CN105017699A - Bio-based degradable stretched film and preparation method thereof - Google Patents
Bio-based degradable stretched film and preparation method thereof Download PDFInfo
- Publication number
- CN105017699A CN105017699A CN201510475039.3A CN201510475039A CN105017699A CN 105017699 A CN105017699 A CN 105017699A CN 201510475039 A CN201510475039 A CN 201510475039A CN 105017699 A CN105017699 A CN 105017699A
- Authority
- CN
- China
- Prior art keywords
- parts
- bio
- polyvinyl alcohol
- layer
- antioxidant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 67
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 67
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000000088 plastic resin Substances 0.000 claims abstract description 37
- 229920006302 stretch film Polymers 0.000 claims abstract description 22
- 230000004888 barrier function Effects 0.000 claims abstract description 16
- 239000010410 layer Substances 0.000 claims description 66
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 40
- 239000004626 polylactic acid Substances 0.000 claims description 40
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 39
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 37
- 238000001125 extrusion Methods 0.000 claims description 28
- 239000004014 plasticizer Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 239000004970 Chain extender Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 239000000314 lubricant Substances 0.000 claims description 13
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- UXDDRFCJKNROTO-UHFFFAOYSA-N Glycerol 1,2-diacetate Chemical compound CC(=O)OCC(CO)OC(C)=O UXDDRFCJKNROTO-UHFFFAOYSA-N 0.000 claims description 6
- 238000007259 addition reaction Methods 0.000 claims description 6
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229960002622 triacetin Drugs 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000012790 adhesive layer Substances 0.000 claims description 3
- -1 fatty acid ester Chemical class 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 229940057995 liquid paraffin Drugs 0.000 claims description 3
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 3
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 3
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000002457 bidirectional effect Effects 0.000 claims description 2
- 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 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229920000704 biodegradable plastic Polymers 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002985 plastic film Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 239000005022 packaging material Substances 0.000 abstract description 4
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 abstract description 3
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 abstract description 3
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004715 ethylene vinyl alcohol Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 229940127554 medical product Drugs 0.000 abstract description 2
- 239000005033 polyvinylidene chloride Substances 0.000 abstract description 2
- XSBJUSIOTXTIPN-UHFFFAOYSA-N aluminum platinum Chemical compound [Al].[Pt] XSBJUSIOTXTIPN-UHFFFAOYSA-N 0.000 abstract 1
- 230000002860 competitive effect Effects 0.000 abstract 1
- 230000000295 complement effect Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000013520 petroleum-based product Substances 0.000 abstract 1
- 239000000155 melt Substances 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 2
- 230000036760 body temperature Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000011846 petroleum-based material Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 235000014528 Pholiota nameko Nutrition 0.000 description 1
- 244000168667 Pholiota nameko Species 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002953 phosphate buffered saline Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a bio-based degradable stretch film and a preparation method thereof. The bio-based degradable stretch film comprises a polyvinyl alcohol plastic resin layer, and bio-based degradable barrier layers are respectively arranged on the inner side and the outer side of the polyvinyl alcohol plastic resin layer. The invention realizes the compatibility among PVA, PLA and PHA modified resins, organically integrates the material layers by adopting multilayer coextrusion and biaxial stretching processes, and the properties of the materials play a complementary role, so that the stretched film has good thermoplasticity, stretchability and high barrier property, and can replace PVDC, PA and EVOH? The functional packaging materials such as aluminum platinum materials and the like can be completely biodegraded, have strong environmental protection performance, can prevent the pollution to the environment, have the cost performance completely comparable to petroleum-based products, have better competitive advantages, and can be widely applied to the fields of food, medical products and the like.
Description
Technical Field
The invention relates to the technical field of packaging materials, in particular to an environment-friendly high-barrier bio-based degradable stretch film and a preparation method thereof.
Background
The bio-based material aims to replace or partially replace petroleum resin to be used as a packaging material, such as high-barrier materials PVADC, EVOH and PA, and plays an excellent role in quality and freshness preservation of food, medical products and the like, and is widely accepted by the society.
As a bio-based PVA resin having high barrier property, it is excellent in gas barrier property, weak electric resistance, organic solvent resistance and aroma-keeping and flavor-keeping property, but it has a fatal disadvantage that the gas barrier property is poor and the barrier property is drastically lowered in a high humidity state (when the humidity is 60% or more), thereby limiting its usability. Compared with petroleum-based materials, the material has outstanding price advantage, can be completely biodegraded, is environment-friendly, and can prevent pollution to the environment. However, how to apply processing to realize compatibility with other materials is organically integrated with other materials, so that the overall comprehensive performance of the packaging material is improved, and the cost performance is improved, which is an important direction for research in the field of the material.
Chinese patent (102390148A) discloses a high-barrier multilayer co-extruded bio-based blown film, which is processed by PPC polymethyl ethylene carbonate with biodegradability, but the inner and outer layer materials in the multilayer still belong to petroleum-based materials.
Chinese patent (103950257A) discloses a high-barrier bio-based composite membrane, which is made of PLA, PHA and PBS bio-materials, but its barrier layer is PVDC, EVOH and other hydroxy resins, which are not bio-based materials, and they are not degradable and not friendly to environment.
Disclosure of Invention
The invention aims to solve one technical problem of providing a bio-based degradable stretch film which can realize compatibility among materials, is ecological and environment-friendly and has high barrier property.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the bio-based degradable stretch film comprises a polyvinyl alcohol plastic resin layer, wherein bio-based degradable barrier layers are respectively arranged on the inner side and the outer side of the polyvinyl alcohol plastic resin layer.
Preferably, the bio-based degradation barrier layer is a polyhydroxyfatty acid ester layer or a polylactic acid layer.
Preferably, a compatible adhesive layer is arranged between the biological degradation barrier layer and the polyvinyl alcohol plastic resin layer.
Preferably, the polyvinyl alcohol plastic resin layer is prepared from the following raw materials in parts by weight: 80-120 parts of polyvinyl alcohol; 5-30 parts of a plasticizer; 0.1-2 parts of an antioxidant; 0.2-1 part of an extrusion chain extender; 0.2-5 parts of a lubricant; 2-10 parts of a compatilizer.
Preferably, the polyhydroxyalkanoate layer is prepared from the following raw materials in parts by weight: 80-120 parts of polyhydroxyalkanoate; 2-20 parts of a plasticizer; 0.1-2 parts of an antioxidant; 0.5-2.5 parts of an extrusion chain extender; 0.2-5 parts of a lubricant; 2-10 parts of a compatilizer.
Preferably, the polylactic acid layer is prepared from the following raw materials in parts by weight: 80-120 parts of polylactic acid; 2-20 parts of a plasticizer; 0.1-2 parts of an antioxidant; 0.5-2.5 parts of an extrusion chain extender; 0.2-5 parts of a lubricant; 2-10 parts of a compatilizer; 0.1-2 parts of hydrolysis resistant agent.
Preferably, the plasticizer is prepared by the following method: mixing glycerol, propylene glycol, sorbitol, glycerol monoacetate, glycerol diacetate and glycerol triacetate in any proportion, adding 0.1-1 wt% of an auxiliary agent (a plasticizing chain extender and a plasticizing catalyst) for addition reaction, controlling the reaction temperature at 30-90 ℃ and the reaction time at 3-4 hours. Wherein the auxiliary agent comprises a plasticizing chain extender with the weight content of more than or equal to 0.05 percent and a plasticizing catalyst with the weight content of more than or equal to 0.05 percent, and the total weight content of the plasticizing chain extender and the plasticizing catalyst is less than or equal to 1 percent; the plasticizing chain extender can adopt trisnonylphenyl phosphite (TNP) and 1, 4-Butanediol (BDO); the catalyst plasticizing catalyst can adopt adipic acid, phosphoric acid and the like.
Preferably, the antioxidant is one or a mixture of several of antioxidant 300, antioxidant 330, antioxidant 1010, antioxidant 168, antioxidant 264 or antioxidant 1098 in any proportion.
Preferably, the lubricant is one or a mixture of more of liquid paraffin, polyethylene glycol, oleamide, erucamide, oxidized polyethylene wax, talcum powder or titanium dioxide in any proportion.
Wherein the preferred polymerization degree of the polyvinyl alcohol is 1700-3000, and the alcoholysis degree is more than or equal to 88-99.8%;
wherein, the extrusion chain extender can adopt trisnonylphenyl phosphite (TNP) or TMP-6000 (produced by Hangzhou xi metallocene new materials science and technology Co., Ltd.);
wherein, the compatilizer can adopt EMA4210, EMA3210, ZQ-T400, TMP-1000 or EQ-501; EMA4210 and EMA3210 are produced by Achima, France, and ZQ-T400, TMP-1000 and EQ-501 are produced by Nameko New Material science and technology Co., Ltd;
wherein, the anti-hydrolysis agent can adopt carbodiimide or triglycidyl isocyanate;
the invention also provides a preparation method of the bio-based degradable stretch film, which comprises the following steps:
step one, preparing a plasticizer:
mixing glycerol, propylene glycol, sorbitol, glycerol monoacetate, glycerol diacetate and glycerol triacetate in any proportion, adding 0.1-1 wt% of an auxiliary agent (a plasticizing chain extender and a plasticizing catalyst) for addition reaction, controlling the reaction temperature at 30-90 ℃ and the reaction time for 3-4 hours to prepare a plasticizer;
step two, resin modification processing:
a) preparation of polyvinyl alcohol plastic resin (PVA): mixing and stirring the raw materials, heating to raise the temperature for pre-plasticizing reaction at the same time, controlling the heating temperature to be 50-120 ℃, controlling the mixing reaction time to be 30-60 min, and preparing polyvinyl alcohol plastic resin, wherein the melting point of the resin is 145-175 ℃, the melt index is 0.5-10 g/10min (190 ℃, 2.16 Kg), and the thermal deformation temperature is 45-55 ℃;
b) preparation of polyhydroxyalkanoate resin (PHA) granules: the raw materials are melted and extruded to prepare the polyhydroxyalkanoate resin particles, and the resin density is 1.24g/cm3The melting point is 80-160 ℃, the Vicat thermal deformation temperature is 70-80 ℃, the melt index is 5-8 g/10min (190 ℃, under the condition of 2.16 Kg), and the glass state temperature is-20 ℃; or,
preparation of polylactic acid resin (PLA) pellets: melt-extruding the raw materials to obtain polylactic resin particles with the resin density of 1.3 +/-0.1 g/cm3The melting point is 135-141 ℃, the melt index is 3-8 g/10min (190 ℃, 2.16 Kg), and the thermal deformation temperature is 40-50 ℃;
step three, co-extrusion and stretching:
and (3) taking the polyvinyl alcohol plastic resin prepared in the step two as a raw material of a middle layer, and carrying out multilayer co-extrusion and two-way stretching of three layers or five layers and the like on the polyvinyl alcohol plastic resin and the polyhydroxyalkanoate resin particles or polylactic acid resin particles used as raw materials of outer layers on two sides to prepare the bio-based degradable stretch film. Wherein, a compatible adhesive layer can be added between the polyvinyl alcohol plastic resin layer and the polyhydroxyalkanoate resin layer or the polylactic acid resin layer during the five-layer coextrusion. The compatible adhesive can be EMA4210 and EMA3210 produced by Achima, France, or ZQ-T400, TMP-1000 and EQ-501 produced by Hangzhou xi Mao new materials science and technology limited.
By adopting the technical scheme, the invention realizes the compatibility among PVA, PLA and PHA modified resin, organically integrates the material layers into a whole by adopting multilayer co-extrusion and bidirectional stretching processes, and the material properties are complemented and play a role, so that the stretched film has good thermoplasticity, stretchability and high barrier property, PLA and PHA have good moisture resistance, and the PVA barrier layer is placed in the PHA or PLA to realize the effects of gas and water resistance.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
The bio-based degradable tensile membrane comprises a polyvinyl alcohol plastic resin (PVA) layer, wherein a Polyhydroxyalkanoate (PHA) layer is respectively arranged on the inner side and the outer side of the PVA plastic resin layer, namely the tensile membrane is in a PHA/PVA/PHA structure.
The preparation method comprises the following steps:
step one, preparing a plasticizer:
adding 9 mass percent of glycerol, 50 mass percent of glycerol monoacetate, 20 mass percent of glycerol diacetate, 20 mass percent of glycerol triacetate, 0.5 mass percent of 1, 4-butanediol, 0.3 mass percent of adipic acid and 0.2 mass percent of TNP into a reaction kettle for addition reaction, controlling the reaction temperature at 30-90 ℃, reacting for 3 hours, adjusting the pH value to 5-7, cooling and standing to prepare a plasticizer A for later use;
step two, resin modification processing:
a) preparation of polyvinyl alcohol plastic resin (PVA): 100 parts of polyvinyl alcohol; 20 parts of a plasticizer A; 0.2 part of antioxidant K330; 0.2 part of antioxidant K300; 0.6 part of TNP; 0.8 part of lubricant PEG 600; 5 parts of a compatilizer ZQ-T400, mixing and stirring the compatilizer ZQ-T400 in a high-speed mixer, heating the mixture to raise the temperature for pre-plasticizing reaction, controlling the heating temperature to be 50-120 ℃, and controlling the pre-plasticizing mixing reaction time to be 30-60 min to prepare polyvinyl alcohol plastic resin;
b) preparation of polyhydroxyalkanoate resin (PHA) granules: 100 parts of polyhydroxyalkanoate; 5 parts of a plasticizer A; 0.5 part of antioxidant K300; 1.5 parts of extrusion chain extender TMP-6000; 1 part of lubricant oxidized polyethylene wax; 2 parts of lubricant PEG 400; 5 parts of compatilizer ZQ-T400, and performing melt extrusion granulation to prepare polyhydroxyalkanoate resin particles, wherein the melting point is 140 ℃, and the melt index is 5g/10min (190 ℃ and 2.16 Kg);
step three, co-extrusion and stretching:
respectively putting the polyhydroxyalkanoate resin (PHA) particles, polyvinyl alcohol plastic resin (PVA) and polyhydroxyalkanoate resin (PHA) particles prepared in the step two into a three-layer co-extrusion extruder, namely a PHA/PVA/PHA structure, wherein the interlayer thickness ratio is 35%/30%/35%, the thickness of a melt extrusion sheet is 240 microns, introducing into a longitudinal drawing machine, drawing at a temperature of 90-110 ℃, longitudinally drawing 4 times, and longitudinally drawing at a thickness of 60 microns, and transversely drawing 3 times in the longitudinal drawing machine to prepare a 20-micron biaxially oriented film;
example 2
A bio-based degradable stretch film comprises a polyvinyl alcohol plastic resin (PVA) layer, wherein a layer of polylactic acid resin (PLA) layer is respectively arranged on the inner side and the outer side of the PVA plastic resin layer, namely the stretch film is of a PLA/PVA/PLA structure.
The preparation method comprises the following steps:
step one, preparing a plasticizer:
adding 9 mass percent of glycerol, 50 mass percent of glycerol monoacetate, 20 mass percent of glycerol diacetate, 20 mass percent of glycerol triacetate, 0.5 mass percent of 1, 4-butanediol, 0.3 mass percent of adipic acid and 0.2 mass percent of TNP into a reaction kettle for addition reaction, controlling the reaction temperature at 30-90 ℃, reacting for 3 hours, adjusting the pH value to 5-7, cooling and standing to prepare a plasticizer A for later use;
step two, resin modification processing:
a) preparation of polyvinyl alcohol plastic resin (PVA): 100 parts of polyvinyl alcohol; 20 parts of a plasticizer A; 0.2 part of antioxidant K330; 0.2 part of antioxidant K300; 0.6 part of TNP; 0.8 part of lubricant PEG 600; 5 parts of a compatilizer ZQ-T400, mixing and stirring the compatilizer ZQ-T400 in a high-speed mixer, heating the mixture to raise the temperature for pre-plasticizing reaction, controlling the heating temperature to be 50-120 ℃, and controlling the pre-plasticizing mixing reaction time to be 30-60 min to prepare polyvinyl alcohol plastic resin;
b) preparation of polylactic acid resin (PLA) pellets: 100 parts of polylactic acid; 10 parts of a plasticizer A; 0.5 part of antioxidant K300; 0.5 part of an extrusion chain extender; 0.7 part of lubricant liquid paraffin; 5 parts of a compatilizer ZQ-T400; 1 part of compatilizer TMP-1000; 0.3 part of hydrolysis resistant agent is put into a double-screw granulator and is subjected to melt extrusion granulation at the temperature of 120-220 ℃ to prepare polylactic resin particles, the melting point is 141 ℃, and the melt index is 5g/10min (190 ℃ and 2.16 Kg);
step three, co-extrusion and stretching:
respectively putting the polylactic acid resin (PLA) particles, the polyvinyl alcohol plastic resin (PVA) and the polylactic acid resin (PLA) particles prepared in the step two into a three-layer co-extrusion extruder, namely PLA/PVA/PLA, wherein the interlayer thickness ratio is 35%/30%/35%, the thickness of a melt extrusion sheet is 240 microns, introducing the melt extrusion sheet into a longitudinal drawing machine, wherein the longitudinal drawing multiplying power is 3.5 times, the drawing temperature and the film body temperature are 90-105 ℃, the longitudinal drawing thickness is 68 microns, and then, the transverse drawing is 4 times, and the three-layer co-extrusion film product is a 20-micron biaxially oriented film.
Example 3
The bio-based degradable tensile film comprises a polyvinyl alcohol plastic resin (PVA) layer, wherein a Polyhydroxyalkanoate (PHA) layer is respectively arranged on the inner side and the outer side of the PVA plastic resin layer, and a compatible bonding layer is arranged between the PHA layer and the PVA plastic resin (PVA), namely the tensile film is of a five-layer structure of PHA/compatible bonding layer/PVA/compatible bonding layer/PHA.
The preparation method comprises the following steps:
step one, preparing a plasticizer: the same as example 1;
step two, resin modification processing: the same as example 1;
step three, co-extrusion and stretching:
preparing compatible adhesive EMA4210, respectively putting polyhydroxyalkanoate resin (PHA) particles, EMA4210, polyvinyl alcohol plastic resin (PVA), EMA4210 and polyhydroxyalkanoate resin (PHA) particles into a five-layer co-extrusion extruder, namely a PHA/EMA4210/PVA/EMA4210/PHA structure, wherein the interlayer thickness ratio is 35%/30%/35%, melting and extruding a sheet, introducing the sheet with the thickness of 240 mu m into a longitudinal drawing machine, and the drawing ratio is 3.5 times. The stretching temperature and the film body temperature are 90-105 ℃, the film is longitudinally stretched to a thickness of 68 mu m, and then the film is stretched by 4 times in a transverse stretcher to obtain the five-layer co-extruded biaxially oriented film with the thickness of about 20 mu m.
Example 4
A bio-based degradable stretch film comprises a polyvinyl alcohol plastic resin (PVA) layer, wherein one polylactic acid resin (PLA) layer is respectively arranged on the inner side and the outer side of the polyvinyl alcohol plastic resin layer, a compatible bonding layer is arranged between the polylactic acid resin (PLA) layer and the polyvinyl alcohol plastic resin (PVA), namely, the stretch film is of a five-layer structure of PLA/the compatible bonding layer/PVA/the compatible bonding layer/PLA.
The preparation method comprises the following steps:
step one, preparing a plasticizer: the same as example 2;
step two, resin modification processing: the same as example 2;
step three, co-extrusion and stretching:
preparing a compatible adhesive EMA3210, respectively putting polylactic acid resin (PLA) particles, EMA3210, polyvinyl alcohol plastic resin (PVA), EMA3210 and polylactic acid resin (PLA) particles into a five-layer co-extrusion extruder, namely a PLA/EMA3210/PVA/EMA3210/PLA structure, wherein the interlayer thickness ratio is 30%/5%/30%/5%/30%, melting and extruding a sheet with the sheet thickness of 240 microns, introducing the sheet into a longitudinal stretcher for 3.5 times to stretch the film, stretching at 90-110 ℃, longitudinally stretching the film to the thickness of 68 microns, and then introducing the sheet into a transverse stretcher for stretching by 4 times to prepare the five-layer co-extruded biaxially oriented film with the thickness of about 20 microns.
The above description is only an exemplary embodiment of the present invention, and is not intended to limit the scope of the present invention. Any equivalent changes and modifications that can be made by one skilled in the art without departing from the spirit and principles of the invention should fall within the protection scope of the invention.
Claims (10)
1. The bio-based degradable stretch film is characterized in that: the biodegradable plastic film comprises a polyvinyl alcohol plastic resin layer, wherein the inner side and the outer side of the polyvinyl alcohol plastic resin layer are respectively provided with a bio-based degradation barrier layer.
2. The bio-based degradable stretch film of claim 1, wherein: the biological-based degradation barrier layer is a polyhydroxyalkanoate layer or a polylactic acid layer.
3. The bio-based degradable stretch film of claim 2, wherein: and a compatible adhesive layer is arranged between the bio-based degradation barrier layer and the polyvinyl alcohol plastic resin layer.
4. The bio-based degradable stretch film according to claim 2, wherein the polyvinyl alcohol plastic resin layer is made of raw materials comprising, by weight: 80-120 parts of polyvinyl alcohol; 5-30 parts of a plasticizer; 0.1-2 parts of an antioxidant; 0.2-1 part of an extrusion chain extender; 0.2-5 parts of a lubricant; 2-10 parts of a compatilizer.
5. The bio-based degradable stretch film of claim 2, wherein: the polyhydroxy fatty acid ester layer is prepared from the following raw materials in parts by weight: 80-120 parts of polyhydroxyalkanoate; 2-20 parts of a plasticizer; 0.1-2 parts of an antioxidant; 0.5-2.5 parts of an extrusion chain extender; 0.2-5 parts of a lubricant; 2-10 parts of a compatilizer.
6. The bio-based degradable stretch film of claim 2, wherein: the polylactic acid layer is prepared from the following raw materials in parts by weight: 80-120 parts of polylactic acid; 2-20 parts of a plasticizer; 0.1-2 parts of an antioxidant; 0.5-2.5 parts of an extrusion chain extender; 0.2-5 parts of a lubricant; 2-10 parts of a compatilizer; 0.1-2 parts of hydrolysis resistant agent.
7. The biodegradable stretch film of claim 4, 5 or 6, wherein the plasticizer is prepared by: mixing glycerol, propylene glycol, sorbitol, glycerol monoacetate, glycerol diacetate and glycerol triacetate in any proportion, adding an auxiliary agent for addition reaction, controlling the reaction temperature to be 30-90 ℃ and the reaction time to be 3-4 hours; wherein, the weight content of the auxiliary agent is 0.1-1.0%.
8. The bio-based degradable stretch film of claim 7, wherein: the auxiliary agent is
A plasticizing chain extender TNP or 1, 4-Butanediol (BDO);
plasticizing catalyst adipic acid or phosphoric acid.
9. The biodegradable stretch film according to claim 4, 5 or 6, wherein:
the antioxidant is one or a mixture of several of antioxidant 300, antioxidant 330, antioxidant 1010, antioxidant 168, antioxidant 264 or antioxidant 1098 in any proportion;
the lubricant is one or a mixture of more of liquid paraffin, polyethylene glycol, oleamide, erucamide, oxidized polyethylene wax, talcum powder or titanium dioxide in any proportion.
10. A method of making a biodegradable stretch film according to claim 2, comprising the steps of:
step one, preparing a plasticizer:
mixing glycerol, propylene glycol, sorbitol, glycerol monoacetate, glycerol diacetate and glycerol triacetate in any proportion, adding an auxiliary agent with the weight content of 0.1-1% for addition reaction, controlling the reaction temperature at 30-90 ℃ and the reaction time for 3-4 hours to prepare the plasticizer;
step two, resin modification processing:
a) preparing polyvinyl alcohol plastic resin: mixing and stirring the raw materials, heating to raise the temperature for pre-plasticizing reaction, controlling the heating temperature to be 50-120 ℃, and controlling the mixing reaction time to be 30-60 min to prepare polyvinyl alcohol plastic resin;
b) preparing polyhydroxyalkanoate resin particles or polylactic acid resin particles: melting and extruding the raw materials to prepare polyhydroxyalkanoate resin particles or polylactic acid resin particles;
step three, co-extrusion and stretching:
and (3) taking the polyvinyl alcohol plastic resin prepared in the step two as a raw material of the middle layer, and carrying out multilayer co-extrusion and bidirectional stretching on the polyvinyl alcohol plastic resin and the polyhydroxyalkanoate resin particles or polylactic acid resin particles used as raw materials of the outer layers on two sides to prepare the bio-based degradable stretch film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510475039.3A CN105017699A (en) | 2015-08-06 | 2015-08-06 | Bio-based degradable stretched film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510475039.3A CN105017699A (en) | 2015-08-06 | 2015-08-06 | Bio-based degradable stretched film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105017699A true CN105017699A (en) | 2015-11-04 |
Family
ID=54408026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510475039.3A Pending CN105017699A (en) | 2015-08-06 | 2015-08-06 | Bio-based degradable stretched film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105017699A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084675A (en) * | 2016-06-06 | 2016-11-09 | 山东天野生物降解新材料科技有限公司 | A kind of whole life cycle design being beneficial to soil moisture conservation and preparation method thereof |
| CN107627706A (en) * | 2017-09-18 | 2018-01-26 | 上海海洋大学 | Degradable high-barrier active fresh-keeping film and preparation method thereof |
| CN110079891A (en) * | 2019-05-05 | 2019-08-02 | 苏州回蓝环保科技有限公司 | A kind of biodegradable PVA melt spinning resin and its application |
| CN110835417A (en) * | 2019-12-11 | 2020-02-25 | 上海海洋大学 | Barrier degradable antibacterial food preservative film and preparation method and application thereof |
| CN110920159A (en) * | 2019-11-22 | 2020-03-27 | 湖北工业大学 | Polysaccharide/protein composite film with high barrier property and preparation method thereof |
| CN111959080A (en) * | 2020-08-24 | 2020-11-20 | 中国科学院长春应用化学研究所 | Biodegradable multilayer composite barrier film and preparation method thereof |
| CN113773532A (en) * | 2021-08-30 | 2021-12-10 | 武汉华丽环保产业有限公司 | High-transparency biodegradable heat shrinkable film and preparation method thereof |
| CN114213825A (en) * | 2022-01-11 | 2022-03-22 | 南通恒鑫新材料有限公司 | Degradable environment-friendly safe preservative film and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604294A (en) * | 2012-03-13 | 2012-07-25 | 朱春英 | Stretched PVA (polyvinyl alcohol) film and preparation method for same |
-
2015
- 2015-08-06 CN CN201510475039.3A patent/CN105017699A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604294A (en) * | 2012-03-13 | 2012-07-25 | 朱春英 | Stretched PVA (polyvinyl alcohol) film and preparation method for same |
Non-Patent Citations (1)
| Title |
|---|
| 朱洪法、朱玉霞: "《工业助剂手册》", 30 June 2007, 金盾出版社 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084675A (en) * | 2016-06-06 | 2016-11-09 | 山东天野生物降解新材料科技有限公司 | A kind of whole life cycle design being beneficial to soil moisture conservation and preparation method thereof |
| CN106084675B (en) * | 2016-06-06 | 2017-08-29 | 山东天野生物降解新材料科技有限公司 | A kind of whole life cycle design for being beneficial to soil moisture conservation and preparation method thereof |
| CN107627706A (en) * | 2017-09-18 | 2018-01-26 | 上海海洋大学 | Degradable high-barrier active fresh-keeping film and preparation method thereof |
| CN110079891A (en) * | 2019-05-05 | 2019-08-02 | 苏州回蓝环保科技有限公司 | A kind of biodegradable PVA melt spinning resin and its application |
| CN110920159A (en) * | 2019-11-22 | 2020-03-27 | 湖北工业大学 | Polysaccharide/protein composite film with high barrier property and preparation method thereof |
| CN110835417A (en) * | 2019-12-11 | 2020-02-25 | 上海海洋大学 | Barrier degradable antibacterial food preservative film and preparation method and application thereof |
| CN110835417B (en) * | 2019-12-11 | 2022-09-23 | 上海海洋大学 | Barrier degradable antibacterial food preservative film and preparation method and application thereof |
| CN111959080A (en) * | 2020-08-24 | 2020-11-20 | 中国科学院长春应用化学研究所 | Biodegradable multilayer composite barrier film and preparation method thereof |
| CN113773532A (en) * | 2021-08-30 | 2021-12-10 | 武汉华丽环保产业有限公司 | High-transparency biodegradable heat shrinkable film and preparation method thereof |
| CN114213825A (en) * | 2022-01-11 | 2022-03-22 | 南通恒鑫新材料有限公司 | Degradable environment-friendly safe preservative film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105017699A (en) | Bio-based degradable stretched film and preparation method thereof | |
| US10752759B2 (en) | Methods for forming blended films including renewable carbohydrate-based polymeric materials with high blow up ratios and/or narrow die gaps for increased strength | |
| KR101525658B1 (en) | Composition for biomass film using food byproduct of wheat bran or soybean hull and biomass film using thereof | |
| US20090179069A1 (en) | Multilayer film and method for manufacturing same | |
| CN107868630B (en) | Adhesive resin with barrier function and preparation method thereof | |
| CA2725222A1 (en) | Thermoformed article made from bio-based biodegradable polymer composition | |
| KR102269358B1 (en) | Biodegradable soft multilayer food packaging material having improved heat resistance, gas-barrier and light-shielding, and method of manufacturing the same | |
| US10457023B2 (en) | Bi-axially stretched article and silage film | |
| TW200427775A (en) | Poly(glycolic acid)-based resin composition and formed article therefrom | |
| KR101443020B1 (en) | Composition for biomass film and biomass film using thereof | |
| CN103694646A (en) | Polyester/thermoplastic starch biodegradable composition and preparation method thereof | |
| CN113185810B (en) | Renewable high-barrier polyester packaging material and preparation method thereof | |
| US20180186129A1 (en) | Biodegradable sheets | |
| JP2013147609A (en) | Resin composition, molded body, film, and bag | |
| EP3135724B1 (en) | Ethylene-vinylalcohol resin composition, molded product, and multilayer structure | |
| CN111923546B (en) | Environment-friendly degradable waterproof coating packaging paper and preparation method thereof | |
| CN103171219A (en) | Membrane consisting of inner-layer structure and outer-layer structure | |
| JP6452129B2 (en) | Multi-layer film structure containing renewable resource materials | |
| JP5623479B2 (en) | Resin composition, and film and laminate using the same | |
| JP5821365B2 (en) | Method for producing resin composition | |
| CN107618245A (en) | A kind of laminated film and preparation method thereof | |
| JP3535468B2 (en) | Biodegradable laminated film | |
| CN114987017B (en) | Low-migration high-barrier flexible packaging film and preparation method thereof | |
| JP2013049760A (en) | Method of producing resin composition, and methods of producing molded product, film, and bag | |
| JP5750347B2 (en) | Resin composition and multilayer structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhao Yumei Inventor after: Zhu Pengtao Inventor after: Wang Xiaokai Inventor after: Li Guanqun Inventor before: Zhao Yumei Inventor before: Zhu Pengtao Inventor before: Wang Xiaokai |
|
| COR | Change of bibliographic data | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151104 |
|
| RJ01 | Rejection of invention patent application after publication |