * | 1995-12-21 | 2003-05-26 | 三井化学株式会社 | 脂肪族ポリエステル成形体の製造方法及びそれにより製造された成形体 |
| JP3694100B2 (ja) * | 1996-05-14 | 2005-09-14 | トヨタ自動車株式会社 | 自発巻縮性複合繊維 |
| JP3698533B2 (ja) * | 1996-11-07 | 2005-09-21 | 三井化学株式会社 | 分解性共重合体を生分解性接着剤として使用する方法 |
| JPH10237166A (ja) * | 1997-02-26 | 1998-09-08 | Daicel Chem Ind Ltd | 脂肪族ポリエステルエラストマーおよびその製造方法 |
| JPH10279732A (ja) * | 1997-04-04 | 1998-10-20 | Kureha Elastomer Kk | 熱可塑性エラストマー組成物 |
| KR100497872B1 (ko) * | 1999-01-28 | 2005-06-29 | 도요 보세키 가부시키가이샤 | 열수축성 폴리에스테르계 필름 |
| IT1307022B1 (it) | 1999-03-15 | 2001-10-23 | Novamont Spa | Processo semplificato per l'ottenimento di poliesteri alifaticibiodegradabili. |
-
2002
- 2002-04-22 IT IT2002MI000864A patent/ITMI20020864A1/it unknown
-
2003
- 2003-04-22 WO PCT/EP2003/004070 patent/WO2003089491A1/en active IP Right Grant
- 2003-04-22 TW TW092109343A patent/TWI259190B/zh active
- 2003-04-22 CA CA2480539A patent/CA2480539C/en not_active Expired - Fee Related
- 2003-04-22 AU AU2003240455A patent/AU2003240455A1/en not_active Abandoned
- 2003-04-22 CN CNB038090872A patent/CN1322021C/zh not_active Expired - Fee Related
- 2003-04-22 JP JP2003586209A patent/JP2005523355A/ja active Pending
- 2003-04-22 DE DE60301144T patent/DE60301144T2/de not_active Expired - Lifetime
- 2003-04-22 ES ES03729929T patent/ES2246477T3/es not_active Expired - Lifetime
- 2003-04-22 EP EP03729929A patent/EP1497352B1/en not_active Expired - Lifetime
- 2003-04-22 AT AT03729929T patent/ATE300567T1/de not_active IP Right Cessation
-
2004
- 2004-10-19 US US10/967,299 patent/US7169860B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3968183A (en) * | 1973-06-30 | 1976-07-06 | Toyo Boseki Kabushiki Kaisha | Film excellent in slip characteristics and its production |
| US4070417A (en) * | 1974-12-19 | 1978-01-24 | Toyobo Co., Ltd. | Stretched polyester film from a polymer blend |
| JP2000218694A (ja) * | 1999-01-28 | 2000-08-08 | Toyobo Co Ltd | 熱収縮性ポリエステル系フィルム |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102597105A (zh) * | 2009-11-05 | 2012-07-18 | 诺瓦蒙特股份公司 | 生物可降解聚酯与至少一种天然来源的聚合物的混合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003240455A1 (en) | 2003-11-03 |
| TWI259190B (en) | 2006-08-01 |
| US20050107572A1 (en) | 2005-05-19 |
| CA2480539C (en) | 2011-10-04 |
| EP1497352B1 (en) | 2005-07-27 |
| WO2003089491A1 (en) | 2003-10-30 |
| DE60301144D1 (en) | 2005-09-01 |
| ES2246477T3 (es) | 2006-02-16 |
| ITMI20020864A1 (it) | 2003-10-22 |
| US7169860B2 (en) | 2007-01-30 |
| JP2005523355A (ja) | 2005-08-04 |
| ATE300567T1 (de) | 2005-08-15 |
| ITMI20020864A0 (it) | 2002-04-22 |
| CN1646595A (zh) | 2005-07-27 |
| TW200307703A (en) | 2003-12-16 |
| CA2480539A1 (en) | 2003-10-30 |
| DE60301144T2 (de) | 2006-04-20 |
| EP1497352A1 (en) | 2005-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1322021C (zh) | 无定形－结晶嵌段共聚物 | |
| AU2009295910B2 (en) | Aliphatic polyester | |
| DE60132525T2 (de) | Schlagzäh-modifizierer und diese modifizierer enthaltende polyesterzusammensetzung | |
| EP1444285B1 (en) | Biodegradable coating | |
| TWI277625B (en) | Biodegradable saturated/unsaturated thermoplastic polyesters | |
| AU751757B2 (en) | Biodegradable lactone copolymers | |
| WO2003037956A9 (fr) | Acide polyglycolique cristallin, composition a base d'acide polyglycolique et procedes de fabrication correspondants | |
| JP2002539309A (ja) | 生分解性脂肪族ポリエステルを製造する簡単な方法 | |
| CA2069498C (en) | Novel copolyesters and articles extrusion blow-molded therefrom | |
| JP2001335623A (ja) | 耐衝撃性付与剤及び該剤を含むポリエステル組成物 | |
| EP2630165B1 (en) | Block copolymers including polylactide | |
| EP0707047B1 (en) | Stretched blow molded articles | |
| JP3712844B2 (ja) | 分解性重合体及びその製造方法 | |
| US8349955B2 (en) | Poly(hydroxyalkanoic acid) plasticized with poly(trimethylene ether) glycol | |
| US20210355271A1 (en) | Bifuran polyesters | |
| US7223815B2 (en) | Polylactic acid composition containing modifier | |
| JP3737302B2 (ja) | 新規なポリエステルペレットおよびポリエステルペレットの製造方法 | |
| KR20210067627A (ko) | 사슬 연장을 통한 지방족 카보네이트 및 방향족 에스테르 공중합체 및 이를 이용한 생분해성 수지 혼합물 | |
| JP4152767B2 (ja) | ポリエステルブロック共重合体及びその製造方法 | |
| WO2014044129A1 (zh) | 一种新型的生物可降解共聚酯及其制备方法 | |
| JP3993938B2 (ja) | 生分解ポリエステル共重合体 | |
| JPH02150417A (ja) | ポリエチレンテレフタレートおよびその用途 | |
| PL226389B1 (pl) | Biodegradowalna kompozycja kopoliestrowa i sposób wytwarzania biodegradowalnej kompozycji kopoliestrowej | |
| MXPA00001929A (en) | Biodegradable lactone copolymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070620 Termination date: 20170422 |