CN1092084A - 一种与淀粉化学结合的可生物降解聚乙烯组合物及其制备方法 - Google Patents
一种与淀粉化学结合的可生物降解聚乙烯组合物及其制备方法 Download PDFInfo
- Publication number
- CN1092084A CN1092084A CN93121454A CN93121454A CN1092084A CN 1092084 A CN1092084 A CN 1092084A CN 93121454 A CN93121454 A CN 93121454A CN 93121454 A CN93121454 A CN 93121454A CN 1092084 A CN1092084 A CN 1092084A
- Authority
- CN
- China
- Prior art keywords
- weight part
- starch
- acid
- biodegradable
- composition
- 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.)
- Pending
Links
- 229920002472 Starch Polymers 0.000 title claims abstract description 59
- 239000008107 starch Substances 0.000 title claims abstract description 59
- 235000019698 starch Nutrition 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- -1 polyethylene Polymers 0.000 title claims abstract description 32
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 24
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 239000004902 Softening Agent Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 17
- 229920001903 high density polyethylene Polymers 0.000 claims description 15
- 239000008188 pellet Substances 0.000 claims description 13
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229920001684 low density polyethylene Polymers 0.000 claims description 10
- 239000004702 low-density polyethylene Substances 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 9
- 239000011968 lewis acid catalyst Substances 0.000 claims description 8
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 5
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- 229940113162 oleylamide Drugs 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000881 Modified starch Polymers 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 235000019426 modified starch Nutrition 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical group CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- 229920002449 FKM Polymers 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
- 239000004368 Modified starch Substances 0.000 claims description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- 238000006266 etherification reaction Methods 0.000 claims description 2
- 229920004889 linear high-density polyethylene Polymers 0.000 claims description 2
- 229960004232 linoleic acid Drugs 0.000 claims description 2
- XYXLRVFDLJOZJC-CVBJKYQLSA-L manganese(2+);(z)-octadec-9-enoate Chemical compound [Mn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O XYXLRVFDLJOZJC-CVBJKYQLSA-L 0.000 claims description 2
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims 1
- 238000005502 peroxidation Methods 0.000 claims 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 239000003377 acid catalyst Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 38
- 238000002156 mixing Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920006238 degradable plastic Polymers 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 229940099112 cornstarch Drugs 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 239000013502 plastic waste Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 1
- 229920013665 Ampacet Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229940126656 GS-4224 Drugs 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Landscapes
- 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)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Medicinal Preparation (AREA)
Abstract
本发明是在有机酸催化剂存在下使用偶联剂对
基质树脂和淀粉进行化学结合从而使物理性能的下
降减至最低程度,同时通过简化工艺而实现生产成本
的降低。提供一种与淀粉化学结合的可生物降解聚
乙烯组合物,包括100重量份基质树脂,5—400重量
份可生物降解掺入物质,0.01—10重量份偶联剂,
0.01—1.0重量份自由基引发剂,0.01—5重量份路易
士酸催化剂,0.01—10重量份自氧化剂和0.01—10
重量份增塑剂并提供制备该组合物的方法。由本发
明制备的聚乙烯组合物的可生物降解能力,在淀粉含
量多于10%(重量)情况下显示出极好的可生物降解
能力。
Description
本发明涉及一种使用聚乙烯是具有广泛应用的聚烯烃,各种有机酸和偶联剂,例如马来酐,甲基丙烯酸酐或马来酰亚胺,通过淀粉与聚乙烯链化学结合的可生物降解聚乙烯组合物,本发明还涉及制备该组合物的方法。
塑料由于其低价格,光学特性以及极好的物理性能而作为金属的取代材料大量生产,它作为日常生活的必需材料已确立。但是,当大批塑料产品的污染问题在世界上日趋严重时,世界各国正在制订各种各样的对策,在南朝鲜为了解决由无用的塑料废料而产生的这种污染问题已成为一件感兴趣的事情。
解决这些问题的方法包括回收,焚烧和掩埋但每种方法都有一定的限制(回收产品在使用上的限制,额外的成本和掩埋的埸地),因此近年来世界各国已怪可降解塑料作了许多研究。
可降解塑料技术可分为可光降解领域,可生物降解领域和可生物光降解领域,近年来涉及可生物光降解领域的产品作为通用塑料产品的取代物已经增加。可光降解领域技术可分为两种类型,引入光敏官能基和加入光敏试剂,前一种类型已由Dow Chemical公司,DuPont公司,Union Carbide公司和Bayer公司市售使用市售乙烯和一氧化碳的共聚物,以及Ecoplastic公司使用市售乙烯基甲酮共聚物,后一种类型由Ampacet公司和Ideamasters公司市售。由Scott-Gilead公司开发添加的金属配合物类型是主要类型。然而,当这些光可降解产品用于作通用薄膜时仍存在高成本问题而且在太阳光被遮断(当它们埋于土壤下时)的情况下可光降解产品不降解,因此,光降解领域的技术不能解决废塑料的这些通用问题于是在许多国家已进行了可生物降解领域技术另一些研究。
尽管有许多种类的可生物降解塑料,例如,衍生物形成聚合物像PHB(聚-β-羟基丁酸酯),用微生物产生生物化学的聚合物,或带有天然聚合物如几丁质或淀粉的聚合物,在本说明书中将叙述有带有淀粉的聚合物的相关现有技术所提及和改进的问题。
由GJL Griffin的美国专利4021388揭示了制备改进的可生物降解薄膜的方法,该方法用硅烷偶联剂处理淀粉的表面使之疏水性,但它在基质树脂和淀粉之间仅提高一点儿物理相互作用强度以致很难解决薄膜在掺入淀粉时物理性能的降低。
尽管由USDA(美国农业部)F.H.otey等人申请的美国专利4133784和4337181揭示了在乙烯-丙烯酸共聚物中加入α-淀粉而制备可生物降解薄膜的方法,但由于乙烯-丙烯酸共聚物价格高而很难商业化且所生产的薄膜物理性能下降。
由Seonil Glucose公司申请的南朝鲜专利公开号90-6336和91-8553揭示了一种方法,通过提高淀粉的疏水性或提高基质树脂的亲水性而提高基质树脂和淀粉之间相互作用强度以达到提高基质树脂和淀粉的相容性。
在本发明中,通过简化艺而减少生产成本,同时通过用偶联剂使基质树脂和淀粉进行化学结合而对物理性能的不利影响减少到最低程度。
本发明的一个目的是提供一种与淀粉化学结合的可生物降解聚乙烯组合物,而本发明的另一目的是提供制备此可生物降解聚乙烯组合物的方法。
本发明的组合物包括100重量份基质树脂,5-400重量份可生物降解掺入物质,0.01-10重量份偶联剂,0.01-1.0重量份自由基引发剂,0.01-5重量份路易斯酸催化剂,0.01-10重量份自氧化剂和0.01-10重量份增塑剂和可有可无的0.01-10重量份的共聚单体。
图1是根据本发明例1的可生物降解薄膜的红外线吸收光谱;和
图2是根据本发明例1的一部分可生物降解薄膜由扫描电子显微镜(X1200)所示的电子显微摄影。
基质树脂是低密度聚乙烯(LDPE),线性低密度聚乙烯(LLDPE)或高密度聚乙烯(HDPE),可生物降解掺入物质是选自由淀粉,酸处理的淀粉(稀煮沸的淀粉),酯化淀粉,醚化淀粉,阳离子淀粉,及其混合物,例如玉米淀粉,乙酸淀粉,磷酸淀粉组成的一组物质中的一个。化学结合基质树脂和淀粉的偶联剂是马来酐、甲基丙烯酸酐或马来酰亚胺,而自由基引发剂是过氧化苯甲酰、二叔丁基过氧化物,偶氮二异丁腈,叔丁基氢过氧化物,过氧化二枯基,Lupersol 101(penn walt公司)或perkadox-14(AKzo公司)。自氧化剂是选自油酸锰,硬脂酸锰油酸亚铁(Ⅱ),硬脂酸亚铁(Ⅱ)及其混合物的一组物质中的一个或多个;增塑剂是例如油酰胺,Viton或Erucamide。共聚单体是选自丙烯腈,苯乙烯和丙烯酸乙酯的一组物质中一个或多个。路易斯酸催化剂是选自油酸[CH3(CH2)7CH∶CH(CH2)7CO2H]油酸[CH3·(CH2)7·CH∶CH·(CH2)7·COOH],亚油酸,硬脂酸,乙酸,对-甲苯磺酸,癸酸,十二烷酸,十四烷酸,草酸,丙二酸,琥珀酸和己二酸。
与淀粉化学结合制备可生物降解聚乙烯组合物的方法实现了本发明的另一目的,该方法包括以一定量混合基质树脂,可生物降解掺入物质,偶联剂,自氧化剂,增塑剂,路易斯酸催化剂和自由基引发剂然后反应挤出该混合物。
采用双螺杆挤出机实施反应挤出方法通过简化工艺而降低了生产成本并在混合淀粉后将物理性能的降低减至最小程度。也就是说,将聚乙烯、自由基引发剂、偶联剂,例如马来酐,甲基丙烯酸酐或马来酰亚胺,玉米淀粉或淀粉衍生物和偶合催化剂同时引入并在150~220℃的温度和50~300rpm的螺杆转速下反应挤出从而酯化淀粉,在此期间发生偶联剂接枝到聚乙烯链上。已经发现使用0.01-10重量份偶联剂,例如马来酐、甲基丙烯酸酐或马来酰亚胺,0.01-1.0重量份自由基引发剂和0.01-5重量份路易斯酸催化剂优选各使用0.3重量份的自由基引发剂和路易斯酸催化剂,物理性能极好。
可生物降解掺入物质是,例如玉米淀粉、改性淀粉像醋酸淀粉、磷酸淀粉、氧化淀粉、阳离子淀粉等,该淀粉事先被干燥使水分含量小于3%避免在形成薄膜时产生气泡,因为工业生产的淀粉所含水分含量在12-15%的范围。
制备可降解粒料的方法是混合一定量的基质树脂,可生物降解掺入物质,偶联剂,自氧化剂,增塑剂,路易斯酸催化剂和自由基引发剂,在塑度记录仪的混合器中熔融该混合物或用配料器放置每种组分,熔融,挤出该混合物,用切粒机将其造粒。可生物降解膜的制备方法是将该粒料制成压塑薄膜或用热压机和制膜挤出机制成吹塑薄膜。压塑膜或吹塑膜也可通过将低密度聚乙烯,线性低密度聚乙烯或高密度聚乙烯加入到粒料中,然后干混并挤出该混合的粒料而制备。可生物降解树脂粒料也可模压成聚乙烯瓶。
可生物降解膜的机械性能例如拉伸强度和拉伸伸长可用Instron测定而物理性能可通过ASTM的标准仪器测定。其表面和断面也可用扫描电子显微镜来研究。可生物降解能力可通过形状变形和薄膜埋在土壤下之后物理性能依时间的变化以及用ASTM G21-70方法进行研究。
以下的例子进一步说明本发明但不限制本发明的范围。
例1
在此例中用马来酐作为偶联剂通过化学结合淀粉和聚乙烯链而制备可生物降解薄膜。
分别将50克马来酐、5克油酸、5克过氧化苯甲酰,50克油酰胺,20克油酸锰和20克油酸亚铁溶解在50ml丙酮中。将5公斤低密度聚乙烯(MI=3,密度=0.919)放入Henschel混合机中然后用上述溶液进行涂覆。
将已涂覆的聚乙烯粒料与60%(重量)的玉米淀粉(以上述低密度聚乙烯为基准)在维持在170℃且螺杆转速为250rpm的挤出机内反应挤出制备可生物降解母料料粒,在其中淀粉与聚乙烯链化学结合。将1.7公斤可生物降解母料和8.3公斤低密度聚乙烯(MI=3,密度=0.919)干混并使其通过薄膜挤出机而制备吹塑薄膜。
为测定所制备的薄膜的物理性能,用Instron测量该拉伸强度和拉伸伸长开根据ASTM G 21-70方法确定可生物降解能力。
在图1中可生物降解薄膜的红外线吸收光谱的1700-1800cm-1处显示了马来酐和淀粉上的羟基反应所产生的羧基的吸收峰,图2显示的是可生物降解薄膜由扫描电子显微镜的断面,该画面显示淀粉颗粒的断面被剖开,这进一步证实由于马来酐偶联剂的影响聚乙烯链与淀粉化学反应。
通过干混上述可生物降解母料和低密度聚乙烯(MI=3,密度=0.919)而制备的可生物降解薄膜的物理性能和可生物降解能力记录在下面表1中。
可生物降解能力根据ASTM G 21-70方法进行测定。在一定的时间(至少21天)之后,根据聚合物表面被真菌菌落覆盖的百分率对增长速率进行分类:
0%:0
少于10%:1
10-30%:2
30-60%:3
60-100%:4
例2-6
重复如例1相同的程序,不同是使用以下重量%(以聚乙烯为基准)的淀粉,用与例1相同的方法所测定的结果记录在下面的表1中。
表1
例号 | 淀粉含量(重量%) | 拉伸强度(kg/cm2) | 拉伸伸长(%) | 可生物降解能力 |
对比例1* | 0 | 180 | 400 | 0 |
1 | 10 | 169 | 346 | 3 |
2 | 20 | 153 | 315 | 4 |
3 | 30 | 127 | 230 | 4 |
4 | 40 | 102 | 155 | 4 |
5 | 50 | 65 | 80 | 4 |
6 | 60 | 43 | 50 | 4 |
*对比例1:用于如例1相同的程序测定,不同是未掺入淀粉。
例7
在此例中用苯乙烯作为偶联剂的共聚单体以增强马来酐,即偶联剂的接枝效率制备可生物降解薄膜。
分别将35克马来酐、35克苯乙烯、5克硬脂酸、20克硬脂酸亚铁、20克硬脂酸锰、50克油酰胺和5克过氧化苯甲酰溶于50ml丙酮中。将5公斤线性低密度聚乙烯(MI=1 密度=0.919)放入Henschel混合机内然后用以上的溶液涂覆。
将已涂覆的聚乙烯粒料与60%(重量)(以上述线性低密度聚乙烯为基准)的氧化淀粉在一维持在170℃且螺杆转速为230rpm的挤出机内反应挤出制备可生物降解母料粒料。
将1.7公斤可生物降解母料粒料和8.3公斤线性低密度聚乙烯(MI=1,密度=0.919)干混,使其通过薄膜挤出机而制备吹塑膜。
通过干混以上的可生物降解母料和线性低密度聚乙烯(MI=1,密度=0.919)而制备的可生物降解膜的物理性能和可生物降解能力记录在下表2中。
例8-12
重复如例7的相同程序,不同是使用以下重量%(以聚乙烯为基准)的淀粉用如例7相同的方法测定的结果记录在以下表2中。
表2
例号 | 淀粉含量(重量%) | 拉伸强度(kg/cm2) | 拉伸伸长(%) | 可生物降解能力 |
对比例2* | 0 | 330 | 600 | 0 |
7 | 10 | 298 | 530 | 3 |
8 | 20 | 254 | 495 | 4 |
9 | 30 | 194 | 435 | 4 |
10 | 40 | 126 | 258 | 4 |
11 | 50 | 95 | 120 | 4 |
12 | 60 | 75 | 75 | 4 |
*对比例2:用如例7相同的程序确定,不同是未掺入淀粉。
例13
在此例中用甲基丙烯酸酐作为偶联剂通过化学结合聚乙烯链和淀粉而制备可生物降解薄膜
分别将100克甲基丙烯酸酐,5克亚油酸,20克油酸锰,20克硬脂酸亚铁,50克油酰胺和5克过氧化苯甲酰溶于50ml丙酮中。将5公斤高密度聚乙烯(MI=0.28密度=0.945)放入Henschel混合机中然后用以上的溶液涂覆。
把该已涂覆的聚乙烯粒料与60重量%(以以上的高密度聚乙烯为基准)的玉米淀粉在维持在170℃且螺杆转速为210rpm的挤出机内进行反应挤出制备可生物降解母料粒料。
用1.7公斤的可生物降解母料和8.3公斤高密度聚乙烯(MI=0.28密度=0.945)干混并使其通过一薄膜挤出机而制备可生物降解吹塑薄膜。
通过干混以上的可生物降解母料和高密度聚乙烯(MI=0.28,密度=0.945)而制备的可生物降解薄膜的物理性能和可生物降解能力记录在下面的表3中。
例14-18
重复如例13相同的程序,不同是使以下重量%(以聚乙烯为基准)的淀粉并用如例13相同的方法进行测定,其结果记录在下面表3中。
表3
例号 | 淀粉含量(重量%) | 拉伸强度(kg/cm2) | 拉伸伸长(%) | 可生物降解能力 |
对比例3* | 0 | 640 | 600 | 0 |
13 | 10 | 585 | 540 | 3 |
14 | 20 | 547 | 505 | 4 |
15 | 30 | 325 | 425 | 4 |
16 | 40 | 216 | 237 | 4 |
17 | 50 | 134 | 115 | 4 |
18 | 60 | 90 | 68 | 4 |
*对比例3:用如例13相同的程序测定,不同是未掺入淀粉。
所制备的含有10%(重量)淀粉的可生物降解薄膜与用基本树脂制备的膜相比通过Instron测量其物理性能没有差别。已发现本发明制备可生物降解薄膜的方法是极好的方法,根据掺入淀粉而使物理性能的下降减小至最低限度,其改进之处在于通过可生物降解化学结合使基质树脂和淀粉颗粒之间的分界不清而淀粉颗粒断面切开的现像显示在用扫描电子显微镜的薄膜断面的观察图上。用10%(重量)以上的淀粉其可生物降解能力最佳。
Claims (17)
1、一种与淀粉化学结合的可生物降解聚乙烯组合物,它含有100重量份基质树脂,5-400重量份可生物降解掺入物质,0.01-10重量份偶联剂,0.01-1.0重量份自由基引发剂,0.01-5重量份路易士酸催化剂,0.01-10份量份自氧化剂和0.01-10重量份增塑剂。
2、根据权利要求1的组合物,其中还含有0.01-10重量份共聚单体。
3、根据权利要求2的组合物,其中共聚单体是选自丙烯腈,苯乙烯和丙烯酸乙酯的一组物质中的一或多个。
4、根据权利要求1的组合物,其中基质树脂是低密度聚乙烯或高密度聚乙烯。
5、根据权利要求1的组合物,其中可生物降解掺入物质是选自玉米淀粉,酸处理的淀粉,酯化淀粉,醚化淀粉,阳离子淀粉及其混合物的一组物质的一种。
6、根据权利要求1的组合物,其中偶联剂是选自马来酐,甲基丙烯酸酐和马来酰亚胺的一组物质中的一个。
7、根据权利要求1的组合物,其中自由基引发剂是过氧化苯甲酰,过氧化二-叔丁基,偶氮二异丁腈,叔丁基氢过氧化物,过氧化二枯基,Lupersol 101或Perkadox-14。
8、根据权利要求1的组合物,其中自氧化剂是选自油酸锰,硬脂酸锰,油酸亚铁(Ⅱ),硬脂酸亚铁(Ⅱ)及其混合物的一组物质中的一个或多个。
9、根据权利要求1的组合物,其中增塑剂是选自油酰胺,Viton和Erucamide的一组物质中的一个。
10、根据权利要求1的组合物,其中路易斯酸催化剂是选自油酸(CH3(CH2)7CH∶CH(CH2)7CO2H),油酸(CH3·(CH2)7·CH∶CH·(CH2)7·COOH),亚油酸,硬脂酸,乙酸,对甲苯磺酸,癸酸,十二烷酸,十四烷酸,草酸,丙二酸,琥珀酸和己二酸的一组物质中的一个或多个。
11、一种与淀粉化学结合的可生物降解聚乙烯组合物的制备方法,包括混合100重量份的基质树脂,5-400重量份的可生物降解掺入物质,0.01-10重量份偶联剂,0.01-1.0重量份自由基引发剂,0.01-5重量份路易斯酸催化剂,0.01-10重量份自氧化剂和0.01-10重量份增塑剂并反应挤出所说的混合物。
12、根据权利要求11的方法,其中还混合选自丙烯腈,苯乙烯和丙烯酸乙酯的一组物质中一个或多个共聚单体,其量为0.01-10重量份。
13、根据权利要求11的方法,其中还包括在反应挤出该混合物前干燥可生物降解掺入物质水份含量低于3%的范围。
14、根据权利要求11的方法,其中所说的混合物在150-220℃的温度以50-300rpm的螺杆速度反应挤出。
15、一种与淀粉化学结合的可生物降解聚乙烯制品包括根据权利要求1-10之一混合聚乙烯组合物,反应挤出该混合物并造粒成母料粒料。
16、根据权利要求15的可生物降解聚乙烯制品,其中还包括在母料粒料中加入低密度聚乙烯,线性低密度聚乙烯或高密度聚乙烯,干混并挤出以上的混合物。
17、根据权利要求16的可生物降解聚乙烯制品,其中可生物降解聚乙烯制品是薄膜或瓶子。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR920022255 | 1992-11-24 | ||
KR22255/92 | 1992-11-24 | ||
KR1019930014072A KR960012444B1 (ko) | 1992-11-24 | 1993-07-23 | 전분이 화학 결합된 생분해성 폴리에틸렌 조성물 및 그 제조방법 |
KR14072/93 | 1993-07-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1092084A true CN1092084A (zh) | 1994-09-14 |
Family
ID=26629373
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN93121454A Pending CN1092084A (zh) | 1992-11-24 | 1993-11-24 | 一种与淀粉化学结合的可生物降解聚乙烯组合物及其制备方法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US5461093A (zh) |
JP (1) | JPH07126449A (zh) |
KR (1) | KR960012444B1 (zh) |
CN (1) | CN1092084A (zh) |
CA (1) | CA2109660A1 (zh) |
GB (1) | GB2272700A (zh) |
IT (1) | IT1265218B1 (zh) |
MY (1) | MY109616A (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1057580C (zh) * | 1996-01-16 | 2000-10-18 | 北京市海淀区太生新工程材料研究所 | 一种降解型组合物及用其制造仿皮料的方法 |
CN101870774A (zh) * | 2010-05-10 | 2010-10-27 | 梁雄辉 | 生物淀粉降解塑料母粒及其生产方法以及降解塑料 |
CN104448398A (zh) * | 2014-11-18 | 2015-03-25 | 东莞市方中运动制品有限公司 | 一种木薯可降解塑料及其生产工艺和生产设备 |
CN110234699A (zh) * | 2016-11-22 | 2019-09-13 | 聚合材料有限公司 | 可降解聚合物组合物及其生产方法 |
CN111073143A (zh) * | 2019-12-26 | 2020-04-28 | 苏州润佳高分子材料有限公司 | 汽车用聚丙烯-聚乙烯改性复合材料 |
Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1100088C (zh) * | 1995-12-29 | 2003-01-29 | 北京市星辰现代控制工程研究所 | 可生物降解的淀粉树脂组合物,制备该组合物的方法及设备 |
US5667574A (en) * | 1996-11-06 | 1997-09-16 | Chi May Co., Ltd. | Starch-based composition for preparing an environment degradable α-olefinic polymer molding material |
KR100257036B1 (ko) * | 1998-03-09 | 2000-05-15 | 권수진 | 반응성이 우수한 열가소성 전분의 제조방법, 이를 함유하는 수지조성물 및 복합재료 |
US6482872B2 (en) | 1999-04-01 | 2002-11-19 | Programmable Materials, Inc. | Process for manufacturing a biodegradable polymeric composition |
KR20020066258A (ko) * | 2001-02-09 | 2002-08-14 | 김희성 | 환경 친화성 수지 조성물 및 그의 제조방법 |
KR20020094104A (ko) * | 2001-06-07 | 2002-12-18 | 주찬하이텍 주식회사 | 분해성 바이오 신 물질 |
KR20040046324A (ko) * | 2002-11-27 | 2004-06-05 | 주식회사 엠씨씨 | 복합분해성 폴리에틸렌 조성물 및 그를 사용한 폴리에틸렌 제품 |
KR100644256B1 (ko) * | 2004-04-30 | 2006-11-10 | 호남석유화학 주식회사 | 자동차 웨더스트립용 코팅재 및 이의 제조방법 |
SE530267C3 (sv) * | 2004-07-19 | 2008-05-13 | Add X Biotech Ab | Nedbrytbar förpackning av en polyolefin |
US8802754B2 (en) * | 2005-01-25 | 2014-08-12 | Mgpi Processing, Inc. | Starch-plastic composite resins and profiles made by extrusion |
WO2007050560A2 (en) * | 2005-10-24 | 2007-05-03 | Mgp Ingredients, Inc. | Thermotolerant starch-polyester composites and methods of making same |
JP5030501B2 (ja) * | 2006-07-31 | 2012-09-19 | 関西ペイント株式会社 | 澱粉系塗料組成物 |
KR20090035743A (ko) * | 2006-08-04 | 2009-04-10 | 플레이텍스 프로덕츠, 인크. | 윤활성 조성물 및 이로부터 제조된 제조물 |
US20080249212A1 (en) * | 2007-04-06 | 2008-10-09 | Sigworth William D | Starch-polyolefin composites with improved performance |
US8613834B2 (en) * | 2008-04-03 | 2013-12-24 | Basf Se | Paper coating or binding formulations and methods of making and using same |
FR2955329B1 (fr) * | 2010-01-15 | 2013-02-01 | Roquette Freres | Procede de preparation de compositions thermoplastiques a base d'amidon plastifie et compositions |
CN102504343A (zh) * | 2011-11-09 | 2012-06-20 | 青岛科技大学 | 一种循环利用式生物包装材料制备方法 |
CN102504344A (zh) * | 2011-11-09 | 2012-06-20 | 青岛科技大学 | 一种循环利用式高强度生物包装材料 |
MY163937A (en) | 2012-03-13 | 2017-11-15 | Texchem Polymers Sdn Bhd | Thermoplastic Starch Composition Derives From Agricultural Waste |
US10919203B2 (en) | 2015-06-30 | 2021-02-16 | BiologiQ, Inc. | Articles formed with biodegradable materials and biodegradability characteristics thereof |
US10995201B2 (en) | 2015-06-30 | 2021-05-04 | BiologiQ, Inc. | Articles formed with biodegradable materials and strength characteristics of the same |
US11111355B2 (en) | 2015-06-30 | 2021-09-07 | BiologiQ, Inc. | Addition of biodegradability lending additives to plastic materials |
US11674018B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics |
US11879058B2 (en) | 2015-06-30 | 2024-01-23 | Biologiq, Inc | Yarn materials and fibers including starch-based polymeric materials |
US11359088B2 (en) | 2015-06-30 | 2022-06-14 | BiologiQ, Inc. | Polymeric articles comprising blends of PBAT, PLA and a carbohydrate-based polymeric material |
US20170002185A1 (en) * | 2015-06-30 | 2017-01-05 | BiologiQ, Inc. | Articles Formed with Biodegradable Materials |
US11926940B2 (en) | 2015-06-30 | 2024-03-12 | BiologiQ, Inc. | Spunbond nonwoven materials and fibers including starch-based polymeric materials |
US11046840B2 (en) | 2015-06-30 | 2021-06-29 | BiologiQ, Inc. | Methods for lending biodegradability to non-biodegradable plastic materials |
US11926929B2 (en) | 2015-06-30 | 2024-03-12 | Biologiq, Inc | Melt blown nonwoven materials and fibers including starch-based polymeric materials |
US11149144B2 (en) | 2015-06-30 | 2021-10-19 | BiologiQ, Inc. | Marine biodegradable plastics comprising a blend of polyester and a carbohydrate-based polymeric material |
US11111363B2 (en) | 2015-06-30 | 2021-09-07 | BiologiQ, Inc. | Articles formed with renewable and/or sustainable green plastic material and carbohydrate-based polymeric materials lending increased strength and/or biodegradability |
US11674014B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Blending of small particle starch powder with synthetic polymers for increased strength and other properties |
US10920044B2 (en) | 2015-06-30 | 2021-02-16 | BiologiQ, Inc. | Carbohydrate-based plastic materials with reduced odor |
US10752759B2 (en) | 2015-06-30 | 2020-08-25 | BiologiQ, Inc. | Methods for forming blended films including renewable carbohydrate-based polymeric materials with high blow up ratios and/or narrow die gaps for increased strength |
CN105482397A (zh) * | 2016-01-26 | 2016-04-13 | 苏州羽帆新材料科技有限公司 | 一种生物可降解耐候复合材料及其制备方法 |
RU2672359C1 (ru) * | 2017-11-22 | 2018-11-14 | федеральное государственное бюджетное образовательное учреждение высшего образования "Кемеровский государственный университет" (КемГУ) | Способ получения биоразлагаемой пленки |
CN109251251B (zh) * | 2018-04-17 | 2020-01-07 | 江南大学 | 一种复合改性淀粉基可降解材料的加工方法 |
CN116535696B (zh) * | 2023-05-09 | 2024-02-09 | 日照西起工贸有限公司 | 一种可降解塑料及其制备方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1485833A (en) * | 1973-11-28 | 1977-09-14 | Coloroll Ltd | Synthetic-resin-based compositions |
DE2436555C3 (de) * | 1974-07-30 | 1979-12-13 | Maizena Gmbh, 2000 Hamburg | Verfahren zur Herstellung von Pfropfpolymeren durch Umsetzen von Stärke mit wasserlöslichen oder in Wasser dispergierbaren Vinyl- und/ oder Acrylpolymeren |
US4337181A (en) * | 1980-01-17 | 1982-06-29 | The United States Of America As Represented By The Secretary Of Agriculture | Biodegradable starch-based blown films |
JPH075688B2 (ja) * | 1983-02-14 | 1995-01-25 | キュノ、インコーポレーテッド | 変性多糖支持体 |
CH671961A5 (zh) * | 1987-02-27 | 1989-10-13 | Amrotex Ag | |
IL93620A0 (en) * | 1989-03-09 | 1990-12-23 | Butterfly Srl | Biodegradable articles based on starch and process for producing them |
US5162392A (en) * | 1989-05-19 | 1992-11-10 | Agri-Tech Industries, Inc. | Injection moldable biodegradable starch polymer composite |
BE1005694A3 (fr) * | 1992-02-07 | 1993-12-21 | Solvay | Composition a base d'amidon. |
US5321064A (en) * | 1992-05-12 | 1994-06-14 | Regents Of The University Of Minnesota | Compositions of biodegradable natural and synthetic polymers |
-
1993
- 1993-07-23 KR KR1019930014072A patent/KR960012444B1/ko not_active IP Right Cessation
- 1993-11-22 CA CA002109660A patent/CA2109660A1/en not_active Abandoned
- 1993-11-23 US US08/156,369 patent/US5461093A/en not_active Expired - Lifetime
- 1993-11-23 GB GB9324071A patent/GB2272700A/en not_active Withdrawn
- 1993-11-24 CN CN93121454A patent/CN1092084A/zh active Pending
- 1993-11-24 MY MYPI93002460A patent/MY109616A/en unknown
- 1993-11-24 IT IT93MI002485A patent/IT1265218B1/it active IP Right Grant
- 1993-11-24 JP JP5317409A patent/JPH07126449A/ja active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1057580C (zh) * | 1996-01-16 | 2000-10-18 | 北京市海淀区太生新工程材料研究所 | 一种降解型组合物及用其制造仿皮料的方法 |
CN101870774A (zh) * | 2010-05-10 | 2010-10-27 | 梁雄辉 | 生物淀粉降解塑料母粒及其生产方法以及降解塑料 |
CN104448398A (zh) * | 2014-11-18 | 2015-03-25 | 东莞市方中运动制品有限公司 | 一种木薯可降解塑料及其生产工艺和生产设备 |
CN110234699A (zh) * | 2016-11-22 | 2019-09-13 | 聚合材料有限公司 | 可降解聚合物组合物及其生产方法 |
US11155702B2 (en) | 2016-11-22 | 2021-10-26 | Polymateria Limited | Degradable polymer and method of production |
CN111073143A (zh) * | 2019-12-26 | 2020-04-28 | 苏州润佳高分子材料有限公司 | 汽车用聚丙烯-聚乙烯改性复合材料 |
Also Published As
Publication number | Publication date |
---|---|
US5461093A (en) | 1995-10-24 |
IT1265218B1 (it) | 1996-10-31 |
KR960012444B1 (ko) | 1996-09-20 |
ITMI932485A1 (it) | 1995-05-24 |
GB2272700A (en) | 1994-05-25 |
CA2109660A1 (en) | 1994-05-25 |
JPH07126449A (ja) | 1995-05-16 |
GB9324071D0 (en) | 1994-01-12 |
ITMI932485A0 (it) | 1993-11-24 |
MY109616A (en) | 1997-03-31 |
KR940011558A (ko) | 1994-06-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1092084A (zh) | 一种与淀粉化学结合的可生物降解聚乙烯组合物及其制备方法 | |
CN1037352C (zh) | 与淀粉结合的可生物降解聚乙烯组合物及其制法和用途 | |
US20080261019A1 (en) | Pvc/Wood Composite | |
CN108948690B (zh) | 一种聚乳酸-木质素-淀粉复合材料及其制备方法 | |
JPH09194696A (ja) | 澱粉がマトリックス樹脂に化学結合された生分解性プラスチック組成物とその製造方法及びそれから製造された成形物 | |
CN1266179C (zh) | 酸改性的聚丙烯树脂的制造方法 | |
CN1230466C (zh) | 一种可完全生物降解塑料母料及其制备方法 | |
KR102579310B1 (ko) | 폴리비닐알코올을 포함하는 생분해성 수지 조성물 및 그 제조방법 | |
EP4071211A1 (en) | Biodegradable resin composition and method for producing same | |
Raj et al. | Biodegradability, thermal, chemical, mechanical and morphological behavior of LDPE/pectin and LDPE/modified pectin blend | |
CN107759990B (zh) | 一种全生物基聚乳酸复合材料及其制备方法 | |
CN1156154A (zh) | 生物可降解的塑料组合物制备该组合物的方法和用该组合物制备的产品 | |
EP0592240B1 (en) | Method for rendering resins compatible and composition comprising such compatibilized resins | |
CN111621114B (zh) | 一种改性聚丙烯家具复合材料及其制备方法和用途 | |
CN1126781C (zh) | 可控环境降解塑料母料 | |
CN107698714B (zh) | 一种衣康酸酐接枝聚乳酸共聚物及其制备方法和应用 | |
HAGHIGHAT et al. | Preparation of biodegradable low density polyethylene by starch-urea composition for agricultural applications | |
CN115322447B (zh) | 一种淀粉基增韧复合材料的加工方法 | |
CN1168778C (zh) | 可降解的聚(β-羟基丁酸酯)三元共混物及其制备方法 | |
CN1594412A (zh) | 高熔体强度聚丙烯及其制备方法 | |
KR960005075B1 (ko) | 중합관능기를 갖는 전분을 이용한 생분해성 폴리에틸렌 조성물 및 그 제조방법 | |
KR970003306B1 (ko) | 에틸렌-비닐 아세테이트 공중합체와 폴리에스터-에틸렌 공중합체로 된 생분해성 플라스틱 조성물 및 그 제조방법 | |
CN1088227A (zh) | 可光降解的聚烯烃组合物 | |
CN117362963A (zh) | 一种高性能可降解塑料及其制备方法 | |
KR20020066258A (ko) | 환경 친화성 수지 조성물 및 그의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C01 | Deemed withdrawal of patent application (patent law 1993) | ||
WD01 | Invention patent application deemed withdrawn after publication |