CN115320201A - Multilayer high-barrier and high-strength biodegradable film and preparation method thereof - Google Patents
Multilayer high-barrier and high-strength biodegradable film and preparation method thereof Download PDFInfo
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- CN115320201A CN115320201A CN202210710208.7A CN202210710208A CN115320201A CN 115320201 A CN115320201 A CN 115320201A CN 202210710208 A CN202210710208 A CN 202210710208A CN 115320201 A CN115320201 A CN 115320201A
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- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 86
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 78
- 239000010410 layer Substances 0.000 claims abstract description 70
- 239000002344 surface layer Substances 0.000 claims abstract description 61
- 229920001896 polybutyrate Polymers 0.000 claims abstract description 56
- 239000004970 Chain extender Substances 0.000 claims abstract description 52
- 239000008187 granular material Substances 0.000 claims abstract description 48
- 239000002981 blocking agent Substances 0.000 claims abstract description 38
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims abstract description 35
- 229920001432 poly(L-lactide) Polymers 0.000 claims abstract description 35
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920001434 poly(D-lactide) Polymers 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000012792 core layer Substances 0.000 claims abstract description 3
- 239000012754 barrier agent Substances 0.000 claims description 33
- 239000004593 Epoxy Substances 0.000 claims description 29
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000004888 barrier function Effects 0.000 claims description 14
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 10
- -1 glycidoxy Chemical group 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 8
- 235000012424 soybean oil Nutrition 0.000 claims description 8
- 239000003549 soybean oil Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- PDQDVWQFXLXTGU-UHFFFAOYSA-N 2-[1-carboxy-2-(3,5-ditert-butyl-4-hydroxyphenyl)ethyl]sulfanyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(=CC(=C1O)C(C)(C)C)CC(C(=O)O)SC(CC2=CC(=C(C(=C2)C(C)(C)C)O)C(C)(C)C)C(=O)O PDQDVWQFXLXTGU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 210000002615 epidermis Anatomy 0.000 claims 1
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- 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 description 10
- 230000000052 comparative effect Effects 0.000 description 9
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- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 description 1
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/73—Hydrophobic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to the field of composite materials, and discloses a multilayer high-barrier and high-strength biodegradable film and a preparation method thereof. The biodegradable film comprises an upper surface layer, a central layer and a lower surface layer which are sequentially overlapped, wherein the upper surface layer and the lower surface layer comprise the following components: PBAT granules, PDLA granules, a modified gas blocking agent, a chain extender, an antioxidant and a compatilizer; the core layer comprises the following components: PBAT granules, PLLA granules, a chain extender, an antioxidant and a compatilizer. The invention is formed by melting and co-extruding three layers of materials at one time, compared with the traditional processing mode, the invention has simple process, short flow and low cost, and can effectively improve the production efficiency.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a multilayer high-barrier and high-strength biodegradable film and a preparation method thereof.
Background
After the traditional plastic film is used, the natural environment is polluted because the traditional plastic film is not easy to recycle and can be treated in the process of treatment. Biodegradable materials are easy to degrade in natural environment after being used, and do not cause pollution to the environment, and biodegradable film materials gradually become a current research and development hotspot due to the characteristics of no toxicity, wide sources and the like.
However, biodegradable plastics also have some disadvantages in themselves, such as: poor processing thermal stability, incompatibility among most biodegradable plastics, low heat distortion temperature and the like. And the single biodegradable plastic is used as a film material, and the barrier property of the single biodegradable plastic also has certain defects, such as too high oxygen, carbon dioxide and water vapor transmission rate and the like. Therefore, the composite material can be used as a substitute of the traditional plastic film after being compounded to obtain a multilayer material by utilizing the respective gas permeability, mechanical property and the like of different biodegradable materials. However, most biodegradable materials are incompatible, which results in poor compatibility and adhesion between polymers in the layers and between layers of the multilayer composite material, thereby making the physical properties of the multilayer material unstable and easy to delaminate.
CN103640290A discloses a high-barrier complete biodegradation composite membrane, which is a three-layer structure, and the outer layer is PBAT; the middle layer is PPC; the inner layer is PLA. In order to improve the compatibility between the inner layer and the outer layer and the middle layer, two block copolymers of PBA-co-PC and PLA-co-PC are respectively adopted as a compatibilizer. The compatibilization effect of the block copolymers is achieved by entanglement between molecular chains physically, and is less effective than the reactive compatibilizer. And the PBA-co-PC and PLA-co-PC copolymer is obtained by polymerizing isocyanate serving as a chain extender and a conventional technology, the synthesis process is relatively complex, and a large number of byproducts are generated.
In CN107471511A, a layer-by-layer casting method is adopted for methylene dichloride solution dissolved with PBAT and PLA to obtain a PBAT/PLA multilayer composite film, but PBAT and PLA are incompatible, and under the condition that no compatilizer is added, layers are mutually independent and have poor compatibility.
Disclosure of Invention
In order to solve the technical problems, the invention provides a multilayer high-barrier and high-strength biodegradable film and a preparation method thereof. In addition, the three-layer material is formed in one step through melt co-extrusion, compared with the traditional processing mode, the method has the advantages of simple process, short flow and low cost, and can effectively improve the production efficiency.
The technical scheme of the invention is as follows:
a multi-layer high-barrier and high-strength biodegradable film comprises an upper surface layer, a central layer and a lower surface layer which are sequentially overlapped,
the upper and lower skin layers comprise the following ingredients: PBAT granules, PDLA granules, a modified gas blocking agent, a chain extender, an antioxidant and a compatilizer;
the core layer comprises the following components: PBAT granules, PLLA granules, a chain extender, an antioxidant and a compatilizer.
Further, the upper surface layer and the lower surface layer are composed of the following components in parts by weight:
100 parts of PBAT granules;
1-5 parts of PDLA granules;
1-5 parts of modified gas barrier agent;
0.5-3 parts of a chain extender;
0.01-0.5 part of antioxidant;
0.5-3 parts of a compatilizer.
Further, the central layer package comprises the following components in parts by weight:
0-100 parts of PBAT granules;
0-100 parts of PLLA granules;
0.5-5 parts of a chain extender;
0.01-0.5 part of antioxidant;
0.5-5 parts of a compatilizer;
wherein the total parts of the PBAT granules and the PLLA granules are less than or equal to 100 parts.
Further, the modified gas blocking agent is obtained by modifying the modified gas blocking agent through an epoxy silane coupling agent and a gas blocking agent.
Furthermore, the epoxy silane coupling agent is one or a mixture of gamma-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and 3- (2,3 glycidoxy) propylmethyldiethoxysilane.
Further, the gas barrier agent is one or a mixture of montmorillonite and graphene.
Further, the antioxidant is composed of hindered phenol antioxidants and sulfo-lipid antioxidants or phosphite antioxidants, wherein the hindered phenol antioxidants are one or more of pentaerythritol tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 2,2' -thiobis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Further, the compatilizer is one or more of polyethylene glycol 2000, tributyl citrate, maleic anhydride or epoxidized soybean oil.
A preparation method of a multilayer high-barrier and high-strength biodegradable film comprises the following steps:
(1) Placing an epoxy silane coupling agent in a mixed solvent of ethanol and water to prepare a mixed solution;
(2) Dispersing the gas barrier agent in the mixed solution, stirring for reaction for 5-6h, taking the precipitate, and drying at 100-110 ℃ to obtain a modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas blocking agent in a solution of PDLA granules and dimethyl sulfoxide, reacting at high temperature by using N, N-dimethylbenzylamine as a catalyst, and centrifuging and cleaning by using dichloromethane and ethanol after the reaction is finished to obtain a product;
(4) Melting and blending the product, PBAT, a chain extender, an antioxidant and a compatilizer in an extruder to prepare raw materials of an upper surface layer and a lower surface layer;
(5) Uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the PBAT, the PLLA, the chain extender, the antioxidant and the compatilizer are used as raw materials of a central layer.
(6) Respectively putting the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 160-190 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain the biodegradable film.
Further, the concentration of the epoxy silane coupling agent in the mixed solution is 2 to 5wt%.
Compared with the prior art, the invention has the advantages that:
(1) The multilayer high-barrier high-strength biodegradable film has a three-layer structure, and the central layer of the film is a PBAT/PLLA composite layer, so that the film has good ductility and elongation at break and good strength.
(2) The method comprises the steps of modifying a gas blocking agent, enabling the surface of the gas blocking agent to be successfully grafted with epoxy groups, controlling the mass ratio of PDLA to the modified gas blocking agent during reaction, ultrasonically dispersing the modified gas blocking agent in a dimethyl sulfoxide solution of PDLA, using N, N-dimethylbenzylamine as a catalyst, reacting for 25 hours at the temperature of 140 ℃, controlling the mass ratio of the modified gas blocking agent to the PDLA, enabling the epoxy groups on the surface of the modified gas blocking agent to perform a ring-opening reaction with terminal carboxyl groups of the PDLA, and simultaneously remaining a part of the epoxy groups. The modified gas blocking agent with the surface grafted with PDLA still has reaction activity, on one hand, the residual epoxy groups on the surface can react with PBAT in situ, so that the compatibility between polymers PBAT and PDLA in a layer is effectively improved, on the other hand, PDLA on the surface can form a stereo composite crystal with PLLA in a central layer due to strong interaction force among molecules, and most of the stereo composite crystal is positioned on the interface between an upper layer/a lower layer and the central layer under the action force among the molecules at two ends, so that the compatibility between the layers is greatly improved and is more stable. Meanwhile, the modified flaky gas barrier agent is more hydrophobic, so that the barrier property of the modified flaky gas barrier agent is further improved. The existence of the interface stereo composite crystal further improves the mechanical property of the film.
(3) In the multilayer blending, the interaction force between the PBAT chain segment on the surface of the modified gas blocking agent and the PBAT in the layer and the hydrogen bond action of the PDLA chain segment on the surface and the PLLA in the central layer enable most of the modified gas blocking agent to be positioned between the layers under the interaction of the two, so that the compatibility between the layers is more stable.
(4) A stereo composite crystal (the essence of the stereo composite crystal is the hydrogen bond action between PDLA and PLLA) is introduced between layers, so that the oxygen barrier property of the composite film is further improved, and the surface of the gas barrier agent is more hydrophobic after being modified.
(5) The invention forms the three layers of materials at one time through melt coextrusion, compared with the traditional processing mode (laminating adhesion or sheet extending-laminating lamination and the like), the invention has the advantages of simple process, short flow and low cost, and can effectively improve the production efficiency.
Drawings
Figure 1 is a schematic view of the layered structure of a multilayer high barrier, high strength biodegradable film of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
As shown in fig. 1, a multi-layer high-barrier, high-strength biodegradable film includes an upper surface layer, a central layer, and a lower surface layer, which are sequentially stacked. The upper surface layer and the lower surface layer are composed of the following components in parts by weight: 100 parts of PBAT granules, 3 parts of PDLA granules, 2 parts of modified gas blocking agent, 0.5 part of chain extender, 1 part of antioxidant and 0.5 part of compatilizer, wherein the chain extender is ADR-4370S, the compatilizer is polyethylene glycol 2000, and the antioxidant adopts 0.5 part of antioxidant 168 and 0.5 part of antioxidant 1010;
the central layer comprises the following components in parts by weight: 50 parts of PBAT granules, 50 parts of PLLA granules, 3.5 parts of a chain extender, 0.02 part of an antioxidant and 2 parts of a compatilizer, wherein the chain extender is ADR-4370S, the compatilizer is polyethylene glycol 2000, and the antioxidant adopts 0.01 part of antioxidant 168 and 0.01 part of antioxidant 1010.
The modified gas barrier agent is obtained by modifying an epoxy silane coupling agent and a gas barrier agent, wherein the epoxy silane coupling agent is gamma-glycidyl ether oxygen propyl trimethoxy silane, and the gas barrier agent is montmorillonite.
The antioxidant consists of hindered phenol antioxidant and sulfo-ester antioxidant or phosphite antioxidant, wherein the hindered phenol antioxidant is tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
A preparation method of a multilayer high-barrier and high-strength biodegradable film comprises the following steps;
(1) Placing the epoxy silane coupling agent in a mixed solvent of ethanol and water to prepare a mixed solution, wherein the concentration of the epoxy silane coupling agent in the mixed solution is 2wt%;
(2) Dispersing the gas barrier agent in the mixed solution, stirring for reaction for 5 hours, taking the precipitate, and drying at the temperature of 100 ℃ to obtain a modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas blocking agent with the mass ratio of 2;
(4) Melting and blending the product, the PBAT, the chain extender, the antioxidant and the compatilizer in an extruder to prepare raw materials of an upper surface layer and a lower surface layer;
(5) Uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the PBAT, the PLLA, the chain extender, the antioxidant and the compatilizer are used as raw materials of a central layer.
(6) And respectively feeding the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 180 ℃, extruding three strands of materials through a co-extrusion molding machine, and sequentially rolling, cooling, drawing and shearing to obtain the biodegradable film. A
Example 2
As shown in fig. 1, a multi-layer high-barrier, high-strength biodegradable film includes an upper surface layer, a central layer, and a lower surface layer, which are sequentially stacked. The upper surface layer and the lower surface layer are composed of the following components in parts by weight: 100 parts of PBAT granules, 2 parts of PDLA granules, 3 parts of modified gas blocking agent, 0.7 part of chain extender, 0.8 part of antioxidant and 1.1 part of compatilizer, wherein the chain extender is SAG, the compatilizer is mixed maleic anhydride and epoxidized soybean oil, and the antioxidant adopts 0.5 part of antioxidant 168 and 0.4 part of antioxidant 1010;
the central layer comprises the following components in parts by weight: 55 parts of PBAT granules, 45 parts of PLLA granules, 4.2 parts of a chain extender, 0.2 part of an antioxidant and 2.3 parts of a compatilizer, wherein the chain extender is SAG, the compatilizer is mixed maleic anhydride and epoxidized soybean oil, and the antioxidant adopts 0.1 part of antioxidant 168 and 0.1 part of antioxidant 1010.
The modified gas blocking agent is obtained by modifying an epoxy silane coupling agent and a gas blocking agent, wherein the epoxy silane coupling agent is 3-glycidyl ether oxypropyl triethoxysilane, and the gas blocking agent is montmorillonite.
The antioxidant consists of hindered phenol antioxidant and thioester antioxidant or phosphite antioxidant, wherein the hindered phenol antioxidant is beta- (3,5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate.
A preparation method of a multilayer high-barrier and high-strength biodegradable film comprises the following steps;
(1) Placing the epoxy silane coupling agent in a mixed solvent of ethanol and water to prepare a mixed solution, wherein the concentration of the epoxy silane coupling agent in the mixed solution is 4wt%;
(2) Dispersing the gas barrier agent in the mixed solution, stirring and reacting for 6 hours, taking the precipitate, and drying at the temperature of 110 ℃ to obtain the modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas blocking agent with the mass ratio of 2;
(4) Melting and blending the product, PBAT, a chain extender, an antioxidant and a compatilizer in an extruder to prepare raw materials of an upper surface layer and a lower surface layer;
(5) Uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the PBAT, the PLLA, the chain extender, the antioxidant and the compatilizer are used as raw materials of a central layer.
(6) Respectively putting the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 180 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain the biodegradable film.
Example 3
As shown in fig. 1, a multi-layer high-barrier, high-strength biodegradable film includes an upper surface layer, a central layer, and a lower surface layer, which are sequentially stacked. The upper surface layer and the lower surface layer are composed of the following components in parts by weight: 100 parts of PBAT granules, 4 parts of PDLA granules, 1 part of modified gas blocking agent, 0.8 part of chain extender, 1 part of antioxidant and 1.3 parts of compatilizer, wherein the chain extender is EGM, the compatilizer is tributyl citrate, and the antioxidant adopts 0.55 part of antioxidant 168 and 0.45 part of antioxidant 1010;
the central layer comprises the following components in parts by weight: 45 parts of PBAT granules, 55 parts of PLLA granules, 3.8 parts of a chain extender, 0.1 part of an antioxidant and 2.1 parts of a compatilizer, wherein the chain extender is EGM, the compatilizer is tributyl citrate, and the antioxidant adopts 0.05 part of antioxidant 168 and 0.05 part of antioxidant 1010.
The modified gas blocking agent is obtained by modifying an epoxy silane coupling agent and a gas blocking agent, wherein the epoxy silane coupling agent is mixed 3-glycidoxypropyltriethoxysilane and 3- (2,3 glycidoxy) propylmethyldiethoxysilane, and the gas blocking agent is montmorillonite.
The antioxidant consists of hindered phenol antioxidant and sulfo-lipid antioxidant or phosphite antioxidant, wherein the hindered phenol antioxidant is mixed beta- (3,5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate and 2,2' -thiobis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ].
A preparation method of a multilayer high-barrier and high-strength biodegradable film comprises the following steps;
(1) Placing the epoxy silane coupling agent in a mixed solvent of ethanol and water to prepare a mixed solution, wherein the concentration of the epoxy silane coupling agent in the mixed solution is 3wt%;
(2) Dispersing the gas barrier agent in the mixed solution, stirring for reaction for 5.5h, taking the precipitate, and drying at 105 ℃ to obtain a modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas blocking agent with the mass ratio of 2;
(4) Melting and blending the product, the PBAT, the chain extender, the antioxidant and the compatilizer in an extruder to prepare raw materials of an upper surface layer and a lower surface layer;
(5) Uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the PBAT, the PLLA, the chain extender, the antioxidant and the compatilizer are used as raw materials of a central layer.
(6) And respectively feeding the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 180 ℃, extruding three strands of materials through a co-extrusion molding machine, and sequentially rolling, cooling, drawing and shearing to obtain the biodegradable film.
Example 4
As shown in fig. 1, a multi-layer high-barrier, high-strength biodegradable film includes an upper surface layer, a central layer, and a lower surface layer, which are sequentially stacked. The upper surface layer and the lower surface layer are composed of the following components in parts by weight: 100 parts of PBAT granules, 2 parts of PDLA granules, 1 part of modified gas blocking agent, 0.9 part of chain extender, 0.66 part of antioxidant and 0.9 part of compatilizer, wherein the chain extender is SAG, the compatilizer is mixed maleic anhydride and epoxidized soybean oil, and the antioxidant adopts 0.33 part of antioxidant 168 and 0.33 part of antioxidant 1010;
the central layer comprises the following components in parts by weight: 55 parts of PBAT granules, 45 parts of PLLA granules, 3.8 parts of a chain extender, 0.6 part of an antioxidant and 2.3 parts of a compatilizer, wherein the chain extender is SAG, the compatilizer is mixed maleic anhydride and epoxidized soybean oil, and the antioxidant adopts 0.3 part of antioxidant 168 and 0.3 part of antioxidant 1010.
The modified gas blocking agent is obtained by modifying an epoxy silane coupling agent and a gas blocking agent, wherein the epoxy silane coupling agent is 3-glycidyl ether oxypropyl triethoxysilane, and the gas blocking agent is montmorillonite.
The antioxidant consists of hindered phenol antioxidant and sulfo-ester antioxidant or phosphite antioxidant, wherein the hindered phenol antioxidant is beta- (3,5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate.
A preparation method of a multilayer high-barrier and high-strength biodegradable film comprises the following steps;
(1) Placing the epoxy silane coupling agent in a mixed solvent of ethanol and water to prepare a mixed solution, wherein the concentration of the epoxy silane coupling agent in the mixed solution is 4wt%;
(2) Dispersing the gas barrier agent in the mixed solution, stirring and reacting for 6 hours, taking the precipitate, and drying at the temperature of 110 ℃ to obtain a modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas blocking agent with the mass ratio of 2;
(4) Melting and blending the product, PBAT, a chain extender, an antioxidant and a compatilizer in an extruder to prepare raw materials of an upper surface layer and a lower surface layer;
(5) Uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the PBAT, the PLLA, the chain extender, the antioxidant and the compatilizer are used as raw materials of a central layer.
(6) Respectively putting the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 180 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain the biodegradable film.
Example 5
As shown in fig. 1, a multi-layer high-barrier, high-strength biodegradable film includes an upper surface layer, a central layer, and a lower surface layer, which are sequentially stacked. The upper surface layer and the lower surface layer are composed of the following components in parts by weight: 100 parts of PBAT granules, 0.5 part of PDLA granules, 0.5 part of modified gas blocking agent, 1.5 parts of chain extender, 0.88 part of antioxidant and 1.4 parts of compatilizer, wherein the chain extender is SAG, the compatilizer is epoxidized soybean oil, and the antioxidant adopts 0.33 part of antioxidant 168 and 0.33 part of antioxidant 1010;
the central layer comprises the following components in parts by weight: 55 parts of PBAT granules, 45 parts of PLLA granules, 3.8 parts of a chain extender, 0.6 part of an antioxidant and 2.3 parts of a compatilizer, wherein the chain extender is SAG, the compatilizer is mixed tributyl citrate and epoxidized soybean oil, and the antioxidant adopts 0.42 part of antioxidant 168 and 0.46 part of antioxidant 1010.
The modified gas barrier agent is obtained by modifying an epoxy silane coupling agent and a gas barrier agent, wherein the epoxy silane coupling agent is 3- (2,3 epoxypropoxy) propyl methyl diethoxysilane, and the gas barrier agent is montmorillonite.
The antioxidant consists of hindered phenol antioxidant and sulfo-lipid antioxidant or phosphite antioxidant, wherein the hindered phenol antioxidant is 2,2' -thiobis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ].
A preparation method of a multilayer high-barrier and high-strength biodegradable film comprises the following steps;
(1) Placing the epoxy silane coupling agent in a mixed solvent of ethanol and water to prepare a mixed solution, wherein the concentration of the epoxy silane coupling agent in the mixed solution is 5wt%;
(2) Dispersing the gas barrier agent in the mixed solution, stirring and reacting for 6 hours, taking the precipitate, and drying at the temperature of 110 ℃ to obtain a modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas blocking agent with the mass ratio of 2;
(4) Melting and blending the product, PBAT, a chain extender, an antioxidant and a compatilizer in an extruder to prepare raw materials of an upper surface layer and a lower surface layer;
(5) Uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the PBAT, the PLLA, the chain extender, the antioxidant and the compatilizer are used as raw materials of a central layer.
(6) Respectively putting the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 180 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain the biodegradable film.
Comparative example 1
PDLA in example 1 was replaced by PLLA, and the rest of the formulation and preparation method were not changed
Comparative example 2
The modified gas barrier agent in the embodiment 1 does not react with the PDLA granules, and the rest proportion and the preparation method are unchanged;
comparative example 3
The modified gas barrier agent in example 1 was changed to a gas barrier agent, and the remaining proportions and preparation methods were unchanged.
Examples 1 to 5 and comparative examples 1 to 3 were tested for tensile strength, elongation at break and impact resilience according to GB/T528-1998 determination of tensile stress strain Properties of vulcanizates or thermoplastic rubbers, and examples 1 to 5 and comparative examples 1 to 3 were tested for oxygen transmission according to GB/T1038-2000, the results of which are shown in Table 1.
Table 1: results of testing the materials of examples 1-5 and comparative examples 1-3;
from the above test data, it can be seen that the multilayer high barrier, high strength biodegradable film of the present invention has excellent tensile strength, elongation at break, impact resilience, and low oxygen transmission rate.
The difference between the example 4 and the comparative example 1 is that the PDLA filler of the upper and lower surface layers is replaced by PLLA, and the original intermolecular strong acting force between the PDLA of the upper and lower surface layers and the PLLA of the central layer is changed into the physical entanglement of molecular chains between the PLLA of the upper and lower surface layers and the PLLA of the central layer, so that on one hand, the acting force is weakened, the compatibility between the layers is reduced, and the mechanical property is lowered; on the other hand, the disappearance of the stereocomplex crystals causes an increase in the oxygen transmission rate.
The difference between the comparative example 2 and the example 1 is that the modified gas barrier agent does not react with PDLA granules, and directly performs melt blending with PDLA and PBAT, and as the reactivity of an epoxy group and a carboxyl end group of the PBAT is greater than that of the PDLA, more modified epoxy montmorillonite is smaller on a layer-to-layer interface in the phase of the PBAT, and further the mechanical property of the composite film is reduced.
The difference between the comparative example 3 and the example 4 is that the gas barrier agent is not modified, so that the gas barrier agent cannot react with PDLA and PBAT in situ, cannot play a role in compatibilization, and causes poor mechanical property and barrier property.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The utility model provides a biodegradable film of multilayer high resistant separates, high strength, includes superimposed upper epidermis, centre layer and lower top layer in proper order, its characterized in that:
the upper and lower skin layers comprise the following ingredients: PBAT granules, PDLA granules, a modified gas blocking agent, a chain extender, an antioxidant and a compatilizer;
the core layer comprises the following components: PBAT granules, PLLA granules, a chain extender, an antioxidant and a compatilizer.
2. The multilayer high barrier, high strength biodegradable film of claim 1, wherein: the upper surface layer and the lower surface layer are composed of the following components in parts by weight:
100 parts of PBAT granules;
1-5 parts of PDLA granules;
1-5 parts of modified gas barrier agent;
0.5-3 parts of a chain extender;
0.01-0.5 part of antioxidant;
0.5-3 parts of a compatilizer.
3. The multilayer high barrier, high strength biodegradable film of claim 1, wherein: the central layer package comprises the following components in parts by weight:
0-100 parts of PBAT granules;
0-100 parts of PLLA granules;
0.5-5 parts of a chain extender;
0.01-0.5 part of antioxidant;
0.5-5 parts of a compatilizer;
wherein the total parts of the PBAT granules and the PLLA granules are less than or equal to 100 parts.
4. The multilayer high barrier, high strength biodegradable film of claim 1, wherein: the modified gas blocking agent is obtained by modifying the epoxy silane coupling agent and the gas blocking agent.
5. The multilayer high barrier, high strength biodegradable film according to claim 4, wherein: the epoxy silane coupling agent is one or a mixture of gamma-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and 3- (2,3 glycidoxy) propylmethyldiethoxysilane.
6. The multilayer high barrier, high strength biodegradable film according to claim 3, wherein: the gas barrier agent is one or a mixture of montmorillonite and graphene.
7. The multilayer high barrier, high strength biodegradable film of claim 1, wherein: the antioxidant consists of hindered phenol antioxidants and sulfo-lipid antioxidants or phosphite antioxidants, wherein the hindered phenol antioxidants are one or more of pentaerythritol tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 2,2' -thiobis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ].
8. The multilayer high barrier, high strength biodegradable film of claim 1, wherein: the compatilizer is one or more of polyethylene glycol 2000, tributyl citrate, maleic anhydride or epoxidized soybean oil.
9. A method of making a multilayer high barrier, high strength biodegradable film as defined in any of claims 1-8, comprising the steps of;
(1) Placing an epoxy silane coupling agent in a mixed solvent of ethanol and water to prepare a mixed solution;
(2) Dispersing the gas barrier agent in the mixed solution, stirring for reaction for 5-6h, taking the precipitate, and drying at 100-110 ℃ to obtain a modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas blocking agent in a solution of PDLA granules and dimethyl sulfoxide, reacting at high temperature by using N, N-dimethylbenzylamine as a catalyst, and centrifugally cleaning by using dichloromethane and ethanol after the reaction is finished to obtain a product;
(4) Melting and blending the product, PBAT, a chain extender, an antioxidant and a compatilizer in an extruder to prepare raw materials of an upper surface layer and a lower surface layer;
(5) Uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the PBAT, the PLLA, the chain extender, the antioxidant and the compatilizer are used as raw materials of a central layer.
(6) Respectively putting the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 160-190 ℃, extruding three strands of materials through a co-extrusion molding machine, and then sequentially rolling, cooling, drawing and shearing to obtain the biodegradable film.
10. The method for preparing a multilayer high-barrier high-strength biodegradable film according to claim 9, wherein the concentration of the epoxy silane coupling agent in the mixed solution is 2-5wt%.
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