CN103319865B - Polylactic acid alloy film and application - Google Patents
Polylactic acid alloy film and application Download PDFInfo
- Publication number
- CN103319865B CN103319865B CN201310228789.1A CN201310228789A CN103319865B CN 103319865 B CN103319865 B CN 103319865B CN 201310228789 A CN201310228789 A CN 201310228789A CN 103319865 B CN103319865 B CN 103319865B
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- polylactic acid
- polylactic
- alloy film
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 33
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 28
- 239000000956 alloy Substances 0.000 title claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 25
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 31
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 19
- -1 polyoxyethylene Polymers 0.000 claims description 41
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 38
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 235000011187 glycerol Nutrition 0.000 claims description 12
- 229920003023 plastic Polymers 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 238000006136 alcoholysis reaction Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 102220043159 rs587780996 Human genes 0.000 claims description 4
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 claims description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 46
- 238000000034 method Methods 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 230000004888 barrier function Effects 0.000 abstract description 10
- 239000010409 thin film Substances 0.000 abstract description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 25
- 238000001125 extrusion Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 8
- 239000004902 Softening Agent Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 229940126680 traditional chinese medicines Drugs 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 229920006381 polylactic acid film Polymers 0.000 description 5
- 238000003856 thermoforming Methods 0.000 description 5
- 229920001634 Copolyester Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000007766 curtain coating Methods 0.000 description 3
- 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 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 6-tert-butyl-m-cresol Natural products CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 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
- 239000007789 gas Substances 0.000 description 2
- 125000005908 glyceryl ester group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- CHJJYTIOLUWORE-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl dihydrogen phosphate Chemical compound CC(C)(C)C1=CC(COP(O)(O)=O)=CC(C(C)(C)C)=C1O CHJJYTIOLUWORE-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- QQGRFMIMXPWKPM-UHFFFAOYSA-N 2,3,4-tributylphenol Chemical compound CCCCC1=CC=C(O)C(CCCC)=C1CCCC QQGRFMIMXPWKPM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- IFTGSFOYLIXWNR-UHFFFAOYSA-N C(CC)(=O)NN.C(C)(C)(C)CC(C(=O)O)(C1=CC=CC(=C1)C(C)(C)C)O Chemical compound C(CC)(=O)NN.C(C)(C)(C)CC(C(=O)O)(C1=CC=CC(=C1)C(C)(C)C)O IFTGSFOYLIXWNR-UHFFFAOYSA-N 0.000 description 1
- GRQZNHCKCPQIPL-UHFFFAOYSA-N CCC(CO)(CO)CO.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O Chemical compound CCC(CO)(CO)CO.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O GRQZNHCKCPQIPL-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000432 Polylactide-block-poly(ethylene glycol)-block-polylactide Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- TYFQFVWCELRYAO-UHFFFAOYSA-L suberate(2-) Chemical compound [O-]C(=O)CCCCCCC([O-])=O TYFQFVWCELRYAO-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a kind of polylactic acid alloy film, it comprises polylactic resin, polyvinyl alcohol resin and expanding material, is 100 parts by weight with the total amount of polylactic resin and polyvinyl alcohol resin, and three's weight content is 1 ~ 99 part, 1 ~ 99 part and 0.05-5 part.Polylactic acid alloy film of the present invention, by under the prerequisite of complete biodegradable and high strength, can effectively improve the oxygen barrier property of polylactic acid alloy film keeping thin-film material.Present invention process method is simple, with low cost, effectively can promote the widespread use of environment-friendly type polylactic acid article.
Description
Technical field
The present invention relates to a kind of polylactic acid film, particularly relate to a kind of biodegradable, polylactic acid alloy film with barrier properties for gases.
Background technology
Petroleum-based plastics goods, especially the widespread use of Plastic Packaging Materials brings a large amount of facility to human lives, but the raw material of common plastics as materials such as polyethylene, polypropylene, polyethylene terephthalates is mainly derived from oil, along with the scarcity day by day of petroleum resources, the raw material sources of conventional alkylene macromolecular material will face huge challenge.In addition, the process after the application of petroleum base macromolecular material is also a very large difficult problem, especially a Plastic Packaging Materials, because its application cycle is shorter, and large usage quantity, the pollution brought to environment is more serious.In prior art, plastic refuse is mainly through burning or burying and process, and burning can discharge by product poisonous in a large number, and plastics bury after due to the stable chemical-biological character of plastics, decompose hardly and residually cause land wastage in a large number.Therefore, the full-biodegradable material developing non-petroleum base is very important.
Wherein, poly(lactic acid) receives much attention with its good physical strength and biodegradability.The raw material of poly(lactic acid) can derive from the farm crop such as corn, utilizes the methods such as fermentation to obtain monomer lactic acid, then obtains poly(lactic acid) by monomer polymerization.This material is discarded into nature after application just can be degraded to nontoxic small molecules, what is more important very soon, and the high dependency of conventional polymer industry on petroleum chemical industry broken away from by this kind of material, has very good application prospect.
On the other hand, because poly(lactic acid) is nontoxic, film product can also be manufactured into or for food flexible packing.Although the oxygen barrier property of poly(lactic acid) is higher than polyolefine materials such as traditional polyethylene, polypropylene, still not enough, oxygen is easier to enter in packing bag by polylactic acid film, causes Food Oxidation, corruption, goes bad.Generally, laminated film technology can be adopted to improve the oxygen-barrier property of polylactic acid film, such as polylactic acid film be made three layers of laminated film of " sandwich " structure with barrier film.Wherein, barrier film is generally ethylene-vinyl alcohol copolymer film, polyvinylidene chloride film, aluminium foil, glassine paper, polyamide layer etc.Chinese invention patent CN1198715C discloses a kind of composite material for package of food be made up of polylactic acid layers and polyvinyl alcohol layer, and the polyvinyl alcohol layer used by it is exactly the effect in order to play waterproof, trapping and heat-sealing.
Especially, the oxygen barrier property of PVA (PVOH) FILM is outstanding, in general the preparation method of PVA (PVOH) FILM comprises wet processes and dry process two kinds of working methods: a. wet processes is mixed with the softening agent that (only) is moisture by polyvinyl alcohol, again under lesser temps (general less than 100 DEG C), pass through thermo forming.Because the polyvinyl alcohol product through wet processes is moisture, so generally need dewater through subsequent handling, as drying, the production cost of product can be caused so higher.B. dry process is mixed with water-free softening agent by polyvinyl alcohol, then under comparatively high temps (general more than 150 DEG C), pass through thermo forming.Because polyvinyl alcohol is to thermo-responsive, when dry process, easily make it be oxidized flavescence, cause the increase of its viscosity, mechanical property variation.
In addition, by by polylactic acid film and PVA (PVOH) FILM compound, although can improve the oxygen barrier property of laminated film, complex method often needs to use solvent, the use of solvent can affect to environment, and facility investment is higher, production efficiency is lower.
Chinese patent CN100406498C uses vulcabond as chainextender (end-capping reagent), prepares vinol/polylactic acid graft copolymer.Because vulcabond is toxic, be unfavorable for environment protection, and the carboxyl contained in polyvinyl alcohol and polylactic resin and moisture also can affect the chain extension effect of vulcabond.
In sum, those skilled in the art need further research, develop a kind of novel poly(lactic acid)-PVA (PVOH) FILM, with while possessing biological degradability, improve its oxygen-barrier property, also can not to environment.
Summary of the invention
The object of the invention is to solve above-mentioned prior art Problems existing, and a kind of biodegradable, polylactic acid alloy film with superior in gas barrier property is provided.
Polylactic acid alloy film of the present invention, its component comprises (A) polylactic resin, (B) polyvinyl alcohol resin and (C) expanding material, wherein, be 100 parts by weight with the total amount of (A) polylactic resin and (B) polyvinyl alcohol resin, (A) weight content of polylactic resin is 1 ~ 99 part, (B) weight content of polyvinyl alcohol resin is 1 ~ 99 part, (C) weight content of expanding material is 0.05-5 part, described polylactic acid alloy film also comprises: (D) weight content is the oxidation inhibitor of 0.01-3 part, wherein, described expanding material is the alkene esters of gallic acid expanding material of band epoxy base side chain or the olefines expanding material of band epoxy base side chain.
Further, described polylactic resin is Pfansteihl homopolymer, D-ALPHA-Hydroxypropionic acid homopolymer or L, one or more in D-ALPHA-Hydroxypropionic acid multipolymer.Preferably, the weight-average molecular weight of described polylactic resin is 10,000 ~ 1,000,000, and more preferably, its weight-average molecular weight is 50,000 ~ 500,000.
Further, described polyvinyl alcohol resin is the polymerization degree 1,000 ~ 10,000, the polyvinyl alcohol of alcoholysis degree 50% ~ 100%.
Further, described expanding material is glycidyl methacrylate graft polyethylene wax, glycidyl methacrylate graft polymethylmethacrylate, glycidyl methacrylate/methacrylic ester/styrol copolymer, ethene/acrylic ester/glycidyl methacrylate copolymer.
In order to improve the color of film better, to be adapted to different occasion and demand, polylactic acid alloy film of the present invention, is 100 parts by weight with the total amount of (A) polylactic resin and (B) polyvinyl alcohol resin, also comprises (D) oxidation inhibitor 0.01-3 weight part.Preferably, its weight content is 0.05-1.5 part.
Further, described oxidation inhibitor includes but not limited to one or more in phenols, amine, phosphorous acid esters, aliphatic ester, pentaerythritol esters, esters of acrylic acid, triazines, the agent of cyanurate class.Be preferably, tri-butyl-phenol, 4, 4 '-sulfo--bis-(3-methyl-6-tert butyl phenol), 2, 2 '-sulfo--bis-(3-methyl-6-tert butyl phenol), two (3, 5-di-tert-butyl-hydroxy phenyl propionic acid propionyl) hydrazine, phosphoric acid [3, 5 (1, 1-dimethyl ethyl)-4-hydroxy phenyl] methyl list ethyl ester calcium salt, triphenyl phosphite, triisodecyl phosphite ester, Wytox 312, 3, 5-di-tert-butyl-4-hydroxyl benzyl phosphoric acid ester, four [B-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, pentaerythritol tetrastearate, 12-hydroxystearin, trimethylolpropane tris stearate, stearic acid 13 ester, Tyox B, thio-2 acid 2 stearyl ester, 2-(4-hydroxyl-3, 5-di-tert-butyl amido)-4, two (n-octylthio)-1 of 6-, 3, one or more in 5-triazine.
Although not necessarily, but in order to the processing characteristics of better improving polylactic acid alloy film and snappiness, polylactic acid alloy film of the present invention, be 100 parts by weight with the total amount of (A) polylactic resin and (B) polyvinyl alcohol resin, also comprise (E) softening agent 1-40 weight part.Preferably, its weight content is 3-25 weight part.
Further, described softening agent includes but not limited to one or more in glycerine, ethylene glycol, polyoxyethylene glycol, propylene glycol, polypropylene glycol, acrylamide, glyceryl ester, citrate, sebate, suberate, phthalic acid ester, lactic acid, rac-Lactide, PLA-PEG copolymer, poly(lactic acid)-polypropylene glycol copolymers, polyethylene glycol-propylene glycol copolymers.Be preferably, one or more in the PLURONIC F-127 of the polyoxyethylene glycol of glycerine, ethylene glycol, vanay, triethyl citrate, tributyl citrate, acetyl triethyl citrate, tributyl acetylcitrate, number-average molecular weight 200-10000, the polypropylene glycol of number-average molecular weight 200-6000, number-average molecular weight 500-10000, the PLA-PEG-PLA triblock copolymer of number-average molecular weight 1000-20000.
Although not necessarily, but in order to the processing characteristics of better improving film and snappiness, polylactic acid alloy film of the present invention, be 100 parts by weight with the total amount of (A) polylactic resin and (B) polyvinyl alcohol resin, also comprise (F) toughner 1-100 weight part.
Further, described toughner is selected from one or more in aliphatic polyester, aliphatic-aromatic copolyester, aliphatic polycarbonate, elastomerics, rubber.Wherein, described aliphatic polyester is one or more in polycaprolactone, poly butylene succinate, poly-succinic tetramethylene adipate, polyhydroxybutyrate-hydroxypentanoic acid copolyesters, poly-Hydroxyoctanoic acid-oxyacetic acid copolyesters, poly-sebacic acid glyceryl ester, poly-hexanodioic acid glyceryl ester.Described aliphatic-aromatic copolyester is one or more in poly terephthalic acid tetramethylene adipate, poly terephthalic acid succinic acid-butanediol ester.Described elastomerics be ethylene-vinyl acetate copolymer, MBS, ethylene-acrylic acid copolymer, E.I.Du Pont Company PARALOIDBPM-500, Sukano company of BiomaxStrong, RohmandHaasChemicals company PLAdcS511, S515 in one or more.Described rubber is one or more in natural rubber, styrene-butadiene rubber(SBR), ethylene-propylene rubber(EPR).
Although not necessarily, but in order to the processing characteristics, snappiness, the barrier that better improve polylactic acid alloy film with reduce costs, polylactic acid alloy film of the present invention, be 100 parts by weight with the total amount of (A) polylactic resin and (B) polyvinyl alcohol resin, also comprise (G) weighting agent 1-80 weight part.Preferably, its weight content is 3-50 weight part.
Further, described weighting agent includes but not limited to calcium carbonate, calcium sulfate, barium sulfate, barium titanate, mica powder, talcum powder, carbon black, silicon-dioxide, titanium dioxide, polynite, zeolite, wilkinite, vermiculite, aluminum oxide, phosphatic rock, glass fibre, hollow glass ball, is preferably one or more in calcium carbonate, calcium sulfate, talcum powder, titanium dioxide, polynite, vermiculite.
Described calcium carbonate, can select the micron order calcium carbonate of mean diameter (D50) 1-10 micron, or the nanometer grade calcium carbonate of mean diameter (D50) 5 nanometer-900 nanometer.In order to obtain good mechanical property, especially in order to improve toughness, the nanometer grade calcium carbonate of preferred average diameter (D50) 10 nanometer-100 nanometer.
Described calcium carbonate can carry out surface modification further with surface-modifying agent.Described surface-modifying agent is one or more in phosphoric acid ester, stearic acid, silane coupling agent, titanate coupling agent or above-mentioned (E) softening agent.
Carry out surface modification to described calcium carbonate and can adopt this area routine techniques, such as put in reactor by calcium carbonate and surface-modifying agent, be heated to 60-95 DEG C, after Keep agitation, discharging, namely obtains the calcium carbonate of surface modification.Preferably, described weighting agent is one or more in the nanometer grade calcium carbonate of the nanometer grade calcium carbonate of the nanometer grade calcium carbonate of glycerine surface modification, glycerine and silane coupling agent surface modification, glycerine and titanate coupling agent modified.
Further, but in order to better improve the various performances of alloy firm, the various common agents such as appropriate end-capping reagent, nucleator, fire retardant, UV stabilizer, pigment, whitening agent, lubricant can also be comprised.
Wherein, above-mentioned selectable components (D) oxidation inhibitor 0.01-3 weight part, (E) softening agent 1-40 weight part, (F) toughner 1-100 weight part and (G) weighting agent 1-80 weight part, can carry out the component of adding wherein any one or more according to actual needs.
The preparation method of polylactic acid alloy film of the present invention can with reference to existing thin film preparation process technology.A kind of preparation method provided by the invention comprises: each component mixed; Join twin screw extruder, extrude in 150 DEG C ~ 220 DEG C melt blendings; At 180-210 DEG C, film is blow molded into after granulation.
Another kind of preparation method provided by the invention comprises: each component mixed; Join twin screw extruder, extrude in 150 DEG C ~ 220 DEG C melt blendings; At 180-210 DEG C, curtain coating becomes film.
The preparation method of polylactic acid alloy film of the present invention also comprises: carry out unidirectional or two-way stretching, to give its more mechanical property.
The preparation method of polylactic acid alloy film of the present invention also comprises: at 60-180 DEG C, apply heat setting type, is more conducive to improving mechanical property.
Polylactic acid alloy film of the present invention, can be used for preparing wrapping material, agricultural film or plastics bag, is particularly suitable for the packaging material for food needing oxygen-barrier property.
Wherein, in " one or more " of the present invention " more than " all comprise this number " two kinds ".
Polylactic acid alloy film of the present invention, by under the prerequisite of complete biodegradable and high strength, can effectively improve the oxygen barrier property of polylactic acid alloy film keeping thin-film material.Present invention process method is simple, with low cost, effectively can promote the widespread use of environment-friendly type polylactic acid article.
Embodiment
Mode below by embodiment further illustrates the present invention, does not therefore limit the present invention among described scope of embodiments.
embodiment 1 ~ 9
Table 1 gives formula and the performance evaluation of polylactic acid alloy film embodiment 1 ~ 9.After tentatively mixing by the component shown in table 1, with twin-screw extrusion, extrusion temperature 190 DEG C, water-cooled, pelletizing; Particle after drying, at 180 DEG C with single screw extrusion machine extrude, blowing, prepare the film that thickness is 20 μm.
Wherein, the content of each formula is parts by weight, and various component is as follows:
(A) polylactic resin
A1: Natureworks company of the U.S., 4032D
A2: Natureworks company of the U.S., 4060D
(B) polyvinyl alcohol resin
B1: oil of SPC, the polymerization degree 1700, alcoholysis degree 99%
B2: oil of SPC, the polymerization degree 1700, alcoholysis degree 88%
(C) expanding material
C1:BASF company, JoncyrlADR4368, the polymkeric substance of multi-epoxy functional group
C2: traditional Chinese medicines group, maleic anhydride grafted polyethylene
(D) oxidation inhibitor
D1: traditional Chinese medicines group, triphenyl phosphite
D2: traditional Chinese medicines group, Tyox B
Two (the n-octylthio)-1,3,5-triazines of D3: traditional Chinese medicines group, 2-(4-hydroxyl-3,5-di-tert-butyl amido)-4,6-
Wherein, the performance evaluation in table 1 comprises:
Processing characteristics, can observe each formula by thermo forming film;
Tensile property, tests tensile strength and the elongation at break of sample by GB1040.3-2006;
Oxygen transit dose, tests sample at 23 DEG C, oxygen transit dose under 60%RH by GB/T1038-2000, unit cm
3/ m
2dayatm.
comparative example 1
Table 1 gives formula and the performance evaluation of comparative example 1.After tentatively mixing by the component shown in table 1, with twin-screw extrusion, extrusion temperature 190 DEG C, water-cooled, pelletizing; Particle after drying, at 180 DEG C with single screw extrusion machine extrude, blowing, prepare the film that thickness is 20 μm.
comparative example 2 ~ 4
Table 1 gives formula and the performance evaluation of comparative example 2 ~ 4.After tentatively mixing by the component shown in table 1, with twin-screw extrusion, extrusion temperature 190 DEG C, extrudes instability, and polyvinyl alcohol cannot plastify, and color is sallow, cannot prepare film further.
embodiment 10 ~ 17
Table 2 gives on the basis that A1/A2/B2/C2/D2/D3 is in Table 1 respectively 35/35/30/5/0.2/0.2 weight part, adds formula and the performance evaluation of the embodiment 10 ~ 17 after by the component shown in table 2 further.Tentatively mix by the component shown in table 2, with twin-screw extrusion, extrusion temperature 190 DEG C, curtain coating, prepares the film that thickness is 20 μm.
Wherein, the content of each formula is parts by weight, and various component is as follows:
(E) softening agent
E1: traditional Chinese medicines group, the positive butyl ester of acetyl tributyl citrate
E2: traditional Chinese medicines group, glycerine
E3: traditional Chinese medicines group, polyoxyethylene glycol, number-average molecular weight 1000
(F) toughner
F1:BASF company, Ecoflex7011, poly terephthalic acid tetramethylene adipate
F2: Japanese Showa polymer company, Bionolle3001, poly-succinic tetramethylene adipate
F3: E.I.Du Pont Company, BiomaxStrong100, ethylene-acrylic acid copolymer elastomerics
Wherein, the performance evaluation in table 2 comprises:
Processing characteristics, can observe each formula by thermo forming film;
Tensile property, tests tensile strength and the elongation at break of sample by GB1040.3-2006;
Oxygen transit dose, tests sample at 23 DEG C, oxygen transit dose under 60%RH by GB/T1038-2000, unit cm
3/ m
2dayatm.
embodiment 18 ~ 22
Table 3 gives on the basis that A1/A2/B2/C2/D2/D3 is in Table 1 respectively 35/35/30/5/0.2/0.2/ weight part, after adding in table 2 E3/F1 being respectively 20/10 weight part again, add formula and the performance evaluation of the embodiment 18 ~ 22 after by the component shown in table 3 further.Tentatively mix by the component shown in table 3, with twin-screw extrusion, extrusion temperature 190 DEG C, curtain coating, prepares the film that thickness is 20 μm.
Wherein, the content of each formula is parts by weight, and various component is as follows:
(G) weighting agent
G1: Zibo Sheng Xu Trade Co., Ltd., micron order calcium carbonate, D50=2 ~ 2 micron.
G2: nano material company limited of Ruicheng Xintai City, nanometer grade calcium carbonate, D50=15-25 nanometer.
G3: the nanometer grade calcium carbonate of glycerine surface modification, self-control, joins in reactor by 1kgG2 and 100g glycerine, is heated to 80 DEG C, after Keep agitation, discharging.
G4: the nanometer grade calcium carbonate of glycerine and silane coupling agent KH560 surface modification, self-control, joins in reactor by 1kgG2,100g glycerine and 30gKH560, is heated to 80 DEG C, after Keep agitation, discharging.
G5: Zibo Sheng Xu Trade Co., Ltd., talcum powder, D50=2 ~ 2 micron.
Wherein, the performance evaluation in table 3 comprises:
Processing characteristics, can observe each formula by thermo forming film;
Tensile property, tests tensile strength and the elongation at break of sample by GB1040.3-2006;
Oxygen transit dose, tests sample at 23 DEG C, oxygen transit dose under 60%RH by GB/T1038-2000, unit cm
3/ m
2dayatm.
Table 3
Claims (2)
1. a polylactic acid alloy film, is characterized in that: it is made up of the component of following parts by weight:
(A) polylactic resin, 70 weight parts, comprise the polylactic resin 4032D of 35 weight parts, the polylactic resin 4060D of 35 weight parts;
(B) polyvinyl alcohol resin, 30 weight parts, the described polyvinyl alcohol resin polymerization degree is 1700, alcoholysis degree is 88%;
(C) maleic anhydride grafted polyethylene, 5 weight parts;
(D) Tyox B, 0.2 weight part; Two (the n-octylthio)-1,3,5-triazines of 2-(4-hydroxyl-3,5-di-tert-butyl amido)-4,6-, 0.2 weight part;
(E) polyoxyethylene glycol, 20 weight parts, described polyoxyethylene glycol number-average molecular weight is 1000;
(F) Ecoflex7011, poly terephthalic acid tetramethylene adipate, 10 weight parts;
(G) nanometer grade calcium carbonate of glycerine surface modification: join in reactor by 1kgG2 and 100g glycerine, is heated to 80 DEG C, after Keep agitation, discharging, and G2 is the nanometer grade calcium carbonate of D50=15-25 nanometer, 20 weight parts.
2. polylactic acid alloy film according to claim 1 is as the application of wrapping material, agricultural film or plastics bag.
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