WO2024021039A1 - 基于聚丁内酰胺的可降解多层复合膜及制备方法与应用 - Google Patents

基于聚丁内酰胺的可降解多层复合膜及制备方法与应用 Download PDF

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WO2024021039A1
WO2024021039A1 PCT/CN2022/109034 CN2022109034W WO2024021039A1 WO 2024021039 A1 WO2024021039 A1 WO 2024021039A1 CN 2022109034 W CN2022109034 W CN 2022109034W WO 2024021039 A1 WO2024021039 A1 WO 2024021039A1
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polybutyrolactam
layer
film
barrier layer
liquid
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French (fr)
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赵黎明
张迪
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华东理工大学
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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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/32—Making multilayered or multicoloured articles
    • 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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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

Definitions

  • the invention belongs to the technical field of polymer composite material preparation, and in particular relates to a degradable multi-layer composite film based on polybutyrolactam and its preparation method and application.
  • biodegradable materials including polylactic acid, polycaprolactone, cellulose, starch and other biodegradable materials have achieved industrial production due to their low cost and special performance in the field of food packaging.
  • films made from a single polymer often struggle to meet the oxygen and water barrier requirements of specific food packaging.
  • PA4 Polybutyrolactam
  • GABA ⁇ -aminobutyric acid
  • polyester biodegradable materials including polylactic acid, polycaprolactone, polyhydroxy fatty acid, etc., all of which It shows good hydrophobicity and excellent moisture barrier properties, and can be used in combination with PA4 to achieve synergistic effects.
  • polyester biodegradable materials such as polybutyrolactam and polylactic acid have poor affinity. Phase separation will occur when they are directly blended, resulting in changes in material properties. Difference.
  • Chinese patent CN 111269426 B discloses a method for preparing a polylactic acid-polybutyrolactam biodegradable copolymer.
  • the thiol-terminated polylactic acid and the alkenyl- or alkynyl-terminated polybutyrolactam are passed through thiene or mercaptyyne.
  • the click reaction obtains polylactic acid-polybutyrolactam biodegradable copolymer, and the new material is endowed with special properties by controlling the components.
  • this method is complex to operate and difficult to shape the copolymer product, making it difficult to take advantage of the performance of both.
  • the present invention provides a degradable multi-layer composite film based on polybutyrolactam and its preparation method and application.
  • the present invention uses a solution layer-by-layer casting method to prepare a degradable multi-layer composite film based on polybutyrolactam.
  • the method has a simple process route, and the layers of the composite film are closely adhered and difficult to separate.
  • the composite film exhibits excellent Oxygen barrier, moisture barrier, mechanical strength, etc., can meet the performance requirements of food packaging materials.
  • the invention first provides a degradable multi-layer composite film based on polybutyrolactam.
  • the multi-layer composite film is composed of an oxygen barrier layer, a bonding layer and a moisture barrier layer.
  • the oxygen barrier layer is polybutyrolactam.
  • the adhesive layer is polyvinyl alcohol (PVA), and the moisture barrier layer is a polyester hydrophobic biodegradable polymer.
  • the multilayer composite film is provided with at least three layers, and the oxygen barrier layer, the adhesive layer and the moisture barrier layer are each provided with at least one layer.
  • the combination of the multi-layer composite film is selected from: oxygen barrier layer/adhesive layer/moisture barrier layer, oxygen barrier layer/adhesive layer/moisture barrier layer/adhesive layer/barrier layer Oxygen layer, moisture barrier layer/adhesive layer/oxygen barrier layer/adhesive layer/moisture barrier layer, moisture barrier layer/adhesive layer/oxygen barrier layer/adhesive layer/oxygen barrier layer/adhesive layer/moisture barrier layer .
  • the polyester hydrophobic biodegradable polymer is selected from polylactic acid, polycaprolactone, polycarbonate, polyhydroxy fatty acid, polyethylene furandicarboxylate, polybutylene One or a combination of butylene diphosphate, polypropylene carbonate or polybutylene adipate/terephthalate.
  • the degradable multi-layer composite film based on polybutyrolactam is a polybutyrolactam/polyvinyl alcohol/polyester three-layer composite film, polybutyrolactam film, polyvinyl alcohol film, poly The mass ratio of ester film is (1 ⁇ 20):1:(1 ⁇ 20).
  • the present invention further provides a method for preparing a polybutyrolactam-based degradable multi-layer composite film.
  • the solution casting method is used to form a film layer by layer to obtain the polybutyrolactam-based degradable multi-layer composite film.
  • a method for preparing a polybutyrolactam-based degradable multilayer composite membrane includes the following steps:
  • Polybutyrolactam, polyvinyl alcohol, and polyester hydrophobic biodegradable polymers are dissolved in good solvents to prepare film-forming liquids;
  • polybutyrolactam film liquid On the substrate, polybutyrolactam film liquid, polyvinyl alcohol film liquid, and polyester hydrophobic biodegradable polymer film liquid are cast sequentially, and the next layer of film liquid is cast after the solvent of the previous layer of film liquid evaporates and dries up.
  • the film is finally peeled off from the substrate to obtain a degradable multilayer composite film based on polybutyrolactam.
  • the polybutyrolactam membrane liquid is prepared by dissolving polybutyrolactam in a formic acid/water mixed solution, the volume ratio of formic acid to water is 50:50-100:0, and the solute concentration is 50 ⁇ 100mg/mL, stir evenly at room temperature to obtain polybutyrolactam film liquid.
  • the polyvinyl alcohol film liquid is prepared by dissolving polyvinyl alcohol in deionized water with a solute concentration of 5 to 30 mg/mL, and stirring uniformly at 70 to 90°C to obtain a polyvinyl alcohol film liquid.
  • the polyester hydrophobic biodegradable polymer film liquid is prepared by dissolving the polyester hydrophobic biodegradable polymer in chloroform, trifluoroacetic acid or trifluoroethanol, and the solute concentration The concentration is 30 to 50 mg/mL, stir evenly at room temperature to obtain a polyester hydrophobic biodegradable polymer film liquid.
  • the volume ratio range of polybutyrolactam film liquid, polyvinyl alcohol film liquid, and polyester hydrophobic biodegradable polymer film liquid during casting and molding is 10:1:10 ⁇ 1: 1:1.
  • the substrate is selected from glass or polytetrafluoroethylene.
  • the present invention further provides the application of the polybutyrolactam-based degradable multi-layer composite film.
  • the polybutyrolactam-based degradable multi-layer composite film has excellent barrier properties and mechanical strength and can be directly used as a packaging film. .
  • the invention provides a method for preparing a degradable multi-layer composite film based on polybutyrolactam by using a solution layer-by-layer casting method.
  • the film is cast in the order of oxygen barrier layer-bonding layer-moisture barrier layer. After the solvent of the first layer of film is evaporated and formed, the next layer of film is continued to be cast to form a multi-layer film system.
  • the present invention uses polyvinyl alcohol as the adhesive layer. On the one hand, it utilizes the penetration of the casting solution into the substrate polymer; on the other hand, it utilizes the hydroxyl groups on the polyvinyl alcohol molecular chain to interact with the carbonyl groups and polyester groups in the polyester material structure.
  • the hydrogen bonding effect of the amine groups in the amide material structure allows the layers to penetrate each other and adhere tightly, solving the problem of poor compatibility and easy delamination between polybutyrolactam and polyester materials, and achieving excellent moisture resistance and barrier properties.
  • Multi-layer composite films with excellent oxygen and mechanical properties are expected to be widely used in the field of food packaging.
  • the polybutyrolactam-based degradable multi-layer composite film prepared by the solution layer-by-layer assembly method of the present invention significantly improves the water vapor barrier properties, thermal stability, and light transmittance of polybutyrolactam. etc., and the process route of this method is simple, easy to control and implement, the prepared composite material shows excellent barrier properties, mechanical strength and toughness, high transparency, and has wide applications in the field of biodegradable food packaging.
  • Figure 1 Schematic diagram of the structure of the polybutyrolactam/polyvinyl alcohol/polylactic acid three-layer composite membrane in Example 1.
  • the invention first provides a degradable multi-layer composite film based on polybutyrolactam.
  • the multi-layer composite film is composed of an oxygen barrier layer, a bonding layer and a moisture barrier layer.
  • the oxygen barrier layer is polybutyrolactam.
  • the adhesive layer is polyvinyl alcohol, and the moisture barrier layer is polyester hydrophobic biodegradable polymer.
  • the combination method of the multi-layer composite film is selected from: oxygen barrier layer/adhesive layer/moisture barrier layer, oxygen barrier layer/adhesive layer/moisture barrier layer/adhesive layer/oxygen barrier layer, moisture barrier layer/adhesion Layer/oxygen barrier layer/adhesive layer/moisture barrier layer, moisture barrier layer/adhesive layer/oxygen barrier layer/adhesive layer/oxygen barrier layer/adhesive layer/moisture barrier layer.
  • the polyester hydrophobic biodegradable polymer is selected from polylactic acid, polycaprolactone, polycarbonate, polyhydroxy fatty acid, polyethylene furandicarboxylate, polybutylene One or a combination of butylene diphosphate, polypropylene carbonate or polybutylene adipate/terephthalate.
  • the present invention further provides a method for preparing a polybutyrolactam-based degradable multilayer composite film.
  • the solution casting method is used to form and assemble the film layer by layer to obtain the polybutyrolactam-based degradable multilayer composite film, which specifically includes the following steps. :
  • Polybutyrolactam, polyvinyl alcohol, and polyester hydrophobic biodegradable polymers are dissolved in good solvents to prepare film-forming liquids;
  • polybutyrolactam film liquid On the substrate, polybutyrolactam film liquid, polyvinyl alcohol film liquid, and polyester hydrophobic biodegradable polymer film liquid are cast sequentially, and the next layer of film liquid is cast after the solvent of the previous layer of film liquid evaporates and dries up.
  • the film is peeled off from the substrate to obtain a degradable multilayer composite film based on polybutyrolactam.
  • the polybutyrolactam membrane liquid is prepared by dissolving polybutyrolactam in a formic acid/water mixed solution, the volume ratio of formic acid to water is 50:50-100:0, and the solute concentration is 50 ⁇ 100mg/mL, stir evenly at room temperature to obtain polybutyrolactam film liquid.
  • the preparation method of the polyvinyl alcohol film liquid is to dissolve polyvinyl alcohol in deionized water, with a solute concentration of 5 to 30 mg/mL, and stir evenly at 70 to 90°C to obtain a polyvinyl alcohol film liquid.
  • the polyester hydrophobic biodegradable polymer film liquid is prepared by dissolving the polyester hydrophobic biodegradable polymer in chloroform, trifluoroacetic acid or trifluoroethanol, with a solute concentration of 30 to 50 mg/mL at room temperature. Stir evenly to obtain a polyester hydrophobic biodegradable polymer film liquid.
  • the volume ratio of polybutyrolactam membrane liquid, polyvinyl alcohol membrane liquid, and polyester hydrophobic biodegradable polymer membrane liquid ranges from 10:1:10 to 1:1:1.
  • the present invention further provides the application of the polybutyrolactam-based degradable multi-layer composite film, and the polybutyrolactam-based degradable multi-layer composite film is used to prepare a packaging film.
  • a polylactic acid membrane liquid with a solute fraction of 50 mg/mL was prepared by dissolving it in chloroform at room temperature. All solutions were stirred at room temperature for 24 h.
  • the structure is shown in Figure 1.
  • the mass ratio of polybutyrolactam film, polyethylene film, and polylactic acid film is 5:1. :5.
  • the properties of the prepared multilayer composite materials are shown in Appendix Table 1.
  • a polylactic acid membrane liquid with a solute fraction of 50 mg/mL was prepared by dissolving it in chloroform at room temperature. All solutions were stirred at room temperature for 24 h.
  • a polylactic acid membrane liquid with a solute fraction of 50 mg/mL was prepared by dissolving it in chloroform at room temperature. All solutions were stirred at room temperature for 24 h.
  • the polybutyrolactam/polyvinyl alcohol/polylactic acid three-layer composite film prepared in Examples 1-3 exhibits excellent barrier properties, mechanical strength and toughness, and high transparency.

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Abstract

一种基于聚丁内酰胺的可降解多层复合膜，所述多层复合膜由阻氧层、粘结层和阻湿层组成，所述阻氧层为聚丁内酰胺，所述粘结层为聚乙烯醇，所述阻湿层为聚酯类疏水性生物可降解聚合物；所述的多层复合膜表现出优异的阻隔性、机械强度和韧性，在生物降解的食品包装领域具有广泛的应用。

Description

基于聚丁内酰胺的可降解多层复合膜及制备方法与应用 技术领域
本发明属于高分子复合材料制备技术领域，尤其是涉及一种基于聚丁内酰胺的可降解多层复合膜及制备方法与应用。
背景技术
传统的塑料制品在生态环境中难以自然降解，因此人们期待开发出可生物降解替代品来缓解日益严重的环境问题。包括聚乳酸、聚己内酯、纤维素、淀粉等多种生物可降解材料因其在食品包装领域中的低成本及特别的性能等优势已经实现了工业化生产。然而，由单一聚合物制备的薄膜通常难以满足特定食品包装的隔氧隔水需求。
聚丁内酰胺(Polybutyrolactam，PA4)是目前唯一的生物基且生物可降解聚酰胺类材料，是一种生物基聚合物，其单体2-吡咯烷酮可以由生物质衍生的γ-氨基丁酸(γ-aminobutyric acid，GABA)合成。同时研究表明，PA4可以在海洋、土壤、活性污泥等自然条件下短期内发生降解，具有优异的生物降解性。PA4结构的刚性赋予其高熔点、高氧气阻隔性和高强度等特点，但是PA4表现出较高的亲水性，对水蒸气阻隔性较差。
将PA4与疏水性生物可降解材料复合是一种有效改善材料性能的方式，当前已经开发出多种聚酯类生物可降解材料，包括聚乳酸、聚己内酯、聚羟基脂肪酸等，他们均表现出良好的疏水性，具有优异的阻湿性能，能够与PA4复合使用，达到协同增效的作用。然而由于链段间的分子间相互作用力较弱，聚丁内酰胺和聚乳酸等聚酯类生物可降解材料的亲和性较差，直接共混使用时会出现相分离，导致材料性能变差。中国专利CN 111269426 B公开了一种聚乳酸-聚丁内酰胺生物基可降解共聚物的制备方法，将巯基封端的聚乳酸和烯基或炔基封端的聚丁内酰胺通过巯烯或巯炔点击反应得到聚乳酸-聚丁内酰胺生物基可降解共聚物，通过对组份的调控赋予新材料特殊的性质。然而该方法操作复杂，共聚产物成型困难，难以发挥二者性能上的优势。
发明内容
为解决现有技术中聚丁内酰胺复合材料制备复杂或性能较差的缺陷，本发明提供一种基于聚丁内酰胺的可降解多层复合膜及制备方法与应用。
本发明利用溶液逐层流延法制备基于聚丁内酰胺的可降解多层复合膜，该方法工艺路线简单，所制得的复合膜层间紧密粘合，难以分离，复合膜表现出优异的阻氧性、阻湿性、机械强度等，能够满足对食品包装材料性能的要求。
本发明的目的可以通过以下技术方案来实现：
本发明首先提供一种基于聚丁内酰胺的可降解多层复合膜，所述多层复合膜由阻氧层、粘结层和阻湿层组成，所述阻氧层为聚丁内酰胺，所述粘结层为聚乙烯醇(Polyvinyl alcohol，PVA)，所述阻湿层为聚酯类疏水性生物可降解聚合物。
在本发明的一个实施方式中，所述多层复合膜设置至少3层，阻氧层、粘结层和阻湿层分别至少设置1层。
在本发明的一个实施方式中，所述多层复合膜的组合方式选自：阻氧层/粘合层/阻湿层、阻氧层/粘合层/阻湿层/粘合层/阻氧层、阻湿层/粘合层/阻氧层/粘合层/阻湿层、阻湿层/粘合层/阻氧层/粘合层/阻氧层/粘合层/阻湿层。
在本发明的一个实施方式中，所述聚酯类疏水性生物可降解聚合物选自聚乳酸、聚己内酯、聚碳酸酯、聚羟基脂肪酸、聚呋喃二甲酸乙二醇酯、聚丁二酸丁二酯、聚碳酸亚丙酯或聚己二酸/对苯二甲酸丁二酯中的一种或几种的组合。
在本发明的一个实施方式中，基于聚丁内酰胺的可降解多层复合膜为聚丁内酰胺/聚乙烯醇/聚酯三层复合膜，聚丁内酰胺膜、聚乙烯醇膜、聚酯膜质量比为(1～20)：1：(1～20)。
本发明进一步提供基于聚丁内酰胺的可降解多层复合膜的制备方法，采用溶液流延法逐层成膜得到所述基于聚丁内酰胺的可降解多层复合膜。
在本发明的一个实施方式中，基于聚丁内酰胺的可降解多层复合膜的制备方法包括以下步骤：
聚丁内酰胺、聚乙烯醇、聚酯类疏水性生物可降解聚合物分别溶于良溶剂中，以分别制备成膜液；
在基板上，依次浇铸聚丁内酰胺膜液、聚乙烯醇膜液、聚酯类疏水性生物可降解聚合物膜液，且在前一层膜液溶剂挥发干后浇铸下一层膜液，以获得多层膜体系，最后将薄膜从基板上剥离，得到基于聚丁内酰胺的可降解多层复合膜。
在本发明的一个实施方式中，聚丁内酰胺膜液的制备方式为在甲酸/水混合溶 液中溶解聚丁内酰胺，甲酸与水的体积比为50:50～100:0，溶质浓度为50～100mg/mL，室温下搅拌均匀获得聚丁内酰胺膜液。
在本发明的一个实施方式中，聚乙烯醇膜液的制备方法为在去离子水中溶解聚乙烯醇，溶质浓度为5～30mg/mL，70～90℃下搅拌均匀获得聚乙烯醇膜液。
在本发明的一个实施方式中，聚酯类疏水性生物可降解聚合物膜液的制备方式为在氯仿、三氟乙酸或三氟乙醇中溶解聚酯类疏水性生物可降解聚合物，溶质浓度为30～50mg/mL，室温下搅拌均匀获得聚酯类疏水性生物可降解聚合物膜液。
在本发明的一个实施方式中，聚丁内酰胺膜液、聚乙烯醇膜液、聚酯类疏水性生物可降解聚合物膜液浇铸成型时的体积比范围为10:1:10～1:1:1。
在本发明的一个实施方式中，所述基板选择为玻璃或聚四氟乙烯。
本发明进一步提供所述基于聚丁内酰胺的可降解多层复合膜的应用，所述基于聚丁内酰胺的可降解多层复合膜具有优异的阻隔性能和机械强度，可直接作为包装薄膜使用。
本发明提供了一种利用溶液逐层流延法制备基于聚丁内酰胺的可降解多层复合膜的方法，以阻氧层-粘结层-阻湿层的顺序依次流延，在上一层薄膜溶剂挥发成型后再继续流延下一层膜，以形成多层膜体系。本发明以聚乙烯醇作为粘结层，一方面，利用浇铸溶液在基板聚合物中的渗透作用，另一方面，利用聚乙烯醇分子链上的羟基分别与聚酯类材料结构中羰基和聚酰胺材料结构中胺基的氢键作用，使得层间相互渗透并紧密粘合，解决了聚丁内酰胺与聚酯类材料相容性差、易分层的问题，获得了具有优异阻湿性、阻氧性和机械性能的多层复合膜，有望在食品包装领域中广泛应用。
与现有技术相比，本发明通过溶液逐层组装法制备的基于聚丁内酰胺的可降解多层复合膜，显著提高了聚丁内酰胺的水蒸气阻隔性、热稳定性、透光性等，且该方法工艺路线简单，易于控制和实施，制备的复合材料表现出优异的阻隔性、机械强度和韧性，透明度高，在生物降解的食品包装领域具有广泛的应用。
附图说明
图1：实施例1中聚丁内酰胺/聚乙烯醇/聚乳酸三层复合膜结构示意图。
具体实施方式
本发明首先提供一种基于聚丁内酰胺的可降解多层复合膜，所述多层复合膜由阻氧层、粘结层和阻湿层组成，所述阻氧层为聚丁内酰胺，所述粘结层为聚乙烯醇，所述阻湿层为聚酯类疏水性生物可降解聚合物。所述多层复合膜的组合方式选自：阻氧层/粘合层/阻湿层、阻氧层/粘合层/阻湿层/粘合层/阻氧层、阻湿层/粘合层/阻氧层/粘合层/阻湿层、阻湿层/粘合层/阻氧层/粘合层/阻氧层/粘合层/阻湿层。
在本发明的一些实施方式中，所述聚酯类疏水性生物可降解聚合物选自聚乳酸、聚己内酯、聚碳酸酯、聚羟基脂肪酸、聚呋喃二甲酸乙二醇酯、聚丁二酸丁二酯、聚碳酸亚丙酯或聚己二酸/对苯二甲酸丁二酯中的一种或几种的组合。
本发明进一步提供基于聚丁内酰胺的可降解多层复合膜的制备方法，采用溶液流延法逐层成膜组装得到所述基于聚丁内酰胺的可降解多层复合膜，具体包括以下步骤：
聚丁内酰胺、聚乙烯醇、聚酯类疏水性生物可降解聚合物分别溶于良溶剂中，以分别制备成膜液；
在基板上，依次浇铸聚丁内酰胺膜液、聚乙烯醇膜液、聚酯类疏水性生物可降解聚合物膜液，且在前一层膜液溶剂挥发干后浇铸下一层膜液，将膜从基板上剥离，得到基于聚丁内酰胺的可降解多层复合膜。
在本发明的一些实施方式中，聚丁内酰胺膜液的制备方式为在甲酸/水混合溶液中溶解聚丁内酰胺，甲酸与水的体积比为50:50～100:0，溶质浓度为50～100mg/mL，室温下搅拌均匀获得聚丁内酰胺膜液。聚乙烯醇膜液的制备方法为在去离子水中溶解聚乙烯醇，溶质浓度为5～30mg/mL，70～90℃下搅拌均匀获得聚乙烯醇膜液。聚酯类疏水性生物可降解聚合物膜液的制备方式为在氯仿、三氟乙酸或三氟乙醇中溶解聚酯类疏水性生物可降解聚合物，溶质浓度为30～50mg/mL，室温下搅拌均匀获得聚酯类疏水性生物可降解聚合物膜液。聚丁内酰胺膜液、聚乙烯醇膜液、聚酯类疏水性生物可降解聚合物膜液体积比范围为10:1:10～1:1:1。
本发明进一步提供所述基于聚丁内酰胺的可降解多层复合膜的应用，所述基于聚丁内酰胺的可降解多层复合膜用于制备得到包装膜。
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
将聚丁内酰胺溶于甲酸/水(70:30，v/v)混合物中，室温下制备出溶质分数为50mg/mL的聚丁内酰胺膜液。用去离子水在90℃下溶解聚乙烯醇，制得溶质分数为 20mg/mL的PVA膜液。用氯仿在室温下溶解制备了溶质分数为50mg/mL的聚乳酸膜液。所有溶液在室温下搅拌24h。在25cm×25cm的玻璃板上浇铸40mL聚丁内酰胺膜液，35℃、55％RH条件下干燥6h，获得固定在玻璃板上的聚丁内酰胺膜。在干燥的聚丁内酰胺膜上浇铸20mL聚乙烯醇膜液，35℃、55％RH条件下干燥6h后，浇铸40mL聚乳酸膜液，35℃、55％RH条件下干燥2h后，将薄膜从玻璃板上揭下，得到聚丁内酰胺/聚乙烯醇/聚乳酸三层复合膜，结构如图1所示，聚丁内酰胺膜、聚乙烯膜、聚乳酸膜质量比为5：1：5。制备的多层复合材料性能见附表1。
实施例2
将聚丁内酰胺溶于甲酸/水(70:30，v/v)混合物中，室温下制备出溶质分数为50mg/mL的聚丁内酰胺膜液。用去离子水在90℃下溶解聚乙烯醇，制得溶质分数为20mg/mL的PVA膜液。用氯仿在室温下溶解制备了溶质分数为50mg/mL的聚乳酸膜液。所有溶液在室温下搅拌24h。在25cm×25cm的玻璃板上浇铸27mL聚丁内酰胺膜液，35℃、55％RH条件下干燥6h，获得固定在玻璃板上的聚丁内酰胺膜。在干燥的聚丁内酰胺膜上浇铸20mL聚乙烯醇膜液，35℃、55％RH条件下干燥6h后，浇铸54mL聚乳酸膜液，35℃、55％RH条件下干燥2h后，将薄膜从玻璃板上揭下，得到聚丁内酰胺/聚乙烯醇/聚乳酸三层复合膜，三者质量比为3.3：1：6.7。制备的多层复合材料性能见附表1。
实施例3
将聚丁内酰胺溶于甲酸/水(70:30，v/v)混合物中，室温下制备出溶质分数为50mg/mL的聚丁内酰胺膜液。用去离子水在90℃下溶解聚乙烯醇，制得溶质分数为20mg/mL的PVA膜液。用氯仿在室温下溶解制备了溶质分数为50mg/mL的聚乳酸膜液。所有溶液在室温下搅拌24h。在25cm×25cm的玻璃板上浇铸54mL聚丁内酰胺膜液，35℃、55％RH条件下干燥6h，获得固定在玻璃板上的聚丁内酰胺膜。在干燥的聚丁内酰胺膜上浇铸20mL聚乙烯醇膜液，35℃、55％RH条件下干燥6h后，浇铸27mL聚乳酸膜液，35℃、55％RH条件下干燥2h后，将薄膜从玻璃板上揭下，得到聚丁内酰胺/聚乙烯醇/聚乳酸三层复合膜，三者质量比为6.7：1：3.3。制备的多层复合材料性能见附表1。
表1 实施例1-3所得聚丁内酰胺/聚乙烯醇/聚乳酸三层复合膜材料性能
Figure PCTCN2022109034-appb-000001
从表1可以看出，实施例1-3制备得到的聚丁内酰胺/聚乙烯醇/聚乳酸三层复合膜表现出了优异的阻隔性、机械强度和韧性，透明度高。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (10)

  1. 一种基于聚丁内酰胺的可降解多层复合膜，其特征在于，所述多层复合膜由阻氧层、粘结层和阻湿层组成，所述阻氧层为聚丁内酰胺，所述粘结层为聚乙烯醇，所述阻湿层为聚酯类疏水性生物可降解聚合物。
  2. 根据权利要求1所述的一种基于聚丁内酰胺的可降解多层复合膜，其特征在于，所述多层复合膜的组合方式选自：阻氧层/粘合层/阻湿层、阻氧层/粘合层/阻湿层/粘合层/阻氧层、阻湿层/粘合层/阻氧层/粘合层/阻湿层、阻湿层/粘合层/阻氧层/粘合层/阻氧层/粘合层/阻湿层。
  3. 根据权利要求1所述的一种基于聚丁内酰胺的可降解多层复合膜，其特征在于，所述聚酯类疏水性生物可降解聚合物选自聚乳酸、聚己内酯、聚碳酸酯、聚羟基脂肪酸、聚呋喃二甲酸乙二醇酯、聚丁二酸丁二酯、聚碳酸亚丙酯或聚己二酸/对苯二甲酸丁二酯中的一种或几种的组合。
  4. 根据权利要求1所述的一种基于聚丁内酰胺的可降解多层复合膜，其特征在于，基于聚丁内酰胺的可降解多层复合膜为聚丁内酰胺/聚乙烯醇/聚酯三层复合膜，聚丁内酰胺膜、聚乙烯醇膜、聚酯膜质量比为(1～20)：1：(1～20)。
  5. 权利要求1-4中任一项所述基于聚丁内酰胺的可降解多层复合膜的制备方法，其特征在于，包括以下步骤：
    聚丁内酰胺、聚乙烯醇、聚酯类疏水性生物可降解聚合物分别溶于其良溶剂中，以分别制备成膜液；
    在基板上，依次浇铸聚丁内酰胺膜液、聚乙烯醇膜液、聚酯类疏水性生物可降解聚合物膜液，且在前一层膜液溶剂挥发干后浇铸下一层膜液，以获得多层膜体系，最后将薄膜从基板上剥离，得到基于聚丁内酰胺的可降解多层复合膜。
  6. 根据权利要求5所述基于聚丁内酰胺的可降解多层复合膜的制备方法，其特征在于，聚丁内酰胺膜液的制备方式为在甲酸/水混合溶液中溶解聚丁内酰胺，甲酸与水的体积比为50:50～100:0，溶质浓度为50～100mg/mL，室温下搅拌均匀获得聚丁内酰胺膜液。
  7. 根据权利要求5所述基于聚丁内酰胺的可降解多层复合膜的制备方法，其特征在于，聚乙烯醇膜液的制备方法为在去离子水中溶解聚乙烯醇，溶质浓度为5～30mg/mL，70～90℃下搅拌均匀获得聚乙烯醇膜液。
  8. 根据权利要求5所述基于聚丁内酰胺的可降解多层复合膜的制备方法，其特征在于，聚酯类疏水性生物可降解聚合物膜液的制备方式为在氯仿、三氟乙酸或三氟乙醇中溶解聚酯类疏水性生物可降解聚合物，溶质浓度为30～50mg/mL，室温下搅拌均匀获得聚酯类疏水性生物可降解聚合物膜液。
  9. 根据权利要求5所述基于聚丁内酰胺的可降解多层复合膜的制备方法，其特征在于，聚丁内酰胺膜液、聚乙烯醇膜液、聚酯类疏水性生物可降解聚合物膜液浇铸成型时的体积比范围为10:1:10～1:1:1。
  10. 权利要求1-4中任一项所述基于聚丁内酰胺的可降解多层复合膜的应用，其特征在于，所述基于聚丁内酰胺的可降解多层复合膜直接作为包装薄膜使用。
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