CN1092083A - 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
- CN1092083A CN1092083A CN93121455A CN93121455A CN1092083A CN 1092083 A CN1092083 A CN 1092083A CN 93121455 A CN93121455 A CN 93121455A CN 93121455 A CN93121455 A CN 93121455A CN 1092083 A CN1092083 A CN 1092083A
- Authority
- CN
- China
- Prior art keywords
- starch
- weight part
- composition
- biodegradable
- polyethylene
- 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.)
- Granted
Links
- 229920002472 Starch Polymers 0.000 title claims abstract description 57
- 239000008107 starch Substances 0.000 title claims abstract description 57
- 235000019698 starch Nutrition 0.000 title claims abstract description 56
- -1 polyethylene Polymers 0.000 title claims abstract description 33
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 25
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 title claims description 35
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 17
- 229920001684 low density polyethylene Polymers 0.000 claims description 10
- 239000004702 low-density polyethylene Substances 0.000 claims description 10
- 239000004700 high-density polyethylene Substances 0.000 claims description 9
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000008188 pellet Substances 0.000 claims description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-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
- 229920001903 high density polyethylene Polymers 0.000 claims description 6
- 239000004902 Softening Agent Substances 0.000 claims description 5
- 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 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 4
- 229920000881 Modified starch Polymers 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019426 modified starch Nutrition 0.000 claims description 4
- 229940113162 oleylamide Drugs 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 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
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 229920004889 linear high-density polyethylene Polymers 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 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 compound 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 compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide 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
- 239000004368 Modified starch Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-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
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 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
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000004291 polyenes Polymers 0.000 abstract 1
- 239000010408 film Substances 0.000 description 28
- 230000000704 physical effect Effects 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 229940099112 cornstarch Drugs 0.000 description 2
- 229920006238 degradable plastic Polymers 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002101 Chitin Polymers 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
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012412 chemical coupling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 241000894007 species Species 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- 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
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2310/00—Masterbatches
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明涉及一种由淀粉和聚烯链化学结合而成
的可生物降解薄膜，它是使用聚乙烯，与淀粉和聚乙
烯键合的偶联剂和酸性催化共聚单体。本发明还涉
及制备此薄膜的方法。以聚乙烯为基准的各组分含
量(重量)：偶联剂为0.01—10％，酸性催化共聚单体
为0.01—10％，自由基引发剂为0.01—10％，应用反
应挤出使工艺简化而降低了生产成本。通过测量所
制备的含有高达20％(重量)淀粉的可生物降解薄膜
与基本树脂制备的薄膜的拉伸强度和拉伸伸长进行
比较没有差别。
Description
本发明涉及一种使用偶联剂例如马来酐，甲基丙烯酸酐或马来酰亚胺偶联剂与淀粉和聚乙烯偶联，而聚乙烯是具有最广泛应用的聚烯烃，和一种酸性催化剂例如丙烯酸和/或甲基丙烯酸（它是一种相容剂和催化剂）通过淀粉与聚乙烯链化学结合的可生物降解组合物，本发明还涉及该组合物的制备方法。
合成塑料因其极好的物理性能，光亮度和低价格从而克服使用天然材料所带来问题及限制。通过开发各种聚合物，尤其是塑料已建立塑料文明，它是现代科技的特点之一。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还正在制订各种各样的对策，解决塑料废料的污染问题已成为一件感兴趣的事情。
回收，焚化和掩埋已被主要用来解决这些由各种固体废料，包括塑料废物所引起的环境污染问题。然而废料通过掩埋的处理以及回收都不能完全解决环境污染问题。
因此，近来对可自身降解的可降解塑料的开发产生极大的兴趣并进行各种研究正日趋增长。可降解塑料技术分为可光降解领域。可生物降解领域，和可光与生物降解技术相结合的生物光降解领域。
尽管有许多种类的生物降解塑料，例如，微生物形成聚合物像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关带有淀粉的聚合物的现有技术所提及和改进的问题。
由G.J.L.，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，但它仅在基体树脂和淀粉之间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的（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推广且所生产的薄膜物理性能下降。
由南朝鲜的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的物理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，通过简化工艺而减少生产成本并且克服物理性能的降低，通过研究得出结论按通过仅仅提高基质树脂和淀粉之间的物理相互作用强度而掺入淀粉来克服薄膜物理性能的降低。
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，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。
本发明的组合物含有100重量份基质树脂，5-400重量份可生物降解掺入材料，0.01-10重量份偶联剂，0.01-10重量份酸性催化共聚单体，0.01-1.0重量份自由基引发剂，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（×1200）所示的电子显微镜摄影。
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），可生物降解掺入材料是选自由淀粉，酸处理的淀粉，酯化淀粉，醚化淀粉，阳离子淀粉和它们的混合物，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，而同时作催化剂和相容剂的酸催化共聚单体是丙烯酸和/或甲基丙烯酸。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（Pennwalt公司）或Perkadox-14（AKEO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的一外或多个，增塑剂是，例如油酰胺（oleamide），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种或多种。
为了达到本发明的另一目的制备与淀粉化学结合的可生物降解聚乙烯组合物的方法，包括以一定量混合基质树脂，可生物降解掺入物质，偶联剂，酸性催化共聚单体，自氧化剂，增塑剂，和自由基引发剂并反应挤出该混合物。
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、甲基丙烯酸或马来酰
亚胺，玉米淀粉或淀粉衍生物和酸性催化共聚单体同时放在一起并在150-220℃的温度和50-300rpm螺杆转速下反应挤出而酯化淀粉，同时偶联剂接枝到聚乙烯链上。
优选使用像马来酐，甲基丙烯酸或马来酰亚胺这样的偶联剂，其量为0.01-10%（重量），酸性催化共聚单体例如丙烯酸或甲基丙烯酸的用量为0.01-10%（重量），自由基引发剂用量为0.01-1.0%（重量），而可生物降解掺入物质用量为5-80%（重量）。
可生物降解掺入物质是，例如玉米淀粉或酸性淀粉并事先干燥，其水分含量在小于3%范围。可生物降解薄膜可通过是以一定量混合基质树脂（聚乙烯），可生物降解掺入物质（淀粉或淀粉衍生物）自由基引发剂，酸性催化共聚单体（丙烯酸或甲基丙烯酸），自氧化剂（油酸，金属油酸盐，等）增塑剂油酰胺（oleamide）），在一塑度纪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，挤出该混合物并用造粒机对其进行造粒，用一台热压机和薄膜挤出机将丸粒制成压塑薄膜或吹塑薄膜而制备。压塑薄膜或吹塑薄膜也可通过把低密度聚乙烯，线性低密度聚乙烯或高密度聚乙烯加入粒料中，干混然后挤出该粒料而制备。可生物降解树脂粒料也可模压成聚乙烯瓶。
UTM（万能测试机）测定根据下列例1-13所制备的可生物降解薄膜的机械性能例如拉伸强度和拉伸伸长而物理性能可用ASTM标准仪器进行测定。其表面和断面也可用扫描电子显微镜来研究。在红外吸收光谱上的1700-1800cm-1处（参考图1）显示为酯羧基的吸收峰，基质树脂和淀粉颗粒之间的界面是不清楚的这一事实以及淀粉颗粒是被分段剖开的这一现象显示在用扫描电子显微镜（参
考图2）的薄膜横断面上。这说明淀粉与聚乙烯链化学结合。
可生物降解能力可通过形状形变和薄膜埋在土壤下以后物理性能依时间的变化以及用ASTM G 21-70方法而进行研究。
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.
在此例中为改进偶联剂的反应效果用马来酐作为偶联剂，丙烯酸作为酸性催化剂共聚单体，苯乙烯作为共聚单体通过淀粉和聚乙烯链之间的化学结合而制备可生物降解薄膜。
分别将37.5克马来酐，12.5克丙烯酸，37.5克苯乙烯，5克过氧化苯甲酰，50克油酰胺，和50克油酸锰溶于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（以上述低密度聚乙烯为基准）的玉米淀粉在维持在170℃且螺杆转速为250rpm的挤出机中反应挤出以制备可生物降解母料粒料其中淀粉与聚乙烯链为化学结合。
将1.7公斤该可生物降解母料和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。
通过干混以上的可生物降解母料和低密度聚乙烯（MI＝3，密度＝0.919）而制备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。在一规定的时间（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的相同程序，不同是使用以下重量%的淀粉（以聚乙烯为基准），用如例1相同的方法所测定的结果记录在下面表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＊123456 | 0102030405060 | 33031529521515312487 | 60056053045027014080 | 0344444 |
＊对比例1：和如例1相同的程序测定，不同是未掺入淀粉。
例7
在此例中用甲基丙基烯酸酐作为偶联剂，用甲基丙烯酸作为酸性催化共聚单体以使聚乙烯链与淀粉化学偶联制备可生物降解薄膜。
分别将50克甲基丙烯酸酐，25克甲基丙烯酸，5克过氧化苯甲酰，50克油酰胺和50克油酸锰溶于50ml丙酮中。将5kg线性低密度聚乙烯（MI＝1，密度＝0.919）放入Henchel混合机中，然后用以上的溶液涂覆。
将已涂覆的聚乙烯粒料60%（重量）（以上述线性低密度聚乙烯为基准）的阳离子淀粉在维持175℃且螺杆转速为200rpm的挤出机内反应挤出制备可生物降解母料粒料其中淀粉与聚乙烯是化学结合的。
将1.7公斤该可生物降解母料和8.3公斤线性低密度聚乙烯（MI＝0.28，密度0.945）干混并使它们通过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线性低密度聚乙烯（MI0.28，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均记录在下面表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下面的表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1＊789101112 | 0102030405060 | 640635614516321189106 | 600580555454335215123 | 0344444 |
＊ 对比例2：用如例1相同的程序测定，不同是未掺入淀粉。
制备含有高达20%（重量）淀粉可生物降解薄膜与基本树脂相比较用Instron测量其拉伸强度和拉伸伸长没有差别。在红外吸收光谱上发现在淀粉和基质树脂之间显示化学结合的酯链这一事实及基质树脂和淀粉颗粒之间的界限不清楚这一现象，以及淀粉颗粒被断面剖开均显示在用扫描电子显微镜的薄膜断面图上，这证实了淀粉和基质之间的化学结合。高于10%（重量）的淀粉时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，0.01-10重量份酸性催化共聚单体，0.01-1.0重量份自由基引发剂，0.01-10重量份自氧化剂和0.01-10重量份增塑剂。
2、根据权利要求1的组合物，其中还包括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个或多个
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，线性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淀粉，酸处理的淀粉，酯化淀粉，醚化淀粉，阳离子淀粉和其混合物的一组物质中的一个。
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的一组物质中一个。
10、根据权利要求1的组合物，其中同时作为催化剂和相容剂的酸性催化共聚单体是丙烯酸和/或甲基丙烯酸。
11、一种制备与淀粉化学结合的可生物降解聚乙烯组合物的方法，包括混合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重量份偶联制，0.01-10重量份酸性催化共聚单体，0.01-1.0重量份自由基引发剂，0.01-10重量份自氧化剂和0.01-10重量份增塑剂，然后反应挤出该混合物。
12、根据权利要求11的方法，其中还混合以0.01-10重量份的量选自丙烯腈，苯乙烯和丙烯酸乙酯的一组物质中的一个或多个。
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之前干燥该可生物降解掺入物质于水份含量低于3%的范围内。
14、根据权利要求11的方法，其中所说的混合物在150-220℃的温度和50-300rpm的螺杆转速下反应挤出。
15、一种与淀粉化学结合的可生物降解聚乙烯制品包括混合根据权利要求1-10之一的聚乙烯组合物，反应挤出该混合物并造粒成为母粒粒料。
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母料粒料中，干混并挤出以上的混合料。
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 |
|---|---|---|---|
| KR22256/92 | 1992-11-24 | ||
| KR920022256 | 1992-11-24 | ||
| KR1019930014073A KR960012445B1 (ko) | 1992-11-24 | 1993-07-23 | 전분이 화학결합된 생분해성 폴리에틸렌 조성물 및 그 제조방법 |
| KR14073/93 | 1993-07-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1092083A true CN1092083A (zh) | 1994-09-14 |
| CN1037352C CN1037352C (zh) | 1998-02-11 |
Family
ID=26629374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93121455A Expired - Fee Related CN1037352C (zh) | 1992-11-24 | 1993-11-24 | 与淀粉结合的可生物降解聚乙烯组合物及其制法和用途 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5461094A (zh) |
| JP (1) | JPH06316655A (zh) |
| KR (1) | KR960012445B1 (zh) |
| CN (1) | CN1037352C (zh) |
| CA (1) | CA2109657A1 (zh) |
| GB (1) | GB2272699B (zh) |
| IT (1) | IT1265219B1 (zh) |
| TW (1) | TW316274B (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417648A (zh) * | 2011-11-23 | 2012-04-18 | 吴江明峰聚氨酯制品有限公司 | 一种可生物降解的聚乙烯塑料膜 |
| CN107835837A (zh) * | 2015-06-30 | 2018-03-23 | 白鸥逻辑股份有限公司 | 由生物可降解材料形成的物件 |
| 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 |
Families Citing this family (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2997995B2 (ja) * | 1995-09-13 | 2000-01-11 | 日本コーンスターチ株式会社 | 生分解性樹脂組成物の水系分散液 |
| 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 |
| KR100368738B1 (ko) * | 1996-12-12 | 2003-04-21 | 에스케이 주식회사 | 생/광분해성 농업용 멀칭필름 조성물과 이의 제조방법 및 이로 부터 제조된 성형물 |
| JP2001098081A (ja) * | 1999-09-30 | 2001-04-10 | Sakae Riken Kogyo Kk | オレフィン系樹脂組成物及びその製造方法 |
| WO2001068744A2 (en) * | 2000-03-16 | 2001-09-20 | Sanjiv Satyendra Nevgi | Modified plastic granules for manufacturing flammable type polythene film |
| KR20020066258A (ko) * | 2001-02-09 | 2002-08-14 | 김희성 | 환경 친화성 수지 조성물 및 그의 제조방법 |
| KR100458042B1 (ko) * | 2001-09-11 | 2004-11-26 | 호남석유화학 주식회사 | 전분함유 폴리에틸렌 생붕괴성 수지 조성물 및 그 제조방법 |
| KR20030037530A (ko) * | 2001-11-06 | 2003-05-14 | 박재석 | 일회용 전분제 용기 및 그 제조방법 |
| AU2002357177A1 (en) * | 2001-12-12 | 2003-06-23 | North Carolina State University | Methods of co2-assisted reactive extrusion |
| WO2003074604A1 (en) * | 2002-02-28 | 2003-09-12 | Board Of Trustees Of The University Of Arkansas | Biodegradable materials from starch-grafted polymers |
| KR100481420B1 (ko) * | 2002-10-22 | 2005-04-08 | 주식회사 이래화학 | 생분해성 소재를 이용한 혈관주사용 주사바늘 |
| KR100602386B1 (ko) * | 2003-07-11 | 2006-07-20 | 김찬형 | 복합분해성 열가소성 중합체 조성물 및 이로부터 제조되는복합분해성 열가소성 중합체 제품 및 그의 제조 방법 |
| US20080036115A1 (en) * | 2004-03-10 | 2008-02-14 | Minoru Ueda | Starch Resin Composition, Molded Product Using the Same and Method for Producing the Same |
| US20080249212A1 (en) * | 2007-04-06 | 2008-10-09 | Sigworth William D | Starch-polyolefin composites with improved performance |
| US8361947B2 (en) * | 2007-04-30 | 2013-01-29 | Peel Away Limited | Paint remover |
| US8613834B2 (en) * | 2008-04-03 | 2013-12-24 | Basf Se | Paper coating or binding formulations and methods of making and using same |
| US20090275699A1 (en) * | 2008-05-05 | 2009-11-05 | Mingfu Zhang | Starch containing formaldehyde-free thermoset binders for fiber products |
| FR2955329B1 (fr) * | 2010-01-15 | 2013-02-01 | Roquette Freres | Procede de preparation de compositions thermoplastiques a base d'amidon plastifie et compositions |
| US9718258B2 (en) | 2011-12-20 | 2017-08-01 | Kimberly-Clark Worldwide, Inc. | Multi-layered film containing a biopolymer |
| US9327438B2 (en) | 2011-12-20 | 2016-05-03 | Kimberly-Clark Worldwide, Inc. | Method for forming a thermoplastic composition that contains a plasticized starch polymer |
| US9815949B2 (en) * | 2013-07-31 | 2017-11-14 | Abdul Rasoul Oromiehie | Biodegradable nanocomposites containing nanoclay and titanium dioxide nanoparticles |
| US9464188B2 (en) | 2013-08-30 | 2016-10-11 | Kimberly-Clark Worldwide, Inc. | Simultaneous plasticization and compatibilization process and compositions |
| WO2016088124A1 (en) * | 2014-12-02 | 2016-06-09 | B. G. Negev Technologies And Applications Ltd., At Ben-Gurion University | Modified polysaccharides for use as anti-microbial agents |
| US10995201B2 (en) | 2015-06-30 | 2021-05-04 | BiologiQ, Inc. | Articles formed with biodegradable materials and strength characteristics of the same |
| US10920044B2 (en) | 2015-06-30 | 2021-02-16 | BiologiQ, Inc. | Carbohydrate-based plastic materials with reduced odor |
| 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 |
| 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 |
| US11879058B2 (en) | 2015-06-30 | 2024-01-23 | Biologiq, Inc | Yarn materials and fibers including starch-based polymeric materials |
| 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 |
| US11149144B2 (en) | 2015-06-30 | 2021-10-19 | BiologiQ, Inc. | Marine biodegradable plastics comprising a blend of polyester and a carbohydrate-based polymeric material |
| US11926929B2 (en) | 2015-06-30 | 2024-03-12 | Biologiq, Inc | Melt blown nonwoven materials and fibers including starch-based polymeric materials |
| US11926940B2 (en) | 2015-06-30 | 2024-03-12 | BiologiQ, Inc. | Spunbond nonwoven materials and fibers including starch-based polymeric materials |
| US10919203B2 (en) * | 2015-06-30 | 2021-02-16 | BiologiQ, Inc. | Articles formed with biodegradable materials and biodegradability characteristics thereof |
| US11359088B2 (en) | 2015-06-30 | 2022-06-14 | BiologiQ, Inc. | Polymeric articles comprising blends of PBAT, PLA and a carbohydrate-based polymeric material |
| US11674018B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics |
| US11111355B2 (en) | 2015-06-30 | 2021-09-07 | BiologiQ, Inc. | Addition of biodegradability lending additives to plastic materials |
| US11046840B2 (en) | 2015-06-30 | 2021-06-29 | BiologiQ, Inc. | Methods for lending biodegradability to non-biodegradable plastic materials |
| TR201808556T4 (tr) | 2015-10-27 | 2018-07-23 | Pep Licensing Ltd | Bir biyobozunur, biyogübrelenebilir, biyoçürütülebilir plastik. |
| US9925707B2 (en) | 2015-12-22 | 2018-03-27 | Pep Licensing Limited | Process for preparation of biodegradable biocompostable biodigestible polyolefins |
| US11505687B2 (en) | 2020-08-05 | 2022-11-22 | Nano And Advanced Materials Institute Limited | Environmentally degradable foamed master batch composition and using thereof |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1485833A (en) * | 1973-11-28 | 1977-09-14 | Coloroll Ltd | Synthetic-resin-based compositions |
| US3867324A (en) * | 1972-07-28 | 1975-02-18 | Union Carbide Corp | Environmentally degradable-biodegradable blend of an oxyalkanoyl polymer and an environmentally degradable ethylene polymer |
| 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 |
| GB1600496A (en) * | 1977-09-16 | 1981-10-14 | Coloroll Ltd | Plasticsbased composition |
| 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 |
| US4375535A (en) * | 1980-04-28 | 1983-03-01 | Standard Brands Incorporated | Stable liquid, amylopectin starch graft copolymer compositions |
| WO1984003053A1 (en) * | 1983-02-14 | 1984-08-16 | Amf Inc | Modified polysaccharide supports |
| CH671961A5 (zh) * | 1987-02-27 | 1989-10-13 | Amrotex Ag | |
| US5162392A (en) * | 1989-05-19 | 1992-11-10 | Agri-Tech Industries, Inc. | Injection moldable biodegradable starch polymer composite |
| US5026745A (en) * | 1989-06-12 | 1991-06-25 | Aristech Chemical Corporation | Biodeteriable plastics and blends |
| IT1240503B (it) * | 1990-07-25 | 1993-12-17 | Butterfly Srl | Miscela polimerica amidacea particolarmente per la produzione di film e simili e procedimento per la sua produzione. |
| 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 KR1019930014073A patent/KR960012445B1/ko not_active IP Right Cessation
- 1993-11-20 TW TW082109789A patent/TW316274B/zh active
- 1993-11-22 CA CA002109657A patent/CA2109657A1/en not_active Abandoned
- 1993-11-23 US US08/156,371 patent/US5461094A/en not_active Expired - Lifetime
- 1993-11-23 GB GB9324058A patent/GB2272699B/en not_active Expired - Fee Related
- 1993-11-24 CN CN93121455A patent/CN1037352C/zh not_active Expired - Fee Related
- 1993-11-24 JP JP5317408A patent/JPH06316655A/ja active Pending
- 1993-11-24 IT IT93MI002486A patent/IT1265219B1/it active IP Right Grant
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417648A (zh) * | 2011-11-23 | 2012-04-18 | 吴江明峰聚氨酯制品有限公司 | 一种可生物降解的聚乙烯塑料膜 |
| CN107835837A (zh) * | 2015-06-30 | 2018-03-23 | 白鸥逻辑股份有限公司 | 由生物可降解材料形成的物件 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| ITMI932486A0 (it) | 1993-11-24 |
| US5461094A (en) | 1995-10-24 |
| KR960012445B1 (ko) | 1996-09-20 |
| TW316274B (zh) | 1997-09-21 |
| KR940011556A (ko) | 1994-06-21 |
| ITMI932486A1 (it) | 1995-05-24 |
| JPH06316655A (ja) | 1994-11-15 |
| GB2272699B (en) | 1997-04-02 |
| GB9324058D0 (en) | 1994-01-12 |
| CA2109657A1 (en) | 1994-05-25 |
| IT1265219B1 (it) | 1996-10-31 |
| CN1037352C (zh) | 1998-02-11 |
| GB2272699A (en) | 1994-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1092083A (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 | |
| 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 | |
| CA2123082C (en) | Thermoplastic polymer alloy composition | |
| CN1124286C (zh) | 基于醋酸乙烯酯树脂的乳液的制备方法,以及含水粘合剂 | |
| CN108948690B (zh) | 一种聚乳酸-木质素-淀粉复合材料及其制备方法 | |
| CN1230466C (zh) | 一种可完全生物降解塑料母料及其制备方法 | |
| CN1208363C (zh) | 功能化聚烯烃树脂的制备方法 | |
| US20220049077A1 (en) | Method of producing bioplastic pellets using livestock manure method of producing bioplastic pellets using livestock manure | |
| CN111423689B (zh) | 一种改性聚丙烯材料及其制备方法与应用 | |
| CN1296423C (zh) | 纳米材料改性聚乙烯地面覆盖薄膜 | |
| CN111621114B (zh) | 一种改性聚丙烯家具复合材料及其制备方法和用途 | |
| CN1109062C (zh) | 无机基料复合降解塑料母料的制造方法 | |
| CN1646617A (zh) | 填充剂组合物 | |
| 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 | |
| CN1478808A (zh) | 淀粉基三元体系完全生物降解膜及吹塑成膜方法 | |
| CN1126781C (zh) | 可控环境降解塑料母料 | |
| CN115322447B (zh) | 一种淀粉基增韧复合材料的加工方法 | |
| CN1651497A (zh) | 制备改性聚烯烃树脂的方法 | |
| CN1227229A (zh) | 热稳定性改进的α－取代的丙烯酸酯接枝共聚物 | |
| JPH0819294B2 (ja) | 複合樹脂組成物、シート成形用複合樹脂組成物およびその成形品 | |
| KR960005075B1 (ko) | 중합관능기를 갖는 전분을 이용한 생분해성 폴리에틸렌 조성물 및 그 제조방법 | |
| CN1594412A (zh) | 高熔体强度聚丙烯及其制备方法 | |
| CN114058116A (zh) | 一种聚丙烯复合材料及其制备方法 | |
| CN117247642A (zh) | 一种改性可降解塑料 | |
| KR970003306B1 (ko) | 에틸렌-비닐 아세테이트 공중합체와 폴리에스터-에틸렌 공중합체로 된 생분해성 플라스틱 조성물 및 그 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |