CN102993654A - Biodegradable barrier thin film, as well as preparation method and application thereof - Google Patents
Biodegradable barrier thin film, as well as preparation method and application thereof Download PDFInfo
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- 230000004888 barrier function Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000010409 thin film Substances 0.000 title abstract 5
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 14
- 229920001634 Copolyester Polymers 0.000 claims abstract description 11
- 238000004806 packaging method and process Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 5
- 238000006731 degradation reaction Methods 0.000 claims description 45
- 230000015556 catabolic process Effects 0.000 claims description 44
- -1 poly(lactic acid) Polymers 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 230000005540 biological transmission Effects 0.000 claims description 10
- 230000035699 permeability Effects 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000009264 composting Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 4
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical compound CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
- 229920002961 polybutylene succinate Polymers 0.000 claims description 4
- 239000004631 polybutylene succinate Substances 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- LMHJFKYQYDSOQO-SECBINFHSA-N (5r)-5-hydroxydecanoic acid Chemical compound CCCCC[C@@H](O)CCCC(O)=O LMHJFKYQYDSOQO-SECBINFHSA-N 0.000 claims description 2
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 claims description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- JKRDADVRIYVCCY-UHFFFAOYSA-N 2-hydroxyoctanoic acid Chemical compound CCCCCCC(O)C(O)=O JKRDADVRIYVCCY-UHFFFAOYSA-N 0.000 claims description 2
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 claims description 2
- YDCRNMJQROAWFT-UHFFFAOYSA-N 5-hydroxyhexanoic acid Chemical compound CC(O)CCCC(O)=O YDCRNMJQROAWFT-UHFFFAOYSA-N 0.000 claims description 2
- PHOJOSOUIAQEDH-UHFFFAOYSA-N 5-hydroxypentanoic acid Chemical compound OCCCCC(O)=O PHOJOSOUIAQEDH-UHFFFAOYSA-N 0.000 claims description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 2
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 claims description 2
- PNAJBOZYCFSQDJ-UHFFFAOYSA-N 7-hydroxyheptanoic acid Chemical compound OCCCCCCC(O)=O PNAJBOZYCFSQDJ-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920000954 Polyglycolide Polymers 0.000 claims description 2
- 239000004902 Softening Agent Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- LMHJFKYQYDSOQO-UHFFFAOYSA-N hydroxydecanoic acid Natural products CCCCCC(O)CCCC(O)=O LMHJFKYQYDSOQO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004633 polyglycolic acid Substances 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- LXNOENXQFNYMGT-UHFFFAOYSA-N xi-5-Hydroxydodecanoic acid Chemical compound CCCCCCCC(O)CCCC(O)=O LXNOENXQFNYMGT-UHFFFAOYSA-N 0.000 claims description 2
- 235000013305 food Nutrition 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract description 6
- 238000006065 biodegradation reaction Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 16
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229920000704 biodegradable plastic Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920008262 Thermoplastic starch Polymers 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004628 starch-based polymer Substances 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical group O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 208000037534 Progressive hemifacial atrophy Diseases 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003413 degradative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012017 passive hemagglutination assay Methods 0.000 description 1
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 description 1
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a biodegradable barrier thin film, as well as a preparation method and application thereof. The biodegradable barrier thin film is prepared from 0-80% of biodegradable homopolyester, 0-80% of biodegradable copolyester, 1-30% of ethylene-vinyl alcohol copolymer and 0-5% of additives. The biodegradable barrier thin film disclosed by the invention is formed by mixing the biodegradable homopolyester with higher biodegradation speed, the biodegradable copolyester with better processing performance and the ethylene-vinyl alcohol copolymer with good barrier property according to different proportions, and the thin film prepared from an obtained composition has biodegradability and barrier property, and can be widely applied to the packaging field, in particular to the food and medicine packaging field.
Description
Technical field
The present invention relates to a kind of biological degradation barrier film and its preparation method and application.
Background technology
General-purpose plastics is widely used in every field because of its excellent combination property, is listed as four large support material with iron and steel, timber, cement, and a year usage quantity constantly rises.General-purpose plastics such as polyethylene (PE), polypropylene (PP) and polystyrene (PS) etc. can steady in a long-termly exist at nature, and hard degradation therefore its discarded being difficult to afterwards recycles, has caused serious pollution to environment.Biodegradable plastic can comparatively fast be degraded under physical environment because of it becomes one of effective way that solves the plastic refuse problem of environmental pollution, thereby has caused showing great attention to of people, and biodegradable plastic is competitively developed in countries in the world.
Biodegradable plastic is a base polymer material that can finally be decomposed into carbonic acid gas and water after process certain hour span under the envrionment conditions that is fit to.This degradation process is divided into two processes usually, and molecular weight diminished after at first macromole was degraded through hydrolysis, light/oxygen, was further fallen by microbial consumption thereafter, and this quasi-microorganism may be bacterium, fungi, yeast, algae etc.The biodegradable plastic in the whole world has reached tens kinds at present, mainly contain: the equal polyester of biological degradation, such as hydroxy fatty acid (salt) polymkeric substance (PHAs), poly(lactic acid) (PLA), poly-hydroxybutyl ester (PHB), polycaprolactone (PCL), hydroxybutyl acid-hydroxypentanoic acid copolyesters (PHBV); Biodegradable Copolyester, such as poly butylene succinate (PBS), poly-(succinic acid-butanediol ester is tetramethylene adipate altogether) (PBSA) etc.; Or have the natural product of polysaccharide structures, such as thermoplastic starch (TPS), cellulose acetate etc.Although above-mentioned degradative plastics has good biodegradability, all greatly limited its large-scale application of using separately as material because of himself defective more or less.Biodegradable material is carried out blending and modifying, choose the suitable biodegradable material component of performance, regulate the proportioning between the biodegradable material component, the materials processing means of improving the consistency between the biodegradable material and taking to suit, can between each biodegradable material, learn from other's strong points to offset one's weaknesses, overcome separately self-defect, develop the various types of materials that can satisfy application requiring, this is one of study hotspot of present biodegradable material.
In recent years, biodegradable material is rapid in plastic wrapping sector application and development, the quality of biological degradation packaging material constantly promotes and output constantly increases, in order to adapt to market to the larger demand of biological degradation packaging material, the multifunction of biological degradation packaging material, barrier has particularly become an important research exploitation direction of biological degradation packaging material.Biological degradation barrier material and film thereof have the characteristic of biological degradability and resistance oxygen and water vapour.During use, can effectively keep the original mouthfeel of content, the smells such as container and the interior food of packing, prevent quality badness, prolong commodity shelf-life and quality guarantee period; After the use, compostable reduces the pollution to environment.
At present, the barrier material that is widely used in the food and medicine field is the film article with multilayered structure that conventional plastic is made, although it has good barrier property, but it can steady in a long-termly exist at occurring in nature, hard degradation, therefore be difficult to recycling after it is discarded, caused serious pollution to environment.And the biodegradable material that is applied to packaging field does not have barrier, can't be widely used in the food and medicine field.
Summary of the invention
The defective that does not have barrier in order to overcome existing biodegradable film, primary and foremost purpose of the present invention is to provide a kind of biological degradation barrier film, this film has barrier, simultaneously biodegradable, can be widely used in the food and medicine field, compostable after it is discarded can reduce the pollution to environment.
The preparation method of the biological degradation barrier film that another object of the present invention is to provide above-mentioned.
The application of the biological degradation barrier film that a further object of the present invention is to provide above-mentioned.
Purpose of the present invention is achieved through the following technical solutions:
A kind of biological degradation barrier film, its raw materials comprises the composition of following mass percent:
The equal polyester of biological degradation: 0-80%
Biodegradable Copolyester: 0-80%
Ethylene-vinyl alcohol copolymer: 1-30%
Additive: 0-5%.
Described biological degradation barrier film, degradation rate reaches more than 90% in 90 days under composting conditions; OTR oxygen transmission rate OTR≤2000ml/m
2Dbar, water vapour permeability WVTR≤100g/m
2D.
The equal polyester of described biological degradation is obtained by condensation reaction or ring-opening polymerization by hydroxy aliphatic acids monomer;
Described hydroxy aliphatic acids monomer is more than one in hydroxyalkyl acid or its cyclisation ester derivative;
The preferred carbonatoms of described hydroxy aliphatic acids monomer is 4 ~ 18 hydroxy fatty acid or in its cyclisation ester derivative more than one;
The preferred oxyacetic acid of described hydroxy aliphatic acids monomer, alpha-hydroxypropionic acid, beta-hydroxy-butanoic acid, hydroxy-butanedioic acid, 5-hydroxypentanoic acid, 3-hydroxycaproic acid, 5-hydroxycaproic acid, 6 hydroxycaproic acid, 7-hydroxyl enanthic acid, 3, more than one in 5-dihydroxyl enanthic acid, Hydroxyoctanoic acid, 5-hydroxydecanoic acid or the 5-hydroxyl dodecanoic acid;
In the preferred poly(lactic acid) of the equal polyester of described biological degradation, polyglycolic acid, poly-3-hydroxybutyrate, poly-3-hydroxypentanoic acid, poly-3-hydroxycaproic acid, polycaprolactone, poly-hydroxybutyl acid esters or the poly-valerolactone more than one.
Described Biodegradable Copolyester is obtained by polyreaction by binary acids monomer and aliphatic dihydroxy alcohol;
Described binary acids monomer is more than one in aliphatic dibasic acid and esterified derivative, aromatic acid and the esterified derivative thereof;
Described aliphatic dihydroxy alcohol, aliphatic dibasic acid and esterified derivative thereof, aromatic acid and esterified derivative thereof, its carbonatoms are 2 ~ 22;
The preferred oxalic acid of described binary acids monomer, Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, hendecane dicarboxylic acid, terephthalic acid, phthalic acid, m-phthalic acid, in phenylene-diacetic acid or the phthalic acid more than one;
The preferred ethylene glycol of described aliphatic dihydroxy alcohol, 1,2-PD, 1,3-PD, 1,2-butyleneglycol, 1,4-butyleneglycol, 1,5-PD, 2，2-dimethyl-1，3-propanediol, the 2-ethyl-2-tertiary butyl-1, ammediol or 2,2,4-trimethylammonium-1, more than one in the 6-hexylene glycol;
The preferred polyethylene glycol succinate of described Biodegradable Copolyester, poly butylene succinate, the common adipic acid ester of poly-succinic acid-butanediol, polybutylene terephthalate are total to more than one in succinate or the common adipic acid ester of polybutylene terephthalate.
Described ethylene-vinyl alcohol copolymer, therein ethylene unit molar content is 5～95%, preferred 45%.
Described additive is more than one in thermo-stabilizer, oxidation inhibitor, pigment, weather resisting agent, fire retardant, softening agent, lubricant, releasing agent, antistatic agent, filler or the dispersion agent.
The preparation method of above-mentioned biological degradation barrier film, be after each raw material is mixed through oven dry, stir, melt extrude with blown film after make the biological degradation barrier film.
Above-mentioned biological degradation barrier film can be widely used in packaging field, particularly the food and medicine packaging field.
The present invention has following advantage and effect with respect to prior art:
The ethylene-vinyl alcohol copolymer that the present invention adopts the equal polyester of biological degradation with very fast biodegradation rate, have the Biodegradable Copolyester of better processing characteristics and have a good barrier is by the different ratios compounding, the film of resulting composition preparation not only has biological degradability but also has barrier, can be widely used in packaging field, particularly the food and medicine packaging field.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1-12
A kind of biological degradation barrier film, its raw material see Table among the 1-4(table 1-4, and the consumption unit of raw material is mass percent), its preparation method may further comprise the steps:
(1) each raw material was dried 5 hours in 80 ℃ of baking ovens;
(2) dried each raw material is added in the high mixer, first stirring at low speed 5 minutes, high-speed stirring is 3 minutes again;
(3) material that mixes is joined in the twin screw extruder, the diameter of forcing machine is 40mm, and length-to-diameter ratio is 36:1, is provided with 9 heating zone and with vacuum pumping hardware.Extrusion is selected following operational condition:
Temperature Setting: 80/150/190/190/190/190/190/190/170 ℃
Rate of feeding: 100kg/h
Screw speed: 300rpm
Vacuum pressure: 0.4 normal atmosphere;
The forcing machine material strip was dried 2 hours for 80 ℃ in dehumidifying heat pump by after earnestly mode causes particle under water, then sent into single Screw Extrusion inflation film manufacturing machine and made the film that thickness is 25um.
Measure degraded and the barrier property of each embodiment gained film, the results are shown in Table 1-4.
The testing method of degraded and barrier property is as follows:
1. biological degradation rate: with reference to the method test of ISO14855, with the CO of material compost after 90 days
2Burst size is the degradation property index.
2. OTR oxygen transmission rate OTR: with reference to the method test of ASTM D3985.
3. water vapour permeability WVTR: with reference to the method test of ASTM D1653.
Comparative Examples 1-3
A kind of film, its raw material sees Table 1-3, and its preparation method is with embodiment 1-12.Degraded and Test Method of Barrier Properties the results are shown in Table 1-3 with embodiment 1-12.
Table 1
Annotate: among the table 1-4, the molar content of ethylene unit is 45% in the ethylene-vinyl alcohol copolymer.
As shown in Table 1, the resulting film of embodiment 1-3, biological degradation rate reaches more than 90% in 90 days under composting conditions, OTR oxygen transmission rate OTR≤2000ml/m
2Dbar, water vapour permeability WVTR≤100g/m
2D.Compare with Comparative Examples 1, among the embodiment 2 because of blend ethylene-vinyl alcohol copolymer (EVOH), its OTR oxygen transmission rate and water vapour permeability have had obvious lifting.
Table 2
As shown in Table 2, the resulting film of embodiment 4-6, biological degradation rate reaches more than 90% in 90 days under composting conditions, OTR oxygen transmission rate OTR≤2000ml/m
2Dbar, water vapour permeability WVTR≤100g/m
2D.Compare with Comparative Examples 2, among the embodiment 5 because of blend ethylene-vinyl alcohol copolymer (EVOH), its OTR oxygen transmission rate and water vapour permeability have had obvious lifting.
Table 3
As shown in Table 3, the resulting film of embodiment 7-9, biological degradation rate reaches more than 90% in 90 days under composting conditions, OTR oxygen transmission rate OTR≤2000ml/m
2Dbar, water vapour permeability WVTR≤100g/m
2D.Compare with Comparative Examples 3, among the embodiment 8 because of blend ethylene-vinyl alcohol copolymer (EVOH), its OTR oxygen transmission rate and water vapour permeability have had obvious lifting.
Table 4
As shown in Table 4, the resulting film of embodiment 10-12, biological degradation rate reaches more than 90% in 90 days under composting conditions, OTR oxygen transmission rate OTR≤2000ml/m
2Dbar, water vapour permeability WVTR≤100g/m
2D.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. biological degradation barrier film, be characterised in that: its raw materials comprises the composition of following mass percent:
The equal polyester of biological degradation: 0-80%
Biodegradable Copolyester: 0-80%
Ethylene-vinyl alcohol copolymer: 1-30%
Additive: 0-5%;
The equal polyester of described biological degradation is obtained by condensation reaction or ring-opening polymerization by hydroxy aliphatic acids monomer;
Described Biodegradable Copolyester is obtained by polyreaction by binary acids monomer and aliphatic dihydroxy alcohol.
2. biological degradation barrier film according to claim 1 is characterized in that: described amyloid biological degradation barrier film, and degradation rate reaches more than 90% in 90 days under composting conditions; OTR oxygen transmission rate≤2000ml/m
2Dbar, water vapour permeability≤100g/m
2D.
3. biological degradation barrier film according to claim 1 is characterized in that:
Described hydroxy aliphatic acids monomer is more than one in hydroxyalkyl acid or its cyclisation ester derivative;
Described binary acids monomer is more than one in aliphatic dibasic acid and esterified derivative, aromatic acid and the esterified derivative thereof.
4. biological degradation barrier film according to claim 1 is characterized in that:
Described hydroxy aliphatic acids monomer is oxyacetic acid, alpha-hydroxypropionic acid, beta-hydroxy-butanoic acid, hydroxy-butanedioic acid, 5-hydroxypentanoic acid, 3-hydroxycaproic acid, 5-hydroxycaproic acid, 6 hydroxycaproic acid, 7-hydroxyl enanthic acid, 3, more than one in 5-dihydroxyl enanthic acid, Hydroxyoctanoic acid, 5-hydroxydecanoic acid or the 5-hydroxyl dodecanoic acid;
Described binary acids monomer is oxalic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, hendecane dicarboxylic acid, terephthalic acid, phthalic acid, m-phthalic acid, in phenylene-diacetic acid or the phthalic acid more than one;
Described aliphatic dihydroxy alcohol is ethylene glycol, 1,2-PD, 1,3-PD, 1,2-butyleneglycol, 1,4-butyleneglycol, 1,5-PD, 2，2-dimethyl-1，3-propanediol, the 2-ethyl-2-tertiary butyl-1, ammediol or 2,2,4-trimethylammonium-1, more than one in the 6-hexylene glycol.
5. biological degradation barrier film according to claim 1 is characterized in that:
The equal polyester of described biological degradation is more than one in poly(lactic acid), polyglycolic acid, poly-3-hydroxybutyrate, poly-3-hydroxypentanoic acid, poly-3-hydroxycaproic acid, polycaprolactone, poly-hydroxybutyl acid esters or the poly-valerolactone;
Described Biodegradable Copolyester is that polyethylene glycol succinate, poly butylene succinate, the common adipic acid ester of poly-succinic acid-butanediol, the common succinate of polybutylene terephthalate or polybutylene terephthalate are total to more than one in the adipic acid ester;
Described ethylene-vinyl alcohol copolymer, the molar content of therein ethylene unit are 45%.
6. biological degradation barrier film according to claim 1, it is characterized in that: described additive is more than one in thermo-stabilizer, oxidation inhibitor, pigment, weather resisting agent, fire retardant, softening agent, lubricant, releasing agent, antistatic agent, filler or the dispersion agent.
7. the preparation method of each described biological degradation barrier film of claim 1-6 is characterized in that may further comprise the steps: after each raw material is mixed through oven dry, stir, melt extrude with blown film after make the biological degradation barrier film.
8. each described biological degradation barrier film application in packaging field of claim 1-6.
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| CN106674949A (en) * | 2016-07-14 | 2017-05-17 | 东莞市常平信安实业有限公司 | PC/PHA plastic for thin-walled injection molding and preparation method thereof |
| CN106496967B (en) * | 2016-11-04 | 2018-07-10 | 汕头市东发印务有限公司 | A kind of high obstructing degradable packaging material and preparation method thereof |
| CN106496967A (en) * | 2016-11-04 | 2017-03-15 | 金福兴 | A kind of high obstructing degradable packaging material and preparation method thereof |
| CN108102310A (en) * | 2017-12-21 | 2018-06-01 | 佛山市南方包装有限公司 | A kind of wet polyester plastics of high resistant and polyester plastics container |
| CN107987494A (en) * | 2017-12-21 | 2018-05-04 | 江苏理工学院 | A kind of biodegradable polyethylene terephthalate blend and preparation method thereof |
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Application publication date: 20130327 |