CN108099322A - 一种氧化石墨烯基高阻隔纳米复合薄膜及其制备方法 - Google Patents
一种氧化石墨烯基高阻隔纳米复合薄膜及其制备方法 Download PDFInfo
- Publication number
- CN108099322A CN108099322A CN201711339351.5A CN201711339351A CN108099322A CN 108099322 A CN108099322 A CN 108099322A CN 201711339351 A CN201711339351 A CN 201711339351A CN 108099322 A CN108099322 A CN 108099322A
- Authority
- CN
- China
- Prior art keywords
- film
- adhesive
- graphene oxide
- graphite oxide
- barrier
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 41
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000001070 adhesive effect Effects 0.000 claims abstract description 43
- 239000000853 adhesive Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 34
- 239000010439 graphite Substances 0.000 claims description 34
- 125000003342 alkenyl group Chemical group 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229920002635 polyurethane Polymers 0.000 claims description 20
- 239000004814 polyurethane Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- -1 Polypropylene Polymers 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 230000035800 maturation Effects 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 230000006798 recombination Effects 0.000 claims description 5
- 238000005215 recombination Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- YJLIKUSWRSEPSM-WGQQHEPDSA-N (2r,3r,4s,5r)-2-[6-amino-8-[(4-phenylphenyl)methylamino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1CNC1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O YJLIKUSWRSEPSM-WGQQHEPDSA-N 0.000 claims description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 2
- 239000002313 adhesive film Substances 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 2
- 239000002552 dosage form Substances 0.000 claims 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 18
- 235000013305 food Nutrition 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract description 5
- 229940079593 drug Drugs 0.000 abstract description 4
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- 230000002787 reinforcement Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 76
- 239000005025 cast polypropylene Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 230000002457 bidirectional effect Effects 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000002955 isolation Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 239000002651 laminated plastic film Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
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
- B32B27/06—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
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0036—Heat treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/107—Ceramic
- B32B2264/108—Carbon, e.g. graphite particles
-
- 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
-
- 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
- B32B2439/80—Medical packaging
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Fluid Mechanics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
本发明公开了一种氧化石墨烯基高阻隔纳米复合薄膜及其制备方法,其是以未改性或硅烷改性的氧化石墨烯为增强体,通过超声、搅拌的方法均匀分散在水性及溶剂型粘合剂中;然后通过干式复合法,使氧化石墨烯基纳米复合粘合剂在两层通用薄膜之间形成一层中间薄膜,即得到纳米复合薄膜。利用本发明方法制备的氧化石墨烯基纳米复合薄膜不仅透明性好,而且具有优异的阻隔和力学性能,解决了现有柔性透明薄膜阻隔性不佳的问题,适用于对阻隔性要求较高的食品和药品的包装。
Description
技术领域
本发明属于石墨烯材料技术领域,具体涉及一种氧化石墨烯基高阻隔纳米复合薄膜。
背景技术
聚合物薄膜材料以其优异的综合性能,作为玻璃、陶瓷和金属等的替代品在食品及药品的包装中得到了越来越广泛的应用。然而,聚合物薄膜材料存在透气和透湿的缺点,易导致食品变质、药品药性减弱,影响食品药品的长期保存。因此,提高聚合物薄膜材料的阻隔性能一直是国内外包装行业研究的热点和重点。目前塑料薄膜包装行业主要采用多层复合薄膜材料解决薄膜阻隔性能差的问题,其中有一层为高阻隔性材料(如铝箔);或者在薄膜基材上镀上一薄层铝。然而,上述复合薄膜包装材料存在透光性差、成本高以及不能微波加热等缺点。自从2004年英国曼彻斯特大学Geim和Novoselov教授发现石墨烯以来,石墨烯引起了世界各国研究人员的兴趣。石墨烯是一种由碳原子以sp2杂化轨道组成六角型蜂巢晶格的新型二维碳材料。碳六元环孔隙尺寸仅0.15nm,比已知的最小气体分子直径(氦气0.25nm)还要小,具备优良的气体阻隔性能,且单层石墨烯对可见光的透过率大于97%。因此,石墨烯是最理想的高效透明阻隔材料。在聚合物/石墨烯纳米复合材料中,一方面纳米石墨烯片层自身具有优异的阻隔性能,另一方面石墨烯具有小的片层厚度和大的宽厚比,纳米石墨烯片层所形成的阻隔网络可以增加气体渗透路径长度、限制气体分子渗透。因此,利用纳米石墨烯片层在聚合物基体中的“纳米阻隔效应”和“多路径渗透效应”,可以有效地改善聚合物薄膜的阻隔性能。
目前利用石墨烯制备高阻隔薄膜材料的方法主要是以石墨烯粉体作为改性填料,借助于溶剂与聚合物混合,然后通过流延、模压、浇筑、吹塑等成型方法制备复合薄膜。例如:专利CN103059434A公开了一种高阻隔聚苯乙烯复合薄膜的制备方法,利用氧化石墨烯(GONSs)作为高效层状纳米阻隔增强填料,通过溶液混合、减压蒸馏的方式,将GONSs包覆在PS微粒表面,获得GONSs/PS微阻隔单元,接着采用热压成型将GONSs/PS微阻隔单元组装构建具有隔离结构的GONSs/PS复合薄膜。专利CN104530686A公开了一种功能石墨烯/TPU薄膜及其制备方法和应用,采用改进Hummers法制备氧化石墨烯,先用十二烷基二甲基溴化胺进行插层改性,再用抗坏血酸进行还原,制得DDAB-RGO,最后以TPU树脂为基体,采用溶液涂覆成膜工艺制得DDAB-RGO/TPU复合薄膜。类似的还有:专利CN102115566A公开了“高阻隔性氧化石墨烯和聚合物纳米复合膜的制备方法”;专利CN103265714A公开了“一种聚乙烯醇/氧化石墨烯复合薄膜的制备方法”;专利CN102827386A公开了“一种聚醚醚酮/氧化石墨烯复合薄膜的制备方法”等。上述专利公布的方法基本上涉及两个步骤:第一步是通过溶剂法将石墨烯分散到聚合物溶液中,此过程需要使用大量的有机溶剂使聚合物溶解,且在成型前需要将溶剂除去;第二步是通过不同的薄膜成型工艺,将聚合物/石墨烯纳米复合材料成型为薄膜材料,此过程需要对现有成型工艺进行探索。因此,上述方法制备工艺复杂、繁琐、成本较高,不符合当前聚合物薄膜包装行业高阻隔薄膜的制备工艺,且需要对现有设备、工艺进行改造,不利于大规模的工业推广和应用。
发明内容
针对现有高阻隔性食品及药品包装薄膜的技术缺陷,本发明提出了一种氧化石墨烯基高阻隔纳米复合薄膜及其制备方法,所要解决的技术问题在于:以未改性及硅烷改性的氧化石墨烯为增强剂,制备具有高阻隔性、高透明度、易加工、低成本、综合性能优良的柔性透明高阻隔纳米复合薄膜。
本发明解决上述技术问题,采用如下技术方案:
本发明首先公开了一种氧化石墨烯基高阻隔纳米复合薄膜,其包括上下两层通用薄膜,在两层通用薄膜之间设置有一层氧化石墨烯基纳米复合粘合剂薄膜。
其中:两层通用薄膜各自独立的选自聚丙烯薄膜、聚乙烯薄膜、聚氯乙烯薄膜、聚乙烯醇薄膜、聚苯乙烯薄膜、聚偏二氯乙烯薄膜、聚酰胺薄膜、聚对苯二甲酸乙二醇酯薄膜、乙烯-醋酸乙烯共聚物薄膜或乙烯-乙烯醇共聚物薄膜。所述的粘合剂为水性丙烯酸类粘合剂、水性聚氨酯类粘合剂、聚酯溶剂型聚氨酯类粘合剂、聚醚溶剂型聚氨酯类粘合剂或聚烯烃溶剂型聚氨酯类粘合剂。所述的氧化石墨烯为未改性的氧化石墨烯或硅烷改性的氧化石墨烯。
本发明氧化石墨烯基高阻隔纳米复合薄膜的制备方法,包括以下步骤:
(1)将氧化石墨烯加入到溶剂中,在室温条件下超声分散40~90min,得到氧化石墨烯的胶体悬浮液;
(2)将所述氧化石墨烯的胶体悬浮液加入到粘合剂中,在20~45℃条件下机械搅拌60~120min,得到氧化石墨烯基纳米复合粘合剂;
(3)利用干式复合法,通过辊压的方式,将氧化石墨烯基纳米复合粘合剂涂覆在一层通用薄膜的表面,待粘合剂干燥形成薄膜后,再在粘合剂的另一面覆盖另一层通用薄膜,使两层通用薄膜粘合在一起;
(4)将复合后的薄膜在30~60℃的熟化室中熟化处理48~120h,即获得氧化石墨烯基高阻隔纳米复合薄膜。
优选的,步骤(1)中,所述的溶剂为蒸馏水或乙酸乙酯。
优选的,步骤(2)中,氧化石墨烯的质量占粘合剂固含量的0.02~2.0wt%。
优选的,步骤(3)中,干式复合法的复合工艺为:干基上胶量为1.5~3.0g/m2,网线辊为140~200目,烘道温度分区设定为40~70℃、50~80℃、60~90℃,复合辊温为50~80℃,复合速度为50~200m/min,复合压力为0.2~0.6MPa。
与现有技术相比,本发明的有益效果体现在:
1、本发明以氧化石墨烯为增强剂,制备纳米复合薄膜,大幅度提高了薄膜的阻隔性能,尤其是O2和水蒸气的透过率均下降了60%;而且所得复合薄膜的透光性好、力学性能优异,解决了柔性透明薄膜阻隔性能不佳的问题,可应用于对阻隔性能要求较高的食品及药品包装。
2、本发明的制备方法是将氧化石墨烯分散到两层通用复合薄膜间的水性及溶剂型粘合剂中,不需要额外使用有机溶剂,且氧化石墨烯分散性能良好。
3、本发明复合薄膜的成型方法是基于食品包装薄膜行业常规的干式复合方法,技术成熟、工艺简单、成本低廉,具有广阔的发展前景和工业化推广价值。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面通过实施例对本发明的制备方法及所得产品的性能做详细的说明。以下内容仅仅是对本发明的构思所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
下述实施例中:所用溶剂型聚氨酯粘合剂型号为LH-7755,购买自江苏力合粘合剂有限公司;所用水性丙烯酸粘合剂型号为RobondTM L-188/CR-3A,购买自陶氏化学公司;所用水性聚氨酯粘合剂型号为JH-826,购买自江苏百瑞特新材料有限公司;所用未改性氧化石墨烯购买自深圳市图灵进化科技有限公司;所用硅烷改性氧化石墨烯自制,是利用KH550硅烷偶联剂对未改性的氧化石墨烯进行改性获得。
实施例1
称取溶剂型聚氨酯粘合剂主剂(固含量:75wt%)3.85kg、固化剂(固含量75wt%)0.77kg、乙酸乙酯5.38kg,将主剂、固化剂和乙酸乙酯在室温下机械搅拌120min,得到对照溶剂型聚氨酯粘合剂。
选择两层通用薄膜材料为双向拉伸聚丙烯薄膜(BOPP)和流延聚丙烯薄膜(CPP),将混合均匀的对照溶剂型聚氨酯粘合剂倒入粘合剂槽中,待粘合剂中的气泡基本消除后,利用干式复合法得到对照BOPP/CPP复合薄膜。其中干式复合机的复合工艺参数为:干基上胶量为1.5g/m2,网线辊160目,三段烘箱温度分别为56℃、58℃、63℃,复合辊温为50℃,复合速度为100m/min,复合压力为0.3MPa。
将对照BOPP/CPP复合薄膜放置在40℃熟化室,熟化处理48h,最终得到对照BOPP/CPP复合薄膜产品。
经测试,本实施例所得对照BOPP/CPP复合薄膜的性能如下:氧气透过率为1135.78cm3/(m2×24h×0.1MPa),水蒸气透过率为3.56g/(m2×24h);拉断力(纵/横)为80.23/150.64N,断裂伸长率(纵/横)为170.04/29.83%,抗摆锤力为1.10N;剥离力为0.48N/15mm;透光率为92.3%,雾度为3.4%。
实施例2
称取溶剂型聚氨酯粘合剂主剂(固含量:75wt%)3.85kg、固化剂(固含量75wt%)0.77kg、乙酸乙酯5.38kg、硅烷改性氧化石墨烯6.93g。
将硅烷改性氧化石墨烯加入到乙酸乙酯中,在室温条件下超声分散40min,得到氧化石墨烯的胶体悬浮液;然后将氧化石墨烯的胶体悬浮液加入到主剂中,在室温下机械搅拌60min后,加入固化剂,继续机械搅拌60min,得到氧化石墨烯基溶剂型聚氨酯纳米复合粘合剂。
选择两层通用薄膜材料为双向拉伸聚丙烯薄膜(BOPP)和流延聚丙烯薄膜(CPP),将混合均匀的氧化石墨烯基溶剂型聚氨酯纳米复合粘合剂倒入粘合剂槽中,待粘合剂中的气泡基本消除后,利用干式复合法得到氧化石墨烯基高阻隔BOPP/CPP纳米复合薄膜。其中干式复合机复合工艺参数为:干基上胶量为1.5g/m2,网线辊160目,三段烘箱温度分别为56℃、58℃、63℃,复合辊温为50℃,复合速度为100m/min,复合压力为0.3MPa。
将复合薄膜放置在40℃熟化室中,熟化处理48h,最终得到氧化石墨烯基高阻隔BOPP/CPP纳米复合薄膜产品。
经测试,本实施例所得氧化石墨烯基高阻隔BOPP/CPP纳米复合薄膜的性能如下:氧气透过率为541.26cm3/(m2×24h×0.1MPa),水蒸气透过率为1.43g/(m2×24h);拉断力(纵/横)为89.63/153.41N,断裂伸长率(纵/横)为176.46/30.56%,抗摆锤力为1.15N;剥离力为0.80N/15mm;透光率为90.6%,雾度为3.4%。
实施例3
本实施例按实施例2相同的方法制备复合薄膜产品,区别仅在于:将流延聚丙烯薄膜(CPP)改为聚乙烯薄膜(PE)。
经测试,本实施例所得氧化石墨烯基高阻隔BOPP/PE纳米复合薄膜的性能如下:氧气透过率为536.75cm3/(m2×24h×0.1MPa),水蒸气透过率为2.11g/(m2×24h);拉断力(纵/横)为84.45/157.06N,断裂伸长率(纵/横)为174.04/33.02%,抗摆锤力为1.14N;剥离力为0.91N/15mm;透光率为88.2%,雾度为3.4%。
实施例4
称取水性丙烯酸粘合剂主剂(固含量:45wt%)10kg、固化剂0.3kg、未改性氧化石墨烯9.6g、蒸馏水200g。
将未改性氧化石墨烯加入到蒸馏水中,在室温条件下超声分散40min,得到氧化石墨烯的胶体悬浮液;然后将氧化石墨烯的胶体悬浮液加入到水性丙烯酸粘合剂主剂中,在室温下机械搅拌60min后,加入固化剂,继续机械搅拌60min,得到氧化石墨烯基水性丙烯酸纳米复合粘合剂。
选择两层通用薄膜材料为双向拉伸聚丙烯薄膜(BOPP)和流延聚丙烯薄膜(CPP),将混合均匀的氧化石墨烯基水性丙烯酸纳米复合粘合剂倒入粘合剂槽中,待粘合剂中的气泡基本消除后,利用干式复合法得到氧化石墨烯基高阻隔BOPP/CPP纳米复合薄膜。其中干式复合机复合工艺参数为:干基上胶量为2.2g/m2,网线辊140目,三段烘箱温度分别为70℃、80℃、90℃,复合辊温为70℃,复合速度为100m/min,复合压力为0.5MPa。
将复合薄膜放置在30℃熟化室中,熟化处理120h,最终得到氧化石墨烯基高阻隔BOPP/CPP纳米复合薄膜产品。
经测试,本实施例所得氧化石墨烯基高阻隔BOPP/CPP纳米复合薄膜的性能如下:氧气透过率为538.51cm3/(m2×24h×0.1MPa),水蒸气透过率为1.94g/(m2×24h);拉断力(纵/横)为83.79/157.96N,断裂伸长率(纵/横)为174.02/36.86%,抗摆锤力为1.18N;剥离力为0.60N/15mm;透光率为88.4%,雾度为3.5%。
实施例5
称取水性聚氨酯粘合剂主剂(固含量30%)10kg、固化剂0.4kg、未改性氧化石墨烯6.8g、蒸馏水200g。
将未改性氧化石墨烯加入到蒸馏水中,在室温条件下超声分散40min,得到氧化石墨烯的胶体悬浮液;然后将氧化石墨烯的胶体悬浮液加入到水性聚氨酯粘合剂主剂中,在室温下机械搅拌60min后,加入固化剂,继续机械搅拌60min,得到氧化石墨烯基水性聚氨酯纳米复合粘合剂。
选择两层通用薄膜材料为双向拉伸聚丙烯薄膜(BOPP)和流延聚丙烯薄膜(CPP),将混合均匀的氧化石墨烯基水性聚氨酯纳米复合粘合剂倒入粘合剂槽中,待粘合剂中的气泡基本消除后,利用干式复合法得到氧化石墨烯基高阻隔BOPP/CPP纳米复合薄膜。其中干式复合机复合工艺参数为:干基上胶量为2.2g/m2,网线辊140目,三段烘箱温度分别为70℃、80℃、90℃,复合辊温为70℃,复合速度为100m/min,复合压力为0.5MPa。
将复合薄膜放置在30℃熟化室中,熟化处理120h,最终得到氧化石墨烯基高阻隔BOPP/CPP纳米复合薄膜产品。
经测试,本实施例所得氧化石墨烯基高阻隔BOPP/CPP纳米复合薄膜的性能如下:氧气透过率为540.15cm3/(m2×24h×0.1MPa),水蒸气透过率为1.51g/(m2×24h);拉断力(纵/横)为87.37/154.26N,断裂伸长率(纵/横)为175.62/35.32%,抗摆锤力为1.15N;剥离力为0.74N/15mm;透光率为90.2%,雾度为3.4%。
以上仅为本发明的示例性实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种氧化石墨烯基高阻隔纳米复合薄膜,其特征在于:包括上下两层通用薄膜,在两层通用薄膜之间设置有一层氧化石墨烯基纳米复合粘合剂薄膜。
2.根据权利要求1所述的一种氧化石墨烯基高阻隔纳米复合薄膜,其特征在于:两层通用薄膜各自独立的选自聚丙烯薄膜、聚乙烯薄膜、聚氯乙烯薄膜、聚乙烯醇薄膜、聚苯乙烯薄膜、聚偏二氯乙烯薄膜、聚酰胺薄膜、聚对苯二甲酸乙二醇酯薄膜、乙烯-醋酸乙烯共聚物薄膜或乙烯-乙烯醇共聚物薄膜。
3.根据权利要求1所述的一种氧化石墨烯基高阻隔纳米复合薄膜,其特征在于:所述的粘合剂为水性丙烯酸类粘合剂、水性聚氨酯类粘合剂、聚酯溶剂型聚氨酯类粘合剂、聚醚溶剂型聚氨酯类粘合剂或聚烯烃溶剂型聚氨酯类粘合剂。
4.根据权利要求1所述的一种氧化石墨烯基高阻隔纳米复合薄膜,其特征在于:所述的氧化石墨烯为未改性的氧化石墨烯或硅烷改性的氧化石墨烯。
5.一种权利要求1~4中任意一项所述氧化石墨烯基高阻隔纳米复合薄膜的制备方法,其特征在于,包括以下步骤:
(1)将氧化石墨烯加入到溶剂中,在室温条件下超声分散40~90min,得到氧化石墨烯的胶体悬浮液;
(2)将所述氧化石墨烯的胶体悬浮液加入到粘合剂中,在20~45℃条件下机械搅拌60~120min,得到氧化石墨烯基纳米复合粘合剂;
(3)利用干式复合法,通过辊压的方式,将氧化石墨烯基纳米复合粘合剂涂覆在一层通用薄膜的表面,待粘合剂干燥形成薄膜后,再在粘合剂的另一面覆盖另一层通用薄膜,使两层通用薄膜粘合在一起;
(4)将复合后的薄膜在30~60℃的熟化室中熟化处理48~120h,即获得氧化石墨烯基高阻隔纳米复合薄膜。
6.根据权利要求5所述的制备方法,其特征在于:步骤(1)中,所述的溶剂为蒸馏水或乙酸乙酯。
7.根据权利要求5所述的制备方法,其特征在于:步骤(2)中,氧化石墨烯的质量占粘合剂固含量的0.02~2.0wt%。
8.根据权利要求5所述的制备方法,其特征在于:步骤(3)中,干式复合法的复合工艺为:干基上胶量为1.5~3.0g/m2,网线辊为140~200目,烘道温度分区设定为40~70℃、50~80℃、60~90℃,复合辊温为50~80℃,复合速度为50~200m/min,复合压力为0.2~0.6MPa。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711339351.5A CN108099322A (zh) | 2017-12-14 | 2017-12-14 | 一种氧化石墨烯基高阻隔纳米复合薄膜及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711339351.5A CN108099322A (zh) | 2017-12-14 | 2017-12-14 | 一种氧化石墨烯基高阻隔纳米复合薄膜及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108099322A true CN108099322A (zh) | 2018-06-01 |
Family
ID=62216013
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711339351.5A Pending CN108099322A (zh) | 2017-12-14 | 2017-12-14 | 一种氧化石墨烯基高阻隔纳米复合薄膜及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108099322A (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109943275A (zh) * | 2019-03-22 | 2019-06-28 | 江苏理工学院 | 一种氧化石墨烯改性聚氨酯材料的制备方法 |
CN110370780B (zh) * | 2019-06-28 | 2021-09-07 | 佛山佛塑科技集团股份有限公司 | 软包装膜的制备方法 |
CN115534368A (zh) * | 2022-09-21 | 2022-12-30 | 湖北航天化学技术研究所 | 石墨烯基防迁移层制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101306743A (zh) * | 2007-10-19 | 2008-11-19 | 河南双汇投资发展股份有限公司 | 一种牛奶包装膜及其制备方法 |
WO2016033522A1 (en) * | 2014-08-29 | 2016-03-03 | Materion Corporation | Conductive bond foils |
CN105820791A (zh) * | 2016-02-29 | 2016-08-03 | 洛阳尖端技术研究院 | 石墨烯改性聚氨酯组合物、利用其制备的聚氨酯粘合剂、该粘合剂的制备方法及浮空器 |
CN107090252A (zh) * | 2017-04-19 | 2017-08-25 | 无锡云亭石墨烯技术有限公司 | 一种石墨烯uv固化胶的制备及其复合加热玻璃的应用 |
-
2017
- 2017-12-14 CN CN201711339351.5A patent/CN108099322A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101306743A (zh) * | 2007-10-19 | 2008-11-19 | 河南双汇投资发展股份有限公司 | 一种牛奶包装膜及其制备方法 |
WO2016033522A1 (en) * | 2014-08-29 | 2016-03-03 | Materion Corporation | Conductive bond foils |
CN105820791A (zh) * | 2016-02-29 | 2016-08-03 | 洛阳尖端技术研究院 | 石墨烯改性聚氨酯组合物、利用其制备的聚氨酯粘合剂、该粘合剂的制备方法及浮空器 |
CN107090252A (zh) * | 2017-04-19 | 2017-08-25 | 无锡云亭石墨烯技术有限公司 | 一种石墨烯uv固化胶的制备及其复合加热玻璃的应用 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109943275A (zh) * | 2019-03-22 | 2019-06-28 | 江苏理工学院 | 一种氧化石墨烯改性聚氨酯材料的制备方法 |
CN110370780B (zh) * | 2019-06-28 | 2021-09-07 | 佛山佛塑科技集团股份有限公司 | 软包装膜的制备方法 |
CN115534368A (zh) * | 2022-09-21 | 2022-12-30 | 湖北航天化学技术研究所 | 石墨烯基防迁移层制备方法 |
CN115534368B (zh) * | 2022-09-21 | 2024-04-05 | 湖北航天化学技术研究所 | 石墨烯基防迁移层制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108544826A (zh) | 一种蒙脱土基高阻隔纳米复合薄膜及其制备方法 | |
CN108099322A (zh) | 一种氧化石墨烯基高阻隔纳米复合薄膜及其制备方法 | |
CN104968496B (zh) | 具备包含多层结构体的包装材料的制品 | |
CN107353605B (zh) | 一种多功能石墨烯/pet复合膜及其制备方法 | |
CN103112226B (zh) | 七层共挤高阻隔透明膜及其制备方法 | |
US20160362577A1 (en) | A waterproof and oxygen-isolating sealing film and preparation method | |
CN102115566A (zh) | 高阻隔性氧化石墨烯和聚合物纳米复合膜的制备方法 | |
CN103571012A (zh) | 一种防水透气的塑料膜、其制备方法及应用 | |
WO2011123056A1 (en) | A barrier layer, a process of making a barrier layer and uses thereof | |
CN105729967B (zh) | 一种多层聚乳酸复合阻隔高强度膜 | |
CN110373007A (zh) | 一种高韧性石墨烯/pet复合膜组合物的制备方法 | |
CN102019738A (zh) | 一种poss改性高阻隔三层共挤包装薄膜及其制备方法 | |
CN107603058B (zh) | 一种氧化石墨烯增强的pvc/cpe复合管材及其制备方法 | |
CN102501501A (zh) | 一种bopp隔离膜 | |
CN104788867B (zh) | 热收缩自粘性真空镀保护薄膜的制造方法 | |
JP2017052282A (ja) | バリア性積層フィルム | |
CN101717553A (zh) | 一种高阻隔复合材料及其制备工艺 | |
CN110358270A (zh) | 一种高韧性石墨烯/pet复合膜组合物 | |
KR101945736B1 (ko) | 하이 배리어성 코팅 조성물 | |
CN105733081B (zh) | 一种耐腐蚀高阻燃热塑性低烟无卤电缆料及其制备方法 | |
JP2016104564A (ja) | バリア性積層フィルム | |
CN110385905A (zh) | 一种含有双保护核心阻隔层的叠层共挤膜及其生产工艺 | |
CN109177400A (zh) | 一种高抗拉薄膜及生产方法 | |
CN104497934B (zh) | 一种高阻氧阻水汽的粘结树脂 | |
JP2004314564A (ja) | 高ガスバリア性を有する透明積層体 |
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 | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180601 |
|
RJ01 | Rejection of invention patent application after publication |