WO2016008290A1 - Film composite nano-rubans de graphène oxydé/polymère et procédé de préparation associé - Google Patents

Film composite nano-rubans de graphène oxydé/polymère et procédé de préparation associé Download PDF

Info

Publication number
WO2016008290A1
WO2016008290A1 PCT/CN2015/071165 CN2015071165W WO2016008290A1 WO 2016008290 A1 WO2016008290 A1 WO 2016008290A1 CN 2015071165 W CN2015071165 W CN 2015071165W WO 2016008290 A1 WO2016008290 A1 WO 2016008290A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene oxide
composite film
polymer composite
polymer
oxide nanobelt
Prior art date
Application number
PCT/CN2015/071165
Other languages
English (en)
Chinese (zh)
Inventor
郑玉婴
樊志敏
林锦贤
Original Assignee
福州大学
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 福州大学 filed Critical 福州大学
Publication of WO2016008290A1 publication Critical patent/WO2016008290A1/fr

Links

Images

Classifications

    • 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
    • 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
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the invention belongs to the technical field of preparation of polymer composite films, and particularly relates to a graphene oxide nanobelt/polymer composite film and a preparation method thereof.
  • the ideal graphene is a single-layer two-dimensional infinite structure with high crystallinity and semi-metal electrical properties. It has become a research hotspot in the fields of energy storage materials, electronic devices, composite materials, etc., and graphene has excellent impermeability. Sexuality is currently favored in the field of barrier materials, but the surface of graphene sheets prepared in practice often has wrinkle and undulation defects, which will inevitably affect its application in many fields. A new type of carbon material graphene nanobelt that has emerged in recent years has become a best candidate in the fields of transparent electrodes and barrier fillers due to its unique high aspect ratio, low defect, and controllable morphology.
  • the graphene nanoribbon is a thin strip-shaped material formed by a sp 2 hybrid orbital of carbon atoms, and can be prepared by a CVD method, a lithography method, an ultrasonic method, or a longitudinal oxidation-cut carbon nanotube method.
  • Carbon nanotubes are mainly classified into single-walled carbon nanotubes and multi-walled carbon nanotubes. It is known from the known literature that graphene nanoribbons which are conventionally obtained by longitudinal oxidation-oxidation of single-walled carbon nanotubes are easily entangled and are not advantageous for use.
  • the graphene nanoribbons obtained by cutting with multi-wall carbon nanotubes have neat edges, few band structure defects, excellent electron transport performance, mechanical properties, transparency and impermeability, but their preparation costs are relatively expensive. Therefore, it is an effective way to solve the above problems by replacing the graphene nanoribbons with the same impenetrable and low-cost graphene oxide nanobelts, which are used in the field of barriers.
  • the barrier properties of polymers can be improved. .
  • the object of the present invention is to provide a graphene oxide nanobelt/polymer composite film and a preparation method thereof, and the graphene oxide nanobelt/polymer composite film prepared by the method of the invention has excellent barrier properties and mechanical properties, and can Widely used in food, pharmaceutical packaging and electronic surface packaging materials.
  • the preparation method of the invention is scientific and reasonable, simple in process, strong in operability, and suitable for large-scale industrial production.
  • the present invention adopts the following technical solutions:
  • a graphene oxide nanobelt/polymer composite film is a graphene nanobelt in which a multi-walled carbon nanotube is longitudinally cut into a strip structure by oxidation, and then a graphene nanobelt is polymerized by a solution forming method. The compound is composited to form the film.
  • the preparation of the graphene oxide nanobelt/polymer composite film comprises the following steps:
  • step 1) mixing the polymer solution of step 1) and the ultrasonically dispersed graphene oxide nanobelt of step 2) uniformly, dispersing 100W ultrasonically for 1-5 h, and stirring for 1-3 h on a mechanical stirrer to form a paste liquid;
  • the preparation of the graphene oxide nanobelt includes the following steps:
  • step 2) Add 1-1.5 g of multi-walled carbon nanotubes to the solution of step 1), stir for 1-2 h, then slowly add 6-9 g of KMnO 4 to the above mixture in 3 steps in 30 min, and then stir 15 -30min;
  • step 3 Move the reaction system of step 2) to an oil bath at 55-65 ° C, stir the reaction at 300 r / min for 2-6 h, let cool to room temperature, and then pour into 5-10 ml H 2 O 2 The ice water mixture was condensed for 24 hours, at which time the solution turned dark green, indicating that the reaction was complete;
  • step 3) The solution of step 3) is ultrasonically dispersed at a power of 100 W for 20-30 min, repeatedly washed and filtered on a polytetrafluoroethylene film with 10% by mass of HCl and deionized water, and finally vacuum dried at 60 ° C for 24 h to obtain the above.
  • Graphene oxide nanobelts The solution of step 3) is ultrasonically dispersed at a power of 100 W for 20-30 min, repeatedly washed and filtered on a polytetrafluoroethylene film with 10% by mass of HCl and deionized water, and finally vacuum dried at 60 ° C for 24 h to obtain the above.
  • Graphene oxide nanobelts The solution of step 3) is ultrasonically dispersed at a power of 100 W for 20-30 min, repeatedly washed and filtered on a polytetrafluoroethylene film with 10% by mass of HCl and deionized water, and finally vacuum dried at 60 ° C for 24 h to obtain the
  • the polymer is any one of polyester thermoplastic polyurethane, polyether thermoplastic polyurethane, polyvinyl alcohol, polyvinyl chloride, polymethyl methacrylate, polyaniline, polyamide, polystyrene or polyethylene. .
  • the solvent is any one of N-N dimethylformamide, tetrahydrofuran, chloroform, toluene or water.
  • the use of graphene oxide to prepare a composite film has many defects in the base portion of the graphene oxide, so it does not have a good barrier effect on small molecular substances, and the graphene oxide nanoribbon has only the edge of the strip which is defective, and its surface is It can be well contacted with the polymer matrix, and therefore, the composite film prepared by the same has better impermeability than the composite film prepared by using graphene oxide nano.
  • the original multi-walled carbon nanotubes have no obvious effect on the reinforced polymer composite because the multi-walled carbon nanotubes have only a tubular surface contact, and the graphene nanoribbons are cut longitudinally into a strip structure. After that, since both sides of the graphene oxide nanobelt can be well contacted with the polymer matrix, the contact area is significantly increased, thereby being significantly enhanced.
  • the properties of polymer films are significantly increased, thereby being significantly enhanced.
  • the composite film prepared by the invention not only has excellent barrier properties and mechanical properties, but also has certain transparency, and can be widely applied in the fields of food, pharmaceutical packaging and surface packaging materials of electronic products.
  • FIG. 1 is a schematic diagram showing the barrier principle of a graphene oxide nanobelt/polymer composite film.
  • FIG. 2 is an SEM image of a multi-walled carbon nanotube and a graphene oxide nanobelt prepared by the present invention, wherein A is a multi-walled carbon nanotube and B is a graphene oxide nanobelt.
  • FIG. 3 is a TEM image of a multi-walled carbon nanotube and a graphene oxide nanobelt prepared by the present invention, wherein A is a multi-walled carbon nanotube and B is a graphene oxide nanobelt.
  • Figure 5 is a comparison of XRD of multi-walled carbon nanotubes with the graphene oxide nanoribbons prepared by the present invention.
  • FIG. 6 is an infrared contrast diagram of a multi-walled carbon nanotube and a graphene oxide nanobelt prepared by the present invention.
  • the preparation of graphene oxide nanoribbons includes the following steps:
  • step 2) 1g of multi-walled carbon nanotubes were added to the solution of step 1), stirred for 2h, then 6g of KMnO 4 was slowly added to the above mixture in 3 minutes in 30min, and then stirred for 20min;
  • step 3 The reaction system of step 2) was transferred to an oil bath at 55 ° C, stirred at 300 r / min for 2 h, allowed to cool to room temperature, and then poured into an ice water mixture containing 5 ml of H 2 O 2 to coagulate. At 24h, the solution turned dark green, indicating complete reaction;
  • step 3) The solution of step 3) was ultrasonically dispersed at 100 W for 30 min, repeatedly washed and filtered on a polytetrafluoroethylene film with 10% by mass of HCl and deionized water, and finally dried at 60 ° C for 24 h to obtain the graphite oxide. Alkene nanobelts.
  • FIG. 2 is an SEM image of a multi-walled carbon nanotube and a prepared graphene oxide nanobelt
  • FIG. 3 is a multi-walled carbon nanotube and TEM image of the prepared graphene oxide nanobelts.
  • FIG. 4 is a Raman comparison diagram of the multi-walled carbon nanotubes and the prepared graphene oxide nanobelts.
  • the multi-walled carbon nanotubes represent D and G peaks at 1317 cm -1 and 1594 cm -1 , and are cut to obtain graphite oxide.
  • the peak shape of the D peak of 1326 cm -1 and the G peak of 1594 cm -1 of the ene nanobelt relative to the multi-walled carbon nanotube became stronger and wider, indicating that lattice distortion and structural defects increased, demonstrating that the multi-walled carbon nanotube was opened.
  • Figure 5 is a comparison of XRD of multi-walled carbon nanotubes with the prepared graphene oxide nanobelts.
  • the layer spacing of the multi-walled carbon nanotubes is 0.34 nm.
  • the peak shape is relatively flat, indicating that the multi-walled carbon nanotubes are substantially completely oxidized and chopped into graphene oxide nanoribbons.
  • Graphene oxide nanoribbons are examples of the graphene oxide nanoribbons.
  • the preparation of the graphene oxide nanobelt/polymer composite film comprises the following steps:
  • step 1) and the ultrasonically dispersed graphene oxide nanobelt of step 2) are uniformly mixed, ultrasonically dispersed at 100 W for 1 h, and then stirred on a mechanical stirrer for 3 h to form a paste-like liquid;
  • the preparation of the graphene oxide nanobelt/polymer composite film comprises the following steps:
  • step 1) and the 2) ultrasonically dispersed graphene oxide nanobelt are uniformly mixed, 100W ultrasonically dispersed for 3 hours, and then stirred on a mechanical stirrer for 2 hours to form a paste liquid;
  • the pure polyester thermoplastic polyurethane film was prepared in the same manner as in Example 1 without adding graphene oxide nanobelts as Comparative Experiment Group 1.
  • the pure polyether thermoplastic polyurethane film was prepared in the same manner as in Example 2 without adding graphene oxide nanobelts as Comparative Experiment Group 2.
  • Step 2 Dissolve 0.045 g of graphene oxide in 10 ml of NN dimethylformamide, and disperse 100 W ultrasonically for 20 min; prepare a graphene oxide/polyester thermoplastic polyurethane composite film according to the conditions of Example 1 as a comparative experiment group. 3.
  • the film prepared in the examples was subjected to oxygen transmission test; the film sample was a wafer having an area of 50 cm 2 , and the test accuracy was 0.01 cc/m 2 .day.0.1 MPa, and the degree of vacuum was ⁇ 10 Pa.
  • the temperature control method adopts semiconductor bidirectional high-efficiency temperature control, and finally takes the average value of oxygen permeability of three samples of each sample.
  • the graphene oxide nanobelt/polymer composite film prepared by the invention has lower oxygen permeability and better mechanical properties than the pure polymer film; and in the case of equal amount of raw materials.
  • the graphene oxide nanobelt/polymer composite film has better barrier properties than the graphene oxide/polymer composite film. Therefore, it has been experimentally shown that the graphene oxide nanobelt/polymer composite film of the present invention has good performance and is suitable for use in fields with high barrier requirements.

Abstract

L'invention concerne un film composite nano-rubans de graphène oxydé/polymère et un procédé de préparation associé. Selon l'invention, un nano-tube de carbone à parois multiples est coupé longitudinalement en nano-rubans de graphène oxydé avec des structures en forme de bandes, par la mise en oeuvre d'un procédé d'oxydation, puis les nano-rubans de graphène oxydé sont associés à un polymère pour former le film. Le film composite préparé selon l'invention présente d'excellentes propriété barrière et propriété mécanique, et il présente un certain degré de transparence fixe, ce qui permet de l'appliquer largement dans un domaine caractérisé par des exigences de barrière supérieures. À l'heure actuelle, la production en masse de nanotubes de carbone est réalisée aussi bien au plan national qu'à l'étranger, de sorte que le coût de fabrication du nano-ruban de graphène oxydé est considérablement réduit. Les propriétés barrière et mécanique du film composite peuvent être améliorées considérablement avec seulement quelques nano-rubans de graphène oxydé. Le procédé de préparation selon l'invention est simple, facilement exploitable et adapté à une production industrialisée à grande échelle.
PCT/CN2015/071165 2014-07-18 2015-01-21 Film composite nano-rubans de graphène oxydé/polymère et procédé de préparation associé WO2016008290A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410342652.3 2014-07-18
CN201410342652.3A CN104072979B (zh) 2014-07-18 2014-07-18 一种氧化石墨烯纳米带/聚合物复合薄膜及其制备方法

Publications (1)

Publication Number Publication Date
WO2016008290A1 true WO2016008290A1 (fr) 2016-01-21

Family

ID=51594601

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/071165 WO2016008290A1 (fr) 2014-07-18 2015-01-21 Film composite nano-rubans de graphène oxydé/polymère et procédé de préparation associé

Country Status (2)

Country Link
CN (1) CN104072979B (fr)
WO (1) WO2016008290A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112522812A (zh) * 2019-09-18 2021-03-19 中国科学院苏州纳米技术与纳米仿生研究所 一种多孔碳纳米纤维及其制备方法与应用
CN112774468A (zh) * 2020-12-18 2021-05-11 任国峰 一种石墨烯聚砜超滤膜及其制备方法
CN114523746A (zh) * 2022-03-03 2022-05-24 中塑新材料科技（杭州）有限公司 高透明强伸缩高阻隔薄膜
CN115040934A (zh) * 2022-07-18 2022-09-13 安徽昌达织物有限公司 一种高强度工业滤布
CN117263588A (zh) * 2023-11-21 2023-12-22 内蒙古建筑职业技术学院 一种石墨化羟基碳纳米管建筑垃圾泡沫混凝土及其应用

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104072979B (zh) * 2014-07-18 2016-05-04 福州大学 一种氧化石墨烯纳米带/聚合物复合薄膜及其制备方法
CN104371226B (zh) * 2014-11-06 2016-07-20 中国航空工业集团公司北京航空材料研究院 一种羟基化石墨烯-聚合物复合材料的制备方法
CN104448366B (zh) * 2014-12-17 2017-09-22 福州大学 一种管道内衬用高阻隔性tpu薄膜及其制备方法
JP6514343B2 (ja) * 2015-01-14 2019-05-15 日東電工株式会社 酸化グラフェンバリアフィルム
CN107189403B (zh) * 2015-04-23 2020-01-17 天津大学 碳管膜在制备各向异性聚合物中的应用
CN104815608B (zh) * 2015-05-04 2017-07-14 哈尔滨工业大学 基于氧化石墨烯纳米带多功能油水分离材料的制备方法
CN105037762B (zh) * 2015-07-17 2017-11-14 南京邮电大学 一种高机械性能氧化石墨烯聚醚胺复合薄膜的制备方法
CN105778133A (zh) * 2016-03-23 2016-07-20 复旦大学 碳纳米管/氧化石墨烯纳米带-聚合物杂化质子交换膜及其制备方法
CN105778470A (zh) * 2016-04-12 2016-07-20 苏州甫众塑胶有限公司 一种环保型塑胶材料及其制备方法
CN105968777B (zh) * 2016-05-24 2018-09-18 福州大学 一种抗静电复合纳米材料薄膜及其制备方法
CN106147204A (zh) * 2016-08-30 2016-11-23 苏州佰锐生物科技有限公司 一种石墨烯/聚苯胺/聚氨酯导电复合薄膜的制备方法
CN106317578A (zh) * 2016-09-12 2017-01-11 福州大学 一种高紫外屏蔽高阻隔性纳米材料薄膜及其制备方法
CN106366418B (zh) * 2016-09-12 2019-02-22 福州大学 纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法
CN106832880A (zh) * 2017-01-17 2017-06-13 南通强生安全防护科技股份有限公司 石墨烯‑油性pu复合浆料及其制备方法和用途
CN107629446A (zh) * 2017-09-26 2018-01-26 深圳八六三计划材料表面技术研发中心 一种条带状氧化石墨烯增强尼龙复合材料的制备方法
CN107722310A (zh) * 2017-09-26 2018-02-23 深圳八六三计划材料表面技术研发中心 一种条带状石墨烯增强聚甲基丙烯酸甲酯复合材料的制备方法
CN107698857A (zh) * 2017-11-23 2018-02-16 马鞍山松鹤信息科技有限公司 一种农用薄膜材料及其制备工艺
CN107828114B (zh) * 2017-11-28 2020-04-10 安徽益顺塑业有限公司 一种提高药用塑料容器阻透气性的方法
CN108948622A (zh) * 2018-06-28 2018-12-07 合肥艾飞新材料有限公司 一种环氧改性石墨烯薄膜及其制备方法
CN109438968A (zh) * 2018-09-11 2019-03-08 苏州市雄林新材料科技有限公司 一种汽车头枕用高阻隔tpu薄膜及其制备方法
CN109666208A (zh) * 2018-12-18 2019-04-23 北京印刷学院 一种氧化石墨烯@SiO2改性聚乙烯薄膜的方法
CN109912912B (zh) * 2019-03-06 2021-09-21 东华大学 一种柔性、电绝缘氟化石墨烯导热复合膜及其制备和应用
CN115863062B (zh) * 2022-12-27 2023-07-28 武汉立承科技有限公司 石墨烯纳米带/金属氧化物纳米带复合膜及其制备与应用

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102115566A (zh) * 2011-01-06 2011-07-06 西安理工大学 高阻隔性氧化石墨烯和聚合物纳米复合膜的制备方法
US20110223405A1 (en) * 2005-11-18 2011-09-15 Northwestern University Composite polymer film with graphene nanosheets as highly effective barrier property enhancers
KR20120024263A (ko) * 2010-09-06 2012-03-14 동아대학교 산학협력단 기체 차단성 투명 고분자 필름
CN102604137A (zh) * 2012-03-12 2012-07-25 烟台大学 聚氨酯-氧化石墨烯复合耐老化高通透微孔膜材料的制法
CN102634106A (zh) * 2012-04-12 2012-08-15 上海交通大学 一种氧化石墨烯纳米带/极性橡胶复合材料的制备方法
CN102827386A (zh) * 2012-08-21 2012-12-19 江苏大学 一种聚醚醚酮/氧化石墨烯纳米复合薄膜的制备方法
CN103265714A (zh) * 2013-05-20 2013-08-28 西安理工大学 一种聚乙烯醇/氧化石墨烯复合薄膜的制备方法
CN103627139A (zh) * 2013-09-25 2014-03-12 杭州师范大学 一种功能化氧化石墨烯/环氧树脂纳米复合材料的制备方法
CN104072979A (zh) * 2014-07-18 2014-10-01 福州大学 一种氧化石墨烯纳米带/聚合物复合薄膜及其制备方法
CN104212053A (zh) * 2014-09-18 2014-12-17 福州大学 一种防水隔氧密封膜及其制备和应用

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110223405A1 (en) * 2005-11-18 2011-09-15 Northwestern University Composite polymer film with graphene nanosheets as highly effective barrier property enhancers
KR20120024263A (ko) * 2010-09-06 2012-03-14 동아대학교 산학협력단 기체 차단성 투명 고분자 필름
CN102115566A (zh) * 2011-01-06 2011-07-06 西安理工大学 高阻隔性氧化石墨烯和聚合物纳米复合膜的制备方法
CN102604137A (zh) * 2012-03-12 2012-07-25 烟台大学 聚氨酯-氧化石墨烯复合耐老化高通透微孔膜材料的制法
CN102634106A (zh) * 2012-04-12 2012-08-15 上海交通大学 一种氧化石墨烯纳米带/极性橡胶复合材料的制备方法
CN102827386A (zh) * 2012-08-21 2012-12-19 江苏大学 一种聚醚醚酮/氧化石墨烯纳米复合薄膜的制备方法
CN103265714A (zh) * 2013-05-20 2013-08-28 西安理工大学 一种聚乙烯醇/氧化石墨烯复合薄膜的制备方法
CN103627139A (zh) * 2013-09-25 2014-03-12 杭州师范大学 一种功能化氧化石墨烯/环氧树脂纳米复合材料的制备方法
CN104072979A (zh) * 2014-07-18 2014-10-01 福州大学 一种氧化石墨烯纳米带/聚合物复合薄膜及其制备方法
CN104212053A (zh) * 2014-09-18 2014-12-17 福州大学 一种防水隔氧密封膜及其制备和应用

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
AMADA L.HIGGINBOTHAM ET AL.: "Lower defect graphene oxide nanoribbons from mutiwalled carbon nanotubes", ACSNANO, vol. 4, no. 4, 31 December 2010 (2010-12-31), pages 2059 - 2069 *
CHANG SHENG XIANG ET AL., FUNCTIONALIZED LOW DEFECT GRAPHENE NANORIBBONS AND POLYURETHANE COMPOSITE FILM FOR IMPROVED GAS BARRIER AND MECHANICAL PERFORMANCES, vol. 7, 31 December 2013 (2013-12-31), pages 10380 - 10386 *
DMITRY V.KOAYNKIN ET AL.: "Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons", NATURES, 16 April 2009 (2009-04-16), pages 872 - 876, XP002664814, DOI: doi:10.1038/NATURE07872 *
HYE MIN KIM ET AL.: "Transparent and high gas barrier films based on poly(vinyl alcohol)/graphene oxide composited", THIN SOLID FILMS, 31 December 2011 (2011-12-31), pages 7766 - 7771 *
I-HSIANG TSENG ET AL.: "Transparent polyimide/graphene oxide nanocomposite with improved moisture barrier property", MATERIAL CHEMISTRY AND PHYSICS, 31 December 2012 (2012-12-31), pages 247 - 253 *
ZHAO JIAN ET AL.: "Preparation and properties of graphene oxide/polyurethane composites", CHINA RUBBER INDUSTRY, vol. 60, no. 8, 31 December 2013 (2013-12-31), pages 453 - 457 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112522812A (zh) * 2019-09-18 2021-03-19 中国科学院苏州纳米技术与纳米仿生研究所 一种多孔碳纳米纤维及其制备方法与应用
CN112522812B (zh) * 2019-09-18 2023-03-10 中国科学院苏州纳米技术与纳米仿生研究所 一种多孔碳纳米纤维及其制备方法与应用
CN112774468A (zh) * 2020-12-18 2021-05-11 任国峰 一种石墨烯聚砜超滤膜及其制备方法
CN114523746A (zh) * 2022-03-03 2022-05-24 中塑新材料科技（杭州）有限公司 高透明强伸缩高阻隔薄膜
CN115040934A (zh) * 2022-07-18 2022-09-13 安徽昌达织物有限公司 一种高强度工业滤布
CN117263588A (zh) * 2023-11-21 2023-12-22 内蒙古建筑职业技术学院 一种石墨化羟基碳纳米管建筑垃圾泡沫混凝土及其应用
CN117263588B (zh) * 2023-11-21 2024-01-16 内蒙古建筑职业技术学院 一种石墨化羟基碳纳米管建筑垃圾泡沫混凝土及其应用

Also Published As

Publication number Publication date
CN104072979B (zh) 2016-05-04
CN104072979A (zh) 2014-10-01

Similar Documents

Publication Publication Date Title
WO2016008290A1 (fr) Film composite nano-rubans de graphène oxydé/polymère et procédé de préparation associé
Wu et al. Recent progress in the synthesis of graphene/CNT composites and the energy-related applications
Jiang et al. Solvothermal synthesis and electrochemical performance in super-capacitors of Co3O4/C flower-like nanostructures
Guan et al. Three-dimensional graphene-based polymer nanocomposites: preparation, properties and applications
Wu et al. Highly flexible solid-state supercapacitor based on graphene/polypyrrole hydrogel
Qu et al. Hierarchical-graphene-coupled polyaniline aerogels for electrochemical energy storage
Hu et al. Fabrication of flexible free-standing reduced graphene oxide/polyaniline nanocomposite film for all-solid-state flexible supercapacitor
Li et al. Vaper phase polymerized PEDOT/cellulose paper composite for flexible solid-state supercapacitor
Alabadi et al. Graphene oxide-polythiophene derivative hybrid nanosheet for enhancing performance of supercapacitor
Wu et al. Carbonaceous hydrogels and aerogels for supercapacitors
Tan et al. Facile synthesis of functionalized graphene hydrogel for high performance supercapacitor with high volumetric capacitance and ultralong cycling stability
Xu et al. Strong, conductive, lightweight, neat graphene aerogel fibers with aligned pores
Yin et al. Multifunctional boron nitride nanosheet/polymer composite nanofiber membranes
Wang et al. Preparation of graphene oxide/polypyrrole/multi-walled carbon nanotube composite and its application in supercapacitors
Wang et al. Flexible graphene devices related to energy conversion and storage
Xie et al. Synthesis of layered microporous carbons from coal tar by directing, space-confinement and self-sacrificed template strategy for supercapacitors
Sun et al. Developing polymer composite materials: carbon nanotubes or graphene?
Yang et al. Preparation of poly (3-hexylthiophene)/graphene nanocomposite via in situ reduction of modified graphite oxide sheets
Memon et al. Conjunction of conducting polymer nanostructures with macroporous structured graphene thin films for high-performance flexible supercapacitors
CN105368045B (zh) 石墨烯‑聚吡咯复合气凝胶及其制备方法与应用
Ye et al. Producing large-area, foldable graphene paper from graphite oxide suspensions by in-situ chemical reduction process
Liu et al. Flexible and robust sandwich-structured S-doped reduced graphene oxide/carbon nanotubes/polyaniline (S-rGO/CNTs/PANI) composite membranes: excellent candidate as free-standing electrodes for high-performance supercapacitors
WO2015139517A1 (fr) Pellicule de matériau composite en tpu anti-statique barrière et son procédé de préparation
Xu et al. Carboxymethylcellulose-polyaniline/carbon nanotube (CMC-PANI/CNT) film as flexible and highly electrochemical active electrode for supercapacitors
Zhang et al. All-carbon composite paper as a flexible conducting substrate for the direct growth of polyaniline particles and its applications in supercapacitors

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15821635

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 18/07/2017)

122 Ep: pct application non-entry in european phase

Ref document number: 15821635

Country of ref document: EP

Kind code of ref document: A1