CN115464960A - 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 PDFInfo
- Publication number
- CN115464960A CN115464960A CN202210891245.2A CN202210891245A CN115464960A CN 115464960 A CN115464960 A CN 115464960A CN 202210891245 A CN202210891245 A CN 202210891245A CN 115464960 A CN115464960 A CN 115464960A
- Authority
- CN
- China
- Prior art keywords
- polybutyrolactam
- film
- multilayer composite
- polyvinyl alcohol
- layer
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000012528 membrane Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 230000004888 barrier function Effects 0.000 claims abstract description 48
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 44
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 44
- 229920000728 polyester Polymers 0.000 claims abstract description 31
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 26
- 229920002988 biodegradable polymer Polymers 0.000 claims abstract description 25
- 239000004621 biodegradable polymer Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 239000000853 adhesive Substances 0.000 claims description 21
- 230000001070 adhesive effect Effects 0.000 claims description 21
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 20
- 239000004626 polylactic acid Substances 0.000 claims description 20
- -1 polybutylene Polymers 0.000 claims description 19
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- 238000005266 casting Methods 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 4
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 4
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229920006280 packaging film Polymers 0.000 claims description 3
- 239000012785 packaging film Substances 0.000 claims description 3
- 239000004631 polybutylene succinate Substances 0.000 claims description 3
- 229920002961 polybutylene succinate Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 229920006267 polyester film Polymers 0.000 claims description 2
- 150000003951 lactams Chemical class 0.000 claims 5
- 229920001748 polybutylene Polymers 0.000 claims 5
- 235000013305 food Nutrition 0.000 abstract description 5
- 238000010345 tape casting Methods 0.000 abstract description 5
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 238000002834 transmittance Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 10
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011185 multilayer composite material Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 2
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- OGNSCSPNOLGXSM-UHFFFAOYSA-N (+/-)-DABA Natural products NCCC(N)C(O)=O OGNSCSPNOLGXSM-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
本发明涉及基于聚丁内酰胺的可降解多层复合膜及制备方法与应用。所述多层复合膜由阻氧层、粘结层和阻湿层通过溶液逐层流延法制备而成,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。与现有技术相比,本发明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。
Description
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(Polyvinylalcohol,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
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。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210891245.2A CN115464960A (zh) | 2022-07-27 | 2022-07-27 | 基于聚丁内酰胺的可降解多层复合膜及制备方法与应用 |
PCT/CN2022/109034 WO2024021039A1 (zh) | 2022-07-27 | 2022-07-29 | 基于聚丁内酰胺的可降解多层复合膜及制备方法与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210891245.2A CN115464960A (zh) | 2022-07-27 | 2022-07-27 | 基于聚丁内酰胺的可降解多层复合膜及制备方法与应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115464960A true CN115464960A (zh) | 2022-12-13 |
Family
ID=84366119
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210891245.2A Pending CN115464960A (zh) | 2022-07-27 | 2022-07-27 | 基于聚丁内酰胺的可降解多层复合膜及制备方法与应用 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN115464960A (zh) |
WO (1) | WO2024021039A1 (zh) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000202938A (ja) * | 1999-01-18 | 2000-07-25 | Toyobo Co Ltd | ガスバリア性積層フィルム |
CN203110436U (zh) * | 2012-12-21 | 2013-08-07 | 江阴升辉包装材料有限公司 | 一种高防伪的阻隔性复合膜 |
CN103342028A (zh) * | 2013-07-26 | 2013-10-09 | 内蒙古农业大学 | 一种生物可降解材料复合膜及其生产方法 |
CN104693794A (zh) * | 2015-02-27 | 2015-06-10 | 华东理工大学 | 一种尼龙4与聚乳酸的共混材料的改性方法 |
CN205416633U (zh) * | 2015-12-10 | 2016-08-03 | 深圳市万达杰塑料制品有限公司 | 一种高阻隔纸塑复合膜 |
WO2020067488A1 (ja) * | 2018-09-28 | 2020-04-02 | リンテック株式会社 | ガスバリア性積層体 |
KR102244864B1 (ko) * | 2020-09-03 | 2021-04-27 | 하호 | 생분해성 또는 생붕괴성 물질이 적층된 시트 및 그 제조방법 |
WO2022105198A1 (zh) * | 2020-11-23 | 2022-05-27 | 上海若祎新材料科技有限公司 | 改性聚烯烃复合膜组合物和改性聚烯烃复合膜及其制备方法和应用 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007076036A (ja) * | 2005-09-12 | 2007-03-29 | Toppan Printing Co Ltd | 透明ガスバリア性ポリアミド系フィルム及びそれを用いた透明ガスバリア性ポリアミド系積層体 |
WO2016106134A1 (en) * | 2014-12-22 | 2016-06-30 | Schlumberger Canada Limited | Degradable composite structures |
KR20210018856A (ko) * | 2018-05-31 | 2021-02-18 | 멜로디아 리미티드 | 다층 물품 |
CN109955555A (zh) * | 2019-04-22 | 2019-07-02 | 刘建林 | 可生物降解的高阻隔液体包装膜 |
CN112111148B (zh) * | 2019-06-20 | 2022-08-12 | 华东理工大学 | 一种聚酰胺肠衣材料及其制备方法 |
CN110588120B (zh) * | 2019-08-30 | 2021-07-27 | 厦门长塑实业有限公司 | 一种耐高温蒸煮、易剥离的高阻隔尼龙复合膜及其制备方法 |
CN113150536A (zh) * | 2020-12-28 | 2021-07-23 | 金发科技股份有限公司 | 一种包含聚丁内酰胺或其衍生物的组合物及其制备方法和应用 |
-
2022
- 2022-07-27 CN CN202210891245.2A patent/CN115464960A/zh active Pending
- 2022-07-29 WO PCT/CN2022/109034 patent/WO2024021039A1/zh unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000202938A (ja) * | 1999-01-18 | 2000-07-25 | Toyobo Co Ltd | ガスバリア性積層フィルム |
CN203110436U (zh) * | 2012-12-21 | 2013-08-07 | 江阴升辉包装材料有限公司 | 一种高防伪的阻隔性复合膜 |
CN103342028A (zh) * | 2013-07-26 | 2013-10-09 | 内蒙古农业大学 | 一种生物可降解材料复合膜及其生产方法 |
CN104693794A (zh) * | 2015-02-27 | 2015-06-10 | 华东理工大学 | 一种尼龙4与聚乳酸的共混材料的改性方法 |
CN205416633U (zh) * | 2015-12-10 | 2016-08-03 | 深圳市万达杰塑料制品有限公司 | 一种高阻隔纸塑复合膜 |
WO2020067488A1 (ja) * | 2018-09-28 | 2020-04-02 | リンテック株式会社 | ガスバリア性積層体 |
KR102244864B1 (ko) * | 2020-09-03 | 2021-04-27 | 하호 | 생분해성 또는 생붕괴성 물질이 적층된 시트 및 그 제조방법 |
WO2022105198A1 (zh) * | 2020-11-23 | 2022-05-27 | 上海若祎新材料科技有限公司 | 改性聚烯烃复合膜组合物和改性聚烯烃复合膜及其制备方法和应用 |
Non-Patent Citations (1)
Title |
---|
聂嵘: "聚丁内酰胺与聚乳酸的共混改性技术研究", 聚丁内酰胺与聚乳酸的共混改性技术研究, no. 2021, 15 January 2021 (2021-01-15), pages 1 - 2 * |
Also Published As
Publication number | Publication date |
---|---|
WO2024021039A1 (zh) | 2024-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Svang-Ariyaskul et al. | Blended chitosan and polyvinyl alcohol membranes for the pervaporation dehydration of isopropanol | |
CN109161363B (zh) | 高阻隔水性胶粘剂 | |
RU2009139027A (ru) | Способ получения полимера | |
JPH06220334A (ja) | 新規なポリマーブレンド | |
CN102580581A (zh) | 一种复合超滤膜及其制备方法 | |
CN1579600A (zh) | 聚氯乙烯中空过滤膜及其制备方法 | |
CN111433135A (zh) | 药剂包装用膜及包装体 | |
CN115464960A (zh) | 基于聚丁内酰胺的可降解多层复合膜及制备方法与应用 | |
JP2007146033A (ja) | 光学透明材料、これを含有してなる複合材料、その成形品及び光学部品 | |
Qin et al. | Polymer/metal-organic frameworks membranes and pervaporation | |
JP2011000132A (ja) | 耐熱性に優れたガスバリア性医療用チューブ及びその製造方法 | |
Zhang et al. | Development of biodegradable polyamide 4/polyvinyl alcohol/poly (lactic acid) multilayer films with tunable water barrier property and superior oxygen barrier property | |
CN113150270A (zh) | 一种磷脂聚合物及其制备方法与应用 | |
AU3139400A (en) | Two-layer composite membrane | |
US10226743B2 (en) | Gas separation composite membrane, gas separation module, gas separation device, gas separation method, and method of producing gas separation composite membrane | |
WO1998026002A1 (en) | Remeltable thermoset resin | |
CN108102079A (zh) | 一种聚l-乳酸葡萄糖共聚物材料及其制备方法 | |
WO2006115211A1 (ja) | シクロデキストリン含有ポリエステル系重合体及びその製造方法 | |
Mehrabian et al. | Bio-based nonporous membranes: Evolution and benchmarking review | |
WO2002048265A1 (fr) | Composition de resine etanche au gaz, materiau de revetement etanche au gaz et moulage etanche au gaz | |
KR890003440B1 (ko) | 수용성 필름 또는 시이트의 제조방법 | |
JP3992827B2 (ja) | 膜の製造方法 | |
JP4742848B2 (ja) | ガスバリア性容器 | |
US5736467A (en) | Waterproof, vapor-permeable fabric and method for generating same | |
JP2003147265A (ja) | オーバープリントニス組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |