CN107629304A - A kind of bio-based ecological plastic film and preparation method thereof - Google Patents
A kind of bio-based ecological plastic film and preparation method thereof Download PDFInfo
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- CN107629304A CN107629304A CN201710874202.2A CN201710874202A CN107629304A CN 107629304 A CN107629304 A CN 107629304A CN 201710874202 A CN201710874202 A CN 201710874202A CN 107629304 A CN107629304 A CN 107629304A
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- modified starch
- hydrophobic modified
- bio
- plastic
- acid
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Links
- 239000002985 plastic film Substances 0.000 title claims abstract description 57
- 229920006255 plastic film Polymers 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920000881 Modified starch Polymers 0.000 claims abstract description 86
- 239000004368 Modified starch Substances 0.000 claims abstract description 80
- 235000019426 modified starch Nutrition 0.000 claims abstract description 80
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 70
- 238000010525 oxidative degradation reaction Methods 0.000 claims abstract description 59
- 239000000654 additive Substances 0.000 claims abstract description 58
- 230000000996 additive effect Effects 0.000 claims abstract description 55
- 230000003413 degradative effect Effects 0.000 claims abstract description 53
- 239000000088 plastic resin Substances 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 36
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000007664 blowing Methods 0.000 claims abstract description 6
- 229920003023 plastic Polymers 0.000 claims description 56
- 239000004033 plastic Substances 0.000 claims description 52
- 229920002472 Starch Polymers 0.000 claims description 44
- 239000008107 starch Substances 0.000 claims description 44
- 235000019698 starch Nutrition 0.000 claims description 44
- -1 polyethylene Polymers 0.000 claims description 32
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 30
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 18
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 18
- 229910052723 transition metal Inorganic materials 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 14
- 239000008116 calcium stearate Substances 0.000 claims description 14
- 235000013539 calcium stearate Nutrition 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 12
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 229920001903 high density polyethylene Polymers 0.000 claims description 10
- 239000004700 high-density polyethylene Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- 235000019359 magnesium stearate Nutrition 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- 239000004800 polyvinyl chloride Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 6
- XXLFLUJXWKXUGS-UHFFFAOYSA-N 6-methoxyquinoline-4-carboxylic acid Chemical compound N1=CC=C(C(O)=O)C2=CC(OC)=CC=C21 XXLFLUJXWKXUGS-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 244000017020 Ipomoea batatas Species 0.000 claims description 6
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000001630 malic acid Substances 0.000 claims description 6
- 235000011090 malic acid Nutrition 0.000 claims description 6
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 229960005137 succinic acid Drugs 0.000 claims description 2
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000002362 mulch Substances 0.000 description 57
- 238000004519 manufacturing process Methods 0.000 description 25
- 239000002689 soil Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 15
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012545 processing Methods 0.000 description 13
- 238000011056 performance test Methods 0.000 description 9
- 238000004804 winding Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920002261 Corn starch Polymers 0.000 description 5
- 239000008120 corn starch Substances 0.000 description 5
- 229940099112 cornstarch Drugs 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- 239000012634 fragment Substances 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- CTIHZTFULZJBGQ-UHFFFAOYSA-L cobalt(2+);decanoate Chemical compound [Co+2].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O CTIHZTFULZJBGQ-UHFFFAOYSA-L 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000010835 comparative analysis Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000008380 degradant Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- XHQSLVIGPHXVAK-UHFFFAOYSA-K iron(3+);octadecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XHQSLVIGPHXVAK-UHFFFAOYSA-K 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 241000165940 Houjia Species 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 229940070765 laurate Drugs 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000272525 Anas platyrhynchos Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- WHRBSMVATPCWLU-UHFFFAOYSA-K iron(3+);triformate Chemical compound [Fe+3].[O-]C=O.[O-]C=O.[O-]C=O WHRBSMVATPCWLU-UHFFFAOYSA-K 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000021962 pH elevation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
This application provides a kind of bio-based ecology degradative plastic film and preparation method thereof, the ecological degradative plastic film is made by compound by extrusioning blowing process, and the compound includes：Hydrophobic modified starch, plastic resin, oxidative degradation additive, biodegradable auxiliary agent, heat stabilizer and filler；The mass ratio of the hydrophobic modified starch and plastic resin is (5~30)：(70~95)；The oxidative degradation additive is the 1~20% of plastic resin and hydrophobic modified starch gross mass, biodegradable auxiliary agent is the 1~20% of hydrophobic modified starch and plastic resin gross mass, the heat stabilizer is the 0.1~2% of plastic resin and hydrophobic modified starch gross mass, and the filler is the 0.1~2% of plastic resin and hydrophobic modified starch gross mass.Bio-based ecology degradative plastic film provided by the invention can be realized degradable, and it is relatively low to produce and process cost, is easily worked, easy to spread and application.
Description
Technical field
The present invention relates to ground technical field of membrane, more particularly to a kind of bio-based ecology degradative plastic film and preparation method thereof.
Background technology
Mulch film is covered ground film, and it has become one of important substance data of China's agricultural production.Covering with ground sheeting
It is a kind of agriculture cultivation technology, has Meteorological effect, diseases prevention pest-resistant and suppress the effect such as weeds.Current mulch film uses poly- second more
The plastics such as alkene (PE) or polyvinyl chloride (PVC) are made, very slow in the time of nature degraded because its stability is very high,
Take around 100 years or so.Common mulch film fragment is remained in soil and can not be not only decomposed by the microorganisms, nor can quilt
Crop is absorbed, and very big harm is caused to soil.
Therefore, carried out the research work of degradable ecological plastic film extensively both at home and abroad, wherein it is raw to research and develop more
Thing degradative plastic film.Biodegradable mulch be under field conditions (factors), by the vital movement of edaphon and degraded one
Class mulch film, the polymer-based mulch film of chemical synthesis, the major class of natural polymer base film two can be divided into.In terms of mechanism of degradation, biology drop
Solution mulch film can be divided into endless whole life cycle design and fully biodegradable mulch film again.Fully biodegradable mulch film finally divides
The inorganic matter such as Xie Chengshui and carbon dioxide, but this kind of mulch film processing difficulties, poor water resistance be present and processing cost is higher etc. asks
Topic, is difficult to Industry Promotion and application at present.
Wherein, starch base mulch film belongs to natural polymer subbase, one kind of endless whole life cycle design, starch base filled-type
Mulch film is typically to add starch and other additives in general-purpose plastics (PE, PVC etc.) to be made.From the angle for saving fossil resources
For, starch is reproducible biomass resource, and corresponding starch plasticses product is qualified green products, very big
Fossil resources can be saved in degree.Starch can realize degradable in natural environment, the drop of starch plasticses mulch film
What solution relied primarily on is the decomposition of starch ingredients, and plastic basis material can not degrade；However, starch can stay after decomposing on plastic basis material
Lower duck eye or the fragment that whole plastic basis material is become to difficult decomposition.These fragment materials do not have degradation property, and are difficult to reclaim, still
Soil environment is polluted, it is impossible to thoroughly solve " white pollution " problem.
The content of the invention
In view of this, the purpose of the application is to provide a kind of bio-based ecology degradative plastic film and preparation method thereof, this hair
The bio-based ecology degradative plastic film of bright offer can realize degradable, simple processing, easy to spread and application.
The present invention provides a kind of bio-based ecology degradative plastic film, is made by compound by extrusioning blowing process, described mixed
Closing material includes：Hydrophobic modified starch, plastic resin, oxidative degradation additive, biodegradable auxiliary agent, heat stabilizer and filler；
The mass ratio of the hydrophobic modified starch and plastic resin is (5~30)：(70~95)；The oxidative degradation addition
Agent is the 1~20% of plastic resin and hydrophobic modified starch gross mass, and the biodegradable auxiliary agent is hydrophobic modified starch and modeling
Expect the 1~20% of resin gross mass, the heat stabilizer is the 0.1~2% of plastic resin and hydrophobic modified starch gross mass, institute
State 0.1~2% that filler is plastic resin and hydrophobic modified starch gross mass.
Preferably, the plastic resin is selected from low density polyethylene (LDPE), high density polyethylene (HDPE), LLDPE, poly-
One or more in propylene and polyvinyl chloride.
Preferably, the hydrophobic modified starch is reacted by ative starch and modifying agent and is made, and the modifying agent is selected from metal fat
One or more in fat hydrochlorate, aliphatic acid and metal acid esters.
Preferably, one or more of the ative starch in cornstarch, farina and starch from sweet potato.
Preferably, the oxidative degradation additive is by including nano transition metal inorganic matter, transition metal salt and plastics base
The material of body is made；The biodegradable auxiliary agent be selected from 1,3- trimethylen-edinitrilo-tetraacetic acids, citric acid, lactic acid, butanedioic acid, fumaric acid,
One or more in malic acid, quininic acid and oxalic acid.
Preferably, one or more of the heat stabilizer in calcium stearate and magnesium stearate.
Preferably, one or more of the filler in calcium carbonate and talcum powder.
The present invention provides a kind of preparation method of bio-based ecology degradative plastic film, comprises the following steps：
A) plastic resin, oxidative degradation additive, biodegradable auxiliary agent, heat stabilizer and filler are mixed, Ran Houjia
Enter hydrophobic modified starch, obtain compound；The mass ratio of the hydrophobic modified starch and plastic resin is (5~30)：(70~
95)；The oxidative degradation additive is the 1~20% of plastic resin and hydrophobic modified starch gross mass, and the biodegradation helps
Agent is the 1~20% of plastic resin and hydrophobic modified starch gross mass, and the heat stabilizer is plastic resin and hydrophobic modified shallow lake
The 0.1~2% of powder gross mass, the filler are the 0.1~2% of plastic resin and hydrophobic modified starch gross mass；
B the compound) is subjected to extrusion-blown modling, obtains bio-based ecology degradative plastic film.
Preferably, the step A) in mixing temperature be 40~60 DEG C, mix 5~20min after add hydrophobic change
Property starch, continues 5~20min of mixing, obtains compound.
Preferably, the step B) in extrusion-blown modling temperature be 150~180 DEG C
Compared with prior art, under certain proportioning, bio-based ecology degradative plastic film provided by the invention is with hydrophobic modified
Starch is biological active degradation material, and plastic resin is matrix, auxiliary addition oxidative degradation additive, biodegradable auxiliary agent and
Heat stabilizer and filler etc..In the present invention, modified starch shows obvious hydrophobicity, can improve starch plasticity, with
And the compatibility between starch and matrix plastic.Starch on the one hand can be improved in plastic basis material by using hydrophobic modified starch
Dispersiveness, improve the processing characteristics of starch plasticses, reduce difficulty of processing；On the other hand it also ensure that the comprehensive of mulch film
Energy.The present invention adds a certain amount of oxidative degradation additive and biodegradable auxiliary agent in bio-based ecology degradative plastic film, makes modeling
Material body portion has had the double degradation characteristics of oxidative biological concurrently.In addition, by regulating and controlling oxidative degradation additive and biodegradable auxiliary agent
Adding proportion, the degradation speed of degradative plastic film can be controlled, realize the degradable of bio-based ecology degradative plastic film.Therefore,
Each component collective effect in compound of the present invention, the degradable of bio-based ecology degradative plastic film is realized, and produced and processed
Cost is relatively low, simple processing, easy to spread and application.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
The invention provides a kind of bio-based ecology degradative plastic film, is made by compound by extrusioning blowing process, described
Compound includes：Hydrophobic modified starch, plastic resin, oxidative degradation additive, biodegradable auxiliary agent, heat stabilizer and filling
Agent；The mass ratio of the hydrophobic modified starch and plastic resin is (5~30)：(70~95)；The oxidative degradation additive is
The 1~20% of plastic resin and hydrophobic modified starch gross mass, the biodegradable auxiliary agent are plastic resin and hydrophobic modified shallow lake
The 1~20% of powder gross mass, the heat stabilizer is the 0.1~2% of plastic resin and hydrophobic modified starch gross mass, described to fill out
Fill 0.1~2% that agent is plastic resin and hydrophobic modified starch gross mass.
Bio-based ecology degradative plastic film provided by the invention can realize it is degradable, it is environmentally safe；And produce and add
Work cost is relatively low, simple processing, the drawbacks of overcoming general complete biodegradable mulch film processed complex, cost height, be not easy to promote.
Bio-based ecology degradative plastic film provided by the invention, which uses, includes hydrophobic modified starch, plastic resin, oxidative degradation
Additive, biodegradable auxiliary agent, the compound of heat stabilizer and filler, are made by extrusioning blowing process.The plastic tree
Fat is generally belonged to originally in can not be preferably selected from low density polyethylene (LDPE) (LDPE), high density polyethylene (HDPE) by the parts of plastics of natural degradation
(HDPE), the one or more in LLDPE (LLDPE), polypropylene (PP) and polyvinyl chloride (PVC), more preferably
For the one or more in HDPE and LLDPE.The present invention is not particularly limited to the source of the plastic resin, can use city
Product, such as ldpe resin are sold, weight average molecular weight range is 50000~250000, melt index 0.5g/10min
~5g/10min.
Ecological plastic film of the present invention is using modified starch as bioactivity degradation material, the modified starch
With hydrophobicity, starch plasticity, and the compatibility between starch and matrix plastic can be improved, beneficial to the combination property of mulch film
Deng.That is, described compound includes hydrophobic modified starch；And the mass ratio of the hydrophobic modified starch and plastic resin for (5~
30)：(70~95).In an embodiment of the present invention, the addition of the hydrophobic modified starch be 5~30%, preferably 10~
20%；Plastic resin addition is 70~95%.Due to the wide material sources of starch, cost is relatively low, bio-based of the present invention
Ecological degradative plastic film has the significant advantage for reducing cost, improving biomass carbon content in mulch film.
The present invention is not particularly limited to the source of the hydrophobic modified starch, can use hydroxyl hydrogen substitution value >=30%
Or the starch commercially available prod of HLB value≤6.In a preferred embodiment of the invention, the hydrophobic modified starch by ative starch with
Modifying agent reaction is made；Wherein, the ative starch be preferably selected from one kind in cornstarch, farina and starch from sweet potato or
It is a variety of.In the present invention, the modifying agent may be selected from the one or more in metal fatty acid salt, aliphatic acid and metal acid esters.
Described metal fatty acid salt such as stearate, including the one or more in calcium stearate, zinc stearate and magnesium stearate, add
It can be 1~3% to add ratio；Metal esters of gallic acid include Aluminate and titanate esters in one or more, adding proportion can be 1~
3%；Aliphatic acid is preferably the one or more in stearic acid, oleic acid and laurate, and adding proportion can be 1~3%.It is of the invention real
Apply example preferably while add three kinds of different types of modifying agent, processing is modified to ative starch；Reaction in the processing procedure
At a temperature of condition can be 120~190 DEG C, 15~50min is mixed, obtains above-mentioned hydrophobic modified starch；Pass through the work
Hydrophobic modified starch prepared by skill, its surface hydroxyl hydrogen substitution value >=30%.
The compound that the present invention prepares bio-based mulch film includes oxidative degradation additive and biodegradable auxiliary agent；Institute of the present invention
The oxidative degradation of meaning is to make the molecular weight of common plasticses such as polyolefin by oxidative degradation in the environmental conditions such as light, heat or oxygen
It is reduced to less than 10,000；The biodegradable auxiliary agent is the polymer segment for promoting to have occurred the small-molecular-weight of oxidative degradation, micro-
Biological utilisation is simultaneously progressively carried out biodegradable.The embodiment of the present invention adds receiving for different proportion in bio-based ecology degradative plastic film
Meter level oxidative degradation additive, by the effect of light, heat in nature, by plastic basis materials such as the polyethylene of macromolecule in mulch film
Small-molecular-weight plastics are degraded to, under the facilitation of biodegradable auxiliary agent, are by microbial degradation common in soil
Water, carbon dioxide and humus to environment non-secondary pollution, fundamentally solve bio-based plastics mulch film product by crop utilization
Can not be degradable the problem of.
In the present invention, the addition of the oxidative degradation additive and biodegradable auxiliary agent is plastic resin and hydrophobic
The 1~20% of modified starch gross mass, preferably 5~20%；As addition is excessive, then mulch film processing and its comprehensive is influenceed
Energy.In an embodiment of the present invention, the oxidative degradation additive by including nano transition metal inorganic matter, transition metal salt and
The material of plastic substrate is made.The biodegradable auxiliary agent may include 1,3- trimethylen-edinitrilo-tetraacetic acids (PDTA), citric acid, lactic acid,
One or more in amber furmaric acid, malic acid, quininic acid, oxalic acid.Oxidative degradation additive and biodegradable auxiliary agent are total to
With double degradant additives that come from different backgrounds and possess different abilities, the embodiment of the present invention blends a small amount of this additive, energy in bio-based ecology degradative plastic film
Obtain more preferable degradation effect.
In an embodiment of the present invention, the oxidative degradation additive includes nano transition metal inorganic matter, and it is ultraviolet
Photocatalytic degradation composition, particle diameter can be between 5nm~900nm.The nano transition metal inorganic matter preferably is selected from a nanometer mistake
Cross metal oxide or nano transition metal sulfide, more preferably nano-TiO2, nano-ZnO, nanometer ZnS, nano-tube/CdS and receive
The mixture or compound (such as Ti of a kind of inorganic matter or a variety of formation in rice PbSxZnyO2x+y, x, y and 2x+y therein are original
Sub- ratio), most preferably nano-TiO2.The oxidative degradation additive preferably includes 0.1wt%~10wt% nano transition gold
Belong to inorganic matter, the nano transition metal inorganic matter more preferably including 1wt%~8wt%.
The oxidative degradation additive may include transition metal salt, and it is visible light catalytic oxidation degraded and heat catalytic oxidation
Degraded composition.Transition metal in the transition metal salt preferably is selected from cobalt, iron, vanadium, manganese, cerium or zinc；That is, described transition metal salt
Water-soluble organic acid salt or inorganic acid salt including iron, cobalt, vanadium, manganese, cerium, zinc etc..In an embodiment of the present invention, the transition
Metal salt may be selected from formates, acetate, nitrate, sulfate, hydrochloride or the acetylacetone,2,4-pentanedione of iron, cobalt, vanadium, manganese, cerium or zinc
Salt, such as ferric formate, ferric acetate, ferric nitrate, cobalt nitrate, ferric sulfate, the ammonium iron of sulfuric acid two, ferric acetyl acetonade, iron chloride.The oxygen
Change the transition metal salt that degradant additive preferably includes 1wt%~10wt%, the transition gold more preferably including 3wt%~8wt%
Belong to salt.
The oxidative degradation additive includes the plastic substrate of surplus, preferably is selected from polyolefin, polyaniline or polyester, more preferably
For polyethylene, polypropylene, polystyrene, polyvinyl chloride, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene (ABS) tree
One or more in fat, PET and polybutylene terephthalate, most preferably polyethylene, poly- third
Alkene, polystyrene or polyvinyl chloride.Present invention preferably employs the oxidative degradation additive containing polyolefin, itself and film material
Compatibility is more preferable, beneficial to application.The present invention is not particularly limited to source of the plastic substrate etc., is using commercially available prod
Can.
The embodiment of the present invention can mix above-mentioned nano transition metal inorganic matter, transition metal salt and plastic substrate, through squeezing
Go out to be granulated, obtain oxidative degradation additive.Wherein, the mixing is carried out preferably in homogenizer, and the time of stirring is general
For 1 minute~3 minutes.The embodiment of the present invention can use dual-screw pelletizer group to carry out extruding pelletization；The temperature of each extrusion section
Generally 50 DEG C~250 DEG C, extrusion revolution can be 25 revs/min~450 revs/min.
The present invention is not particularly limited to the source of the oxidative degradation additive, can use commercially available prod；The present invention
Embodiment can use model EBP-1205, EBP-1204 and EBP-1203 of Shandong Ecology Benign Plastics Technology Co., Ltd. oxygen
Change the one or more in degradant additive.Specifically, oxidative degradation additive EBP-1203 specific composition and mass fraction
Accounting is：Linear low density polyethylene resin 90%, nano-TiO23%th, nano-ZnO 3%, cobalt nitrate 4%；Oxidative degradation adds
Specific composition and the mass fraction accounting for adding agent EBP-1204 is：Linear low density polyethylene resin 91%, nano-TiO24%th,
Cobalt decanoate 5%；Oxidative degradation additive EBP-1205 specific composition and mass fraction accounting is：LLDPE tree
Fat 90%, nano-TiO22%th, cobalt decanoate 4%, ferric stearate 4%.
The biodegradable auxiliary agent may include multicomponent organic acid, and it is to help biodegradable composition.The multicomponent organic acid is excellent
Elect the one or more in 1,3- trimethylen-edinitrilo-tetraacetic acids (PDTA), tartaric acid, fumaric acid, malic acid and citric acid as, more preferably
For citric acid.The present invention is not particularly limited to the source of the multicomponent organic acid etc., using commercially available prod.
Except oxidative degradation additive and biodegradable auxiliary agent, the mixing of bio-based ecology degradative plastic film provided by the invention
Material includes other additives such as heat stabilizer and filler.The heat stabilizer is preferably selected from calcium stearate and magnesium stearate
It is one or more；The filler is preferably selected from the one or more in calcium carbonate and talcum powder.The heat stabilizer is plastics
The 0.1~2% of resin and hydrophobic modified starch gross mass, preferably 0.5~1.5%；The filler is plastic resin and hated
The 0.1~2% of water modified starch gross mass, preferably 0.5~1.5%.
Correspondingly, the invention provides a kind of preparation method of bio-based ecology degradative plastic film, including：
A) plastic resin, oxidative degradation additive, biodegradable auxiliary agent, heat stabilizer and filler are mixed, Ran Houjia
Enter hydrophobic modified starch, obtain compound；The mass ratio of the hydrophobic modified starch and plastic resin is (5~30)：(70~
95)；The oxidative degradation additive is the 1~20% of plastic resin and hydrophobic modified starch gross mass, and the biodegradation helps
Agent is the 1~20% of plastic resin and hydrophobic modified starch gross mass, and the heat stabilizer is plastic resin and hydrophobic modified shallow lake
The 0.1~2% of powder gross mass, the filler are the 0.1~2% of plastic resin and hydrophobic modified starch gross mass；
B the compound) is subjected to extrusion-blown modling, obtains bio-based ecology degradative plastic film.
In the present invention, described plastic resin, oxidative degradation additive, biodegradable auxiliary agent, heat stabilizer and filling
Agent, and the content of the raw material such as hydrophobic modified starch are consistent with previously described content, will not be repeated here.The embodiment of the present invention
First to ative starch modification to prepare hydrophobic modified starch, specifically, ative starch solid powder is thrown together with modifying agent
It is put in homogenizer, stirring, reaction, obtains hydrophobic modified starch.Wherein, the modifying agent may be selected from fatty acid metal
One or more in salt, aliphatic acid and metal acid esters, specific species and reaction condition etc. are also consistent with previously described content,
Do not repeating one by one herein.Modified starch shows obvious hydrophobicity, can improve starch plasticity and starch and high score
Compatibility between sub- polymer.
The embodiment of the present invention adds plastic resin, oxidative degradation additive, biodegradable auxiliary agent, heat stabilizer, filler
Enter in homogenizer, preferably under conditions of temperature is 40~60 DEG C, mix 5min~20min.After well mixed, then
Add hydrophobic modified starch to continue to mix, after 5min~20min, you can obtain compound.
Above-mentioned compound is added in the hopper of inflation film manufacturing machine by the embodiment of the present invention, and the temperature for preferably controlling blown film group is
150~180 DEG C, by extrusioning blowing process, bio-based ecology degradative plastic film is prepared.Wherein, inflation film manufacturing machine can specifically be set
The temperature of five bringing-up sections is respectively 150 DEG C, 160 DEG C, 175 DEG C, 175 DEG C, 180 DEG C, extruded to be blow molded into uniform films bucket.With
Afterwards, by the traction, segmentation, winding of routine, bio-based ecology degradative plastic film product is obtained.
After bio-based ecology degradative plastic film is made, the present invention carries out performance test to it.The mulch film product transparency >=
80%, thickness range is 4~20 μm；Tensile strength is generally 10MPa~18MPa, and elongation at break is 100%~360%.Should
Mulch film product performance is excellent, disclosure satisfy that mulch film use environment and life requirements, and induction period of degrading is controllable, is adapted to
Crop uses from different places more.According to the difference for applying area and crop, hydrophobic modified starch and oxidative degradation addition are adjusted
Agent, the adding proportion of biodegradable auxiliary agent, realize the control to degradation time.Pass through 60~180 days under the coverage condition of crop field
Time, start degradation process, tensile strength, elongation at break decline rapidly；Under farm environment, after 180~360 days, reach
To degradable, remained in soil without visible plastics.After bio-based ecology degradative plastic film of the present invention reaches its service life
It is degradable, avoid and environment is polluted, solve the problems, such as that traditional starch filled-type mulch film can not be degradable.
Bio-based ecology degradative plastic film of the present invention carries due to the addition of modified starch as bioactivity degradation material
The high biomass carbon content of mulch film.Modified starch also add the compatibility between plastic resin, effectively reduce
Mulch film Product processing cost.In addition, the bio-based ecology degradative plastic film can play insulation soil moisture conservation effect well, improve soil
Earth physicochemical property.Mulch film is degraded in good time after the envelope departure date, promotes soil microbial activity, prevents flood, alleviates soil salt
Alkalinization.Culture underglass is carried out using bio-based ecology degradative plastic film of the present invention, improves ecological environment of soil, simultaneously
The quality and economic benefit of crop are also improved.
For a further understanding of the present invention, with reference to embodiment to bio-based ecology degradative plastic film provided by the invention and
Its preparation method is specifically described.
Embodiment 1
(1) prepared by modified starch：According to quality proportioning, by 93% cornstarch (Jinan Hong Xu Chemical Co., Ltd.s, food
Level, water content≤14%), 3% calcium stearate, 3% butyl titanate and 1% oleic acid add in homogenizer, at 130 DEG C
15min is mixed, obtains hydrophobic modified cornstarch, substitution value 33%.
(2) batch mixing：By linear low density polyethylene resin (LLDPE, Qilu Petrochemical 7042) of the mass fraction for 45%, matter
Measure the high-density polyethylene resin (HDPE, Qilu Petrochemical 6098) and oxidative degradation additive EBP-1203 (mountains that fraction is 45%
Dong Tianzhuan Environmental Protection Technology Co., Ltd), citric acid (Rizhao Jinhe Biochemistry Group Co., Ltd.) add homogenizer in, 40
Calcium stearate (Lu Chuan Chemical Co., Ltd.s of Zibo City, top grade product, 200 mesh) and talcum powder are added after 5min is mixed at DEG C
(upper SeaBird space Chemical Co., Ltd., 400 mesh), and 10% hydrophobic modified cornstarch stirring 5min, obtain compound.Its
In, it is 5% that oxidative degradation additive, the quality of biodegradable auxiliary agent, which account for plastic basis material and modified starch gross mass, stearic acid
Calcium and talcum powder account for 1%, 1% respectively.Oxidative degradation additive EBP-1203 specific composition and mass fraction accounting is：Linearly
Ldpe resin 90% (Qilu Petrochemical 7042), nano-TiO23% (Xuancheng Jingrui New Material Co., Ltd.), nanometer
ZnO 3% (Shandong Bo Ao Industrial Co., Ltd.s) cobalt nitrate 4% (Nanjing Xi Nuo Chemical Industry Science Co., Ltd).
(3) blown film：(Dongfeng, Plastic Machinery Factroy, Zhejiang SJ-50 type high-low pressures blow in above-mentioned compound importing inflation film manufacturing machine hopper
Film unit), the temperature of setting five bringing-up sections of inflation film manufacturing machine is respectively 150 DEG C, 160 DEG C, 175 DEG C, 175 DEG C, 180 DEG C, extruded
It is blow molded into uniform films bucket.Through drawing, splitting, winding after, bio-based ecology degradative plastic film is obtained.
Method as described above, the bio-based ecology degradative plastic film of preparation is subjected to performance test.In farmland cover strip
Under part, by 90 day time, mulch film sample was degraded, and mechanical strength declines, and tensile strength is dropped to by 16.5MPa
10.3MPa.By 240 days, mulch film was degradable, was retained in agricultural land soil without visible plastics.
Embodiment 2
(1) prepared by modified starch：According to quality proportioning, by 94% farina (Jinan Qing An Chemical Co., Ltd.s, food
Grade, moisture content≤18%), 2% ferric stearate, 1% butyl titanate and 3% stearic acid add in homogenizer, in 120
30min is mixed at DEG C, obtains hydrophobic modified farina, substitution value 31%.
(2) batch mixing：By mass fraction be 85% linear low density polyethylene resin (LLDPE, Qilu Petrochemical 7042) and
(Henan Wan-hai chemical products are limited for oxidative degradation additive EBP-1204 (Shandong Ecology Benign Plastics Technology Co., Ltd.), malic acid
Company) add in homogenizer, (Zibo City Shandong river chemical industry is limited for addition magnesium stearate after 10min is mixed at 60 DEG C
Company, top grade product, 200 mesh) and calcium carbonate (Lu Chuan Chemical Co., Ltd.s of Zibo City, top grade product, 200 mesh), and 15% hydrophobic
Modified potato starch stirs 5min, obtains compound.Wherein, oxidative degradation additive, the quality of biodegradable auxiliary agent account for
Plastic basis material and modified starch gross mass are 20%, and magnesium stearate and calcium carbonate account for 0.5%, 1% respectively.Oxidative degradation additive
EBP-1204 specific composition and mass fraction accounting is：Linear low density polyethylene resin 91% (Qilu Petrochemical 7042), receive
Rice TiO24% (Xuancheng Jingrui New Material Co., Ltd.), cobalt decanoate 5% (Zichuan Lu Tai Chemical Co., Ltd.s).
(3) blown film：(Dongfeng, Plastic Machinery Factroy, Zhejiang SJ-50 type high-low pressures blow in above-mentioned compound importing inflation film manufacturing machine hopper
Film unit), the temperature of setting five bringing-up sections of inflation film manufacturing machine is respectively 155 DEG C, 160 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, extruded
It is blow molded into uniform films bucket.Through drawing, splitting, winding after, bio-based ecology degradative plastic film is obtained.
Method as described above, the bio-based ecology degradative plastic film of preparation is subjected to performance test.In farmland cover strip
Under part, by 110 days, mulch film sample was degraded, and mechanical strength declines, and tensile strength drops to 3.3MPa by 12.5MPa.
By 270 days, mulch film was degradable, was retained in agricultural land soil without visible plastics.
Embodiment 3
(1) prepared by modified starch：According to quality proportioning, by 93% starch from sweet potato (Shandong Liangshan red sun starch-based product factory,
Food-grade, water content≤10%), 1% zinc stearate, 3% butyl titanate and 3% laurate add in homogenizer, in
25min is mixed at 160 DEG C, obtains hydrophobic modified starch from sweet potato, substitution value 35%.
(2) batch mixing：By mass fraction be 80% linear low density polyethylene resin (LLDPE, Qilu Petrochemical 7042) and
(sunshine gold standing grain biochemistry group is limited for oxidative degradation additive EBP-1205 (Shandong Ecology Benign Plastics Technology Co., Ltd.), citric acid
Company) add in homogenizer, calcium stearate and calcium carbonate are added after 10min is mixed at 45 DEG C, and 20% hates
Water modified sweet potato starch stirs 5min, obtains compound.Wherein, oxidative degradation additive, the quality of biodegradable auxiliary agent account for
Plastic basis material and modified starch gross mass are 20%, and calcium stearate and talcum powder account for 1%, 0.5% respectively.Oxidative degradation additive
EBP-1205 specific composition and mass fraction accounting is：Linear low density polyethylene resin 90% (Qilu Petrochemical 7042), receive
Rice TiO22% (Xuancheng Jingrui New Material Co., Ltd.), cobalt decanoate 4% (Zichuan Lu Tai Chemical Co., Ltd.s), ferric stearate
4% (Guangdong Weng Jiang chemical reagent Co., Ltd).
(3) blown film：(Dongfeng, Plastic Machinery Factroy, Zhejiang SJ-50 type high-low pressures blow in above-mentioned compound importing inflation film manufacturing machine hopper
Film unit), the temperature of setting five bringing-up sections of inflation film manufacturing machine is respectively 150 DEG C, 160 DEG C, 175 DEG C, 175 DEG C, 180 DEG C, extruded
It is blow molded into uniform films bucket.Through drawing, splitting, winding after, bio-based ecology degradative plastic film is obtained.
Method as described above, the bio-based ecology degradative plastic film of preparation is subjected to performance test.Bar is laid in crop field
Under part, by 100 days, mulch film sample was degraded, and mechanical strength declines, and tensile strength drops to 4.2MPa by 13.3MPa.
By 230 days, mulch film was degradable, was remained in agricultural land soil without plastic sheeting.
Comparative example 1
(1) batch mixing：By mass fraction be 90% linear low density polyethylene resin (LLDPE, Qilu Petrochemical 7042) and
5% oxidative degradation additive EBP-1204 (Shandong Ecology Benign Plastics Technology Co., Ltd.), 5% citric acid (the biochemical collection of sunshine gold standing grain
Co., Ltd of group) add in homogenizer, 10min is mixed at 50 DEG C, obtains compound.
(2) blown film：(Dongfeng, Plastic Machinery Factroy, Zhejiang SJ-50 type high-low pressures blow in above-mentioned compound importing inflation film manufacturing machine hopper
Film unit), the temperature of setting five bringing-up sections of inflation film manufacturing machine is respectively 155 DEG C, 160 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, extruded
It is blow molded into uniform films bucket.Through drawing, splitting, winding after, degradative plastic film is obtained.
Method as described above, the degradative plastic film of preparation is subjected to performance test.Under the construction conditions of crop field, pass through
120 days, mulch film sample was degraded, and mechanical strength declines, and tensile strength drops to 3.6MPa by 14MPa.During by 280 days
Between, mulch film is degradable, is remained in agricultural land soil without plastic sheeting.
Comparative example 2
(1) batch mixing：By mass fraction be 85% linear low density polyethylene resin (LLDPE, Qilu Petrochemical 7042) and
15% native cornstarch, and calcium stearate and talcum powder are added in homogenizer, are mixed 10min at 50 DEG C, are obtained
To compound.Wherein, calcium stearate and talcum powder account for 1%, the 0.5% of plastic basis material and starch gross mass respectively.
(2) blown film：(Dongfeng, Plastic Machinery Factroy, Zhejiang SJ-50 type high-low pressures blow in above-mentioned compound importing inflation film manufacturing machine hopper
Film unit), the temperature of setting five bringing-up sections of inflation film manufacturing machine is respectively 155 DEG C, 160 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, compound
After plasticizing is extruded, expanding, occurring a large amount of cuts in distraction procedure, causing blown film not complete.
Comparative example 3
(1) batch mixing：By mass fraction be 90% linear low density polyethylene resin (LLDPE, Qilu Petrochemical 7042) and
(sunshine gold standing grain biochemistry group is limited for oxidative degradation additive EBP-1204 (Shandong Ecology Benign Plastics Technology Co., Ltd.), citric acid
Company) add in homogenizer, add calcium stearate (the limited public affairs of Zibo City Shandong river chemical industry after 5min is mixed at 50 DEG C
Department, top grade product, 200 mesh) and talcum powder (upper SeaBird space Chemical Co., Ltd., 400 mesh), and 10% former cornstarch, stirring
5min, obtain compound.Wherein, oxidative degradation additive, the quality of biodegradable auxiliary agent account for plastic basis material and former corn forms sediment
Powder gross mass is 5%, and calcium stearate and talcum powder account for 1%, 1% respectively.
(3) blown film：(Dongfeng, Plastic Machinery Factroy, Zhejiang SJ-50 type high-low pressures blow in above-mentioned compound importing inflation film manufacturing machine hopper
Film unit), the temperature of setting five bringing-up sections of inflation film manufacturing machine is respectively 150 DEG C, 160 DEG C, 175 DEG C, 175 DEG C, 180 DEG C, compound
After plasticizing is extruded, expanding, occurring a large amount of cuts in distraction procedure, causing blown film not complete.
Comparative example 4
(1) batch mixing：By mass fraction be 85% linear low density polyethylene resin (LLDPE, Qilu Petrochemical 7042) and
15% modified corn starch (is made) in embodiment 1, and calcium stearate and talcum powder are added in homogenizer, at 50 DEG C
10min is mixed, obtains compound.Wherein, calcium stearate and talcum powder account for plastic basis material and starch gross mass respectively
1%th, 0.5%.
(2) blown film：(Dongfeng, Plastic Machinery Factroy, Zhejiang SJ-50 type high-low pressures blow in above-mentioned compound importing inflation film manufacturing machine hopper
Film unit), the temperature of setting five bringing-up sections of inflation film manufacturing machine is respectively 155 DEG C, 160 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, extruded
It is blow molded into uniform films bucket.Through drawing, splitting, winding after, starch-based degrading mulch film is obtained.
Method as described above, the starch-based degrading mulch film of preparation is subjected to performance test.Under the construction conditions of crop field,
By 90 days, mulch film sample occurred damaged, and a large amount of mulch film relics are remained in soil, and molecule measuring is taken temperature its bright polyethylene
Do not occur effectively to degrade, weight average molecular weight reduces unobvious.
Comparative example 5
(1) batch mixing：By mass fraction be 85% linear low density polyethylene resin (LLDPE, Qilu Petrochemical 7042) and
15% modified corn starch (is made) in embodiment 1, mixes 10min at 50 DEG C, obtains compound.
(2) blown film：(Dongfeng, Plastic Machinery Factroy, Zhejiang SJ-50 type high-low pressures blow in above-mentioned compound importing inflation film manufacturing machine hopper
Film unit), the temperature of setting five bringing-up sections of inflation film manufacturing machine is respectively 155 DEG C, 160 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, extruded
It is blow molded into uniform films bucket.Through drawing, splitting, winding after, starch-based degrading mulch film is obtained.
Method as described above, the starch-based degrading mulch film of preparation is subjected to performance test.Under the construction conditions of crop field,
By 90 day time, mulch film sample occurred damaged, and a large amount of mulch film relics are remained in soil, and molecule measuring is taken temperature its bright polyethylene
Composition does not occur effectively to degrade, and weight average molecular weight reduces unobvious.
Comparative example 6
(1) mass fraction is dropped for 85% linear low density polyethylene resin (LLDPE, Qilu Petrochemical 7042) and oxidation
Solve additive EBP-1204 (Shandong Ecology Benign Plastics Technology Co., Ltd.) to add in homogenizer, mixed at 60 DEG C
Magnesium stearate and calcium carbonate are added after 10min, and stirring 5min (is made) in 15% hydrophobic modified cornstarch in embodiment 1,
Obtain compound.Wherein, oxidative degradation catalyst accounts for the 5% of plastic basis material and modified starch gross mass, magnesium stearate and carbonic acid
Calcium accounts for 0.5%, 1% respectively.
(2) blown film：(Dongfeng, Plastic Machinery Factroy, Zhejiang SJ-50 type high-low pressures blow in above-mentioned compound importing inflation film manufacturing machine hopper
Film unit), the temperature of setting five bringing-up sections of inflation film manufacturing machine is respectively 155 DEG C, 160 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, extruded
It is blow molded into uniform films bucket.Through drawing, splitting, winding after, mulch film is obtained.
Method as described above, the mulch film of preparation is subjected to performance test.Under the coverage condition of farmland, during by 90 days
Mulch film sample is degraded, and mechanical strength declines, and tensile strength drops to 11.2MPa by 16MPa.By 240 days, mulch film tried
It is powder that sample is degradable, and molecule measuring bright weight average molecular weight of taking temperature is reduced to less than 10,000, and explanatorily effective life does not occur for membrane sample
Thing is degraded.
Comparative example 7
(1) by mass fraction be 85% linear low density polyethylene resin (LLDPE, Qilu Petrochemical 7042) and malic acid
(chemical products Co., Ltd of Henan Wan-hai) is added in homogenizer, and stearic acid is added after mixing 10min at 60 DEG C
Stirring 5min (is made) in magnesium and calcium carbonate, and 15% hydrophobic modified cornstarch in embodiment 1, obtain compound.Wherein, lemon
Lemon acid accounts for the 5% of plastic basis material and modified starch gross mass, and magnesium stearate and calcium carbonate account for 0.5%, 1% respectively.
(2) blown film：(Dongfeng, Plastic Machinery Factroy, Zhejiang SJ-50 type high-low pressures blow in above-mentioned compound importing inflation film manufacturing machine hopper
Film unit), the temperature of setting five bringing-up sections of inflation film manufacturing machine is respectively 155 DEG C, 160 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, extruded
It is blow molded into uniform films bucket.Through drawing, splitting, winding after, mulch film is obtained.
Method as described above, the mulch film of preparation is subjected to performance test.Under the construction conditions of crop field, during by 90 days
Between, mulch film sample occurs damaged, and a large amount of mulch film relics are remained in soil, and molecule measuring its bright polyethylene of taking temperature does not occur
Effectively degraded, weight average molecular weight reduce unobvious.
From the comparative analysis of comparative example 1 and each embodiment, using polyvinyl resin and oxidative degradation additive and life
Thing prodegradant blending production degradable mulch, can also reach good degradation effect, and modified starch in each embodiment
Addition, can reduce the dosage of polyethylene, modified starch price is significantly lower than polyethylene, therefore can significantly reduce cost.
From the comparative analysis of comparative example 2, comparative example 3 and each embodiment, the ative starch using non-modified processing enters
The production of row degradable mulch, due to poor compatibility between ative starch and plastic basis material, blown film is caused to fail.
Contrast between comparative example 4, comparative example 5 and each embodiment shows, does not add oxidative degradation addition in polyethylene base material
Agent and biodegradable auxiliary agent, in the case of only adding modified starch, breakage occurs simultaneously after certain time is laid in crop field in mulch film
A large amount of film fragments are remained in agricultural land soil.Detection shows that the film fragments of residual are polyethylene, and weight average molecular weight reduces
Unobvious, show not occur effectively to degrade.
The comparative analysis of comparative example 6,7 and each embodiment is understood, only with oxidative degradation additive or biodegradable auxiliary agent
In the case of adding modified starch after polyethylene blend, mulch film can not be realized degradable after the laying certain time of crop field.
As seen from the above embodiment, the present invention uses hydrophobic modified starch, can improve starch plasticity and starch and base
Compatibility between body plastics, the biomass carbon content of bio-based ecology degradative plastic film is not only increased, effectively reduce production and add
Work cost, and also ensure that the combination property of mulch film.In addition, by regulating and controlling oxidative degradation additive and biodegradable auxiliary agent
Adding proportion, the degradation speed of degradative plastic film can be controlled, realize the controlled degradation of bio-based ecology degradative plastic film.The present invention
Each component collective effect in compound, realize the degradable of bio-based ecology degradative plastic film, and produce and process cost compared with
It is low, simple processing, easy to spread and application.
Claims (10)
1. a kind of bio-based ecology degradative plastic film, it is made by compound by extrusioning blowing process, the compound includes：Hydrophobic
Modified starch, plastic resin, oxidative degradation additive, biodegradable auxiliary agent, heat stabilizer and filler；
The mass ratio of the hydrophobic modified starch and plastic resin is (5~30)：(70~95)；The oxidative degradation additive is
The 1~20% of plastic resin and hydrophobic modified starch gross mass, the biodegradable auxiliary agent are hydrophobic modified starch and plastic tree
The 1~20% of fat gross mass, the heat stabilizer is the 0.1~2% of plastic resin and hydrophobic modified starch gross mass, described to fill out
Fill 0.1~2% that agent is plastic resin and hydrophobic modified starch gross mass.
2. bio-based ecology degradative plastic film according to claim 1, it is characterised in that the plastic resin is selected from low-density
One or more in polyethylene, high density polyethylene (HDPE), LLDPE, polypropylene and polyvinyl chloride.
3. bio-based ecology degradative plastic film according to claim 1, it is characterised in that the hydrophobic modified starch is formed sediment by original
Powder is made with modifying agent reaction, one or more of the modifying agent in metal fatty acid salt, aliphatic acid and metal acid esters.
4. bio-based ecology degradative plastic film according to claim 3, it is characterised in that the ative starch forms sediment selected from corn
One or more in powder, farina and starch from sweet potato.
5. bio-based ecology degradative plastic film according to claim 1, it is characterised in that the oxidative degradation additive is by wrapping
The material for including nano transition metal inorganic matter, transition metal salt and plastic substrate is made；The biodegradable auxiliary agent is selected from 1,3-
One or more in trimethylen-edinitrilo-tetraacetic acid, citric acid, lactic acid, butanedioic acid, fumaric acid, malic acid, quininic acid and oxalic acid.
6. bio-based ecology degradative plastic film according to claim 1, it is characterised in that the heat stabilizer is selected from stearic acid
One or more in calcium and magnesium stearate.
7. bio-based ecology degradative plastic film according to claim 1, it is characterised in that the filler be selected from calcium carbonate and
One or more in talcum powder.
8. a kind of preparation method of bio-based ecology degradative plastic film, comprises the following steps：
A) plastic resin, oxidative degradation additive, biodegradable auxiliary agent, heat stabilizer and filler are mixed, then adds and hates
Water modified starch, obtains compound；The mass ratio of the hydrophobic modified starch and plastic resin is (5~30)：(70~95)；Institute
1~20% that oxidative degradation additive is plastic resin and hydrophobic modified starch gross mass is stated, the biodegradable auxiliary agent is modeling
Expect the 1~20% of resin and hydrophobic modified starch gross mass, the heat stabilizer is plastic resin and the total matter of hydrophobic modified starch
The 0.1~2% of amount, the filler are the 0.1~2% of plastic resin and hydrophobic modified starch gross mass；
B the compound) is subjected to extrusion-blown modling, obtains bio-based ecology degradative plastic film.
9. preparation method according to claim 8, it is characterised in that the step A) in mixing temperature be 40~60
DEG C, hydrophobic modified starch is added after mixing 5~20min, continues 5~20min of mixing, obtains compound.
10. preparation method according to claim 8, it is characterised in that the step B) in extrusion-blown modling temperature be 150
~180 DEG C.
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| CN110204792A (en) * | 2019-04-24 | 2019-09-06 | 天津科技大学 | A kind of preparation method of monascorubin edible film against sunshine |
| CN112708183A (en) * | 2020-12-25 | 2021-04-27 | 易宝（福建）高分子材料股份公司 | Easily-degradable light high-strength PE + EPP mixed foaming material and preparation method thereof |
| CN113754938A (en) * | 2021-08-31 | 2021-12-07 | 安徽乐朗环保新材料有限公司 | Fully-degradable plastic film and preparation method thereof |
| CN114539634A (en) * | 2022-02-08 | 2022-05-27 | 龙群科技(云南)有限公司 | Degradable environment-friendly plastic and preparation method thereof |
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