CN108641111A - 一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料及其制备方法 - Google Patents
一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料及其制备方法 Download PDFInfo
- Publication number
- CN108641111A CN108641111A CN201810391662.4A CN201810391662A CN108641111A CN 108641111 A CN108641111 A CN 108641111A CN 201810391662 A CN201810391662 A CN 201810391662A CN 108641111 A CN108641111 A CN 108641111A
- Authority
- CN
- China
- Prior art keywords
- fullerene
- ether
- polyether
- ketone
- zro
- 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.)
- Granted
Links
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 65
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 61
- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 60
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 37
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 57
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 229910009112 xH2O Inorganic materials 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 125000003184 C60 fullerene group Chemical group 0.000 claims description 8
- 229910003460 diamond Inorganic materials 0.000 claims description 6
- 239000010432 diamond Substances 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims 1
- -1 Ethyl alcohol Chemical compound 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- 230000006872 improvement Effects 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000012826 global research Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- VRLIPUYDFBXWCH-UHFFFAOYSA-N hydridocarbon(.) Chemical compound [CH] VRLIPUYDFBXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Carbon And Carbon Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
本发明提出一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料及其制备方法,包括以下步骤:(1)制备氧化石墨烯;(2)将ZrO(NO3)2·xH2O溶解,制成含Zr4+的水溶液,与氨水溶液和氧化石墨烯溶液加入至烧杯中,调节pH,老化,过滤,洗涤,干燥,焙烧,得到ZrO2@GO;(3)将ZrO2@GO和富勒烯粉末溶解,超声分散,球磨,烘干,过筛,烧结,固体粉碎,过筛,得到ZrO2@GO/富勒烯复合粉末;(4)将聚醚醚酮粉末溶解,加入PEG4000,搅拌均匀,制成膜液,成膜,干燥,冷却,浸入水中取下;(5)将ZrO2@GO/富勒烯复合粉末加入乙醇,得到分散液;将聚醚醚酮膜浸入分散液中,浸泡,取出,烘干,即得所述复合材料。本发明制备的复合材料兼具很好的导电性和聚醚醚酮的优良性能,具有广阔应用前景。
Description
技术领域
本发明属于高分子材料领域,具体涉及一种金属螯合的席夫碱改性石墨烯/聚醚醚酮耐磨损导电复合材料。
背景技术
聚醚醚酮树脂分子链中含有刚性的苯环、柔性的醚键和提高分子间相互作用力的羰基,结构规整,这使得它具有一系列优越的综合性能。因此,聚醚醚酮被广泛应用于电子电气,航空航天,半导体科技,轨道交通,汽车零部件,医疗器械,石油化工等领域。但是单一的聚醚醚酮树脂显然不能满足不同领域的使用要求,因此近年来对聚醚醚酮树脂进行改性成为国内外热门的研究内容之一。通过对其改性不仅可以提高材料的性能而且能拓宽使用范围。目前,聚醚醚酮可以与玻璃纤维、碳纤维等纤维材料复合增强,也可以与三氧化二铝、氧化锌、碳化硅、二氧化锆、二氧化硅等微米或者纳米级颗粒填充改性,还可以与聚四氟乙烯等共混改性,从而改善聚醚醚酮及其复合材料的机械性能(压缩强度、弯曲强度、硬度和拉伸强度等)以及摩擦学性能。
富勒烯是于1985年发现的继金刚石、石墨和线性碳(carbyne)之后碳元素的第四种晶体形态。其中碳60(C60)和和碳70(C70)是最常见的,也是能够量产的富勒烯,富勒烯的成员还有C28、C32、C240、C540等。以C60为代表的富勒烯家族以其独特的形状和良好的性质开辟了物理学、化学和材料科学中一个崭新的研究方向。由于C60分子具有芳香性,溶于苯呈酱红色,可用电阻加热石墨棒或电弧法使石墨蒸发等方法制得;并且C60分子既可以和金属结合,还可以和非金属负离子结合。所以C60是既有科学价值又有应用前景的化合物,在生命科学医学、天体物理等领域也有一定的意义。
在克拉茨奇默和和霍夫曼等人首先制备出宏观数量的C60以后,科学家从实验上制备出大量的富勒烯衍生物并对其性质进行了广泛研究,立即意识到这类新物质的巨大应用潜力富勒烯新材料的许多不寻常特性儿乎都可以在现代科技和工业部门找到实际应用价值,可预见富勒烯材料的应用是多方面的,包括润滑剂、催化剂、研磨剂、高强度碳纤维、半导体、非线性光学器件、超导材料、光导体、高能电池、燃料、传感器、分子器件以及用于医学成像及治疗等方面。
石墨烯最初是在2004年由英国曼彻斯特大学物理学家安德烈·海姆和康斯坦丁·诺沃肖洛夫从石墨中分离得到的。石墨烯的发现引发了全世界的研究热潮,因为它被称为目前为止世界上最薄、强度最大、导电性最好的材料,同时还具有超高导热系数、润滑性好、比表面积大、阻燃性好等优点。因此,越来越多的研究人员通过往聚合物中添加石墨烯或氧化石墨烯来提高材料各方面的性能。
本发明首次将功能化的石墨烯和富勒烯应用到聚醚醚酮材料上,制备成导电性能更优异的复合材料,应用广泛。
发明内容
为了解决上述的技术问题,本发明一种氧化石墨烯基纤维素季铵盐阳离子型沥青乳化剂及其制备方法,本发明制备的沥青乳化剂原料来源广泛,生产成本低,制备工艺简单,可乳化多种不同型号的沥青,制备的乳化沥青细腻均匀,储存稳定性好。
本发明提供一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备方法,包括以下步骤:
(1)氧化石墨烯的制备:采用改进Hummers法制备氧化石墨烯;
(2)功能化石墨烯的制备:将ZrO(NO3)2·xH2O加入去离子水中在水浴70℃下连续搅拌30min配制成含Zr4+浓度为0.4mol/L的水溶液,将Zr4+溶液、氨水溶液和氧化石墨烯溶液并流加入至烧杯中,溶液pH值调至10左右,室温下老化6h,沉淀物经过滤、洗涤后在120℃下过夜干燥,随后在500℃下焙烧4h,得到ZrO2@GO;
(3)ZrO2@GO/富勒烯复合粉末的制备:将ZrO2@GO和富勒烯粉末加入乙醇中,超声均匀分散200-300min,球磨10-12h,烘干后过400目筛,置于马弗炉中325-400℃烧结1h-3h,得到的固体继续用金刚石粉碎分级设备粉碎粉剂,过400目筛,得到ZrO2@GO/富勒烯复合粉末;
(4)聚醚醚酮膜的制备:将聚醚醚酮粉末溶于DMF中,加入PEG4000,搅拌均匀,制成膜液,在洁净的玻璃板上流延成膜,50℃干燥3h,冷却至室温,浸入水中取下;
(5)功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备:将步骤(3)制备的ZrO2@GO/富勒烯复合粉末加入乙醇中,得到分散液;将步骤(4)制备的聚醚醚酮膜浸入分散液中,浸泡3-5h,取出,烘干,得到功能化石墨烯/富勒烯/聚醚醚酮导电复合材料。
作为本发明进一步的改进,ZrO(NO3)2·xH2O与氧化石墨烯的重量比为(3-10):100。
作为本发明进一步的改进,ZrO(NO3)2·xH2O与氧化石墨烯的重量比为(3-5):100。
作为本发明进一步的改进,ZrO2@GO和富勒烯的重量比为(10-50):100。
作为本发明进一步的改进,ZrO2@GO和富勒烯的重量比为(20-30):100。
作为本发明进一步的改进,富勒烯包括C60富勒烯和C70富勒烯。
作为本发明进一步的改进,超声条件为700W超声2h。
作为本发明进一步的改进,ZrO2@GO/富勒烯复合粉末和聚醚醚酮膜的重量比为(10-30):100。
本发明进一步保护一种根据上述方法制得的功能化石墨烯/富勒烯/聚醚醚酮导电复合材料。
本发明进一步保护一种将上述金属螯合的席夫碱改性石墨烯/聚醚醚酮耐磨损导电复合材料的应用。
本发明的有益效果:
1、本发明制备的复合材料在原有基础上具有更加优异的导电性能,应用面广,特别是应用到半导体领域;
2、本发明原料来源广,制备工艺简单,产品便于贮存和运输,可应用于工业化大生产。
附图说明
图1是功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备工艺图。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整的描述,显然,所述的实施例只是本发明的部分具有代表性的实施例,而不是全部实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的其他所有实施例都属于本发明的保护范围。
实施例1功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备
按照以下步骤进行:
(1)氧化石墨烯的制备:采用改进Hummers法制备氧化石墨烯;
(2)功能化石墨烯的制备:将15g ZrO(NO3)2·xH2O加入去离子水中在水浴70℃下连续搅拌30min配制成含Zr4+浓度为0.4mol/L的水溶液,将Zr4+溶液、氨水溶液和溶有500g氧化石墨烯溶液并流加入至烧杯中,溶液pH值调至10左右,室温下老化6h,沉淀物经过滤、洗涤后在120℃下过夜干燥,随后在500℃下焙烧4h,得到ZrO2@GO,得率为55%;
(3)ZrO2@GO/富勒烯复合粉末的制备:将50g ZrO2@GO和500g C60富勒烯粉末加入乙醇中,500W超声30min均匀分散200min,球磨10h,烘干后过400目筛,置于马弗炉中400℃烧结1h,得到的固体继续用金刚石粉碎分级设备粉碎粉剂,过400目筛,得到ZrO2@GO/富勒烯复合粉末,得率为60%;
(4)聚醚醚酮膜的制备:将500g聚醚醚酮粉末溶于DMF中,加入30gPEG4000,搅拌均匀,制成膜液,在洁净的玻璃板上流延成膜,50℃干燥3h,冷却至室温,浸入水中取下;
(5)功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备:将50g步骤(3)制备的ZrO2@GO/富勒烯复合粉末加入乙醇中,得到分散液;将500g步骤(4)制备的聚醚醚酮膜浸入分散液中,浸泡3h,取出,烘干,得到功能化石墨烯/富勒烯/聚醚醚酮导电复合材料,得率为62%。
实施例2功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备
按照以下步骤进行:
(1)氧化石墨烯的制备:采用改进Hummers法制备氧化石墨烯;
(2)功能化石墨烯的制备:将25g ZrO(NO3)2·xH2O加入去离子水中在水浴70℃下连续搅拌30min配制成含Zr4+浓度为0.4mol/L的水溶液,将Zr4+溶液、氨水溶液和溶有500g氧化石墨烯溶液并流加入至烧杯中,溶液pH值调至10左右,室温下老化6h,沉淀物经过滤、洗涤后在120℃下过夜干燥,随后在500℃下焙烧4h,得到ZrO2@GO,得率为82%;
(3)ZrO2@GO/富勒烯复合粉末的制备:将150g ZrO2@GO和500g C60富勒烯粉末加入乙醇中,700W超声2h均匀分散300min,球磨12h,烘干后过400目筛,置于马弗炉中325℃烧结3h,得到的固体继续用金刚石粉碎分级设备粉碎粉剂,过400目筛,得到ZrO2@GO/富勒烯复合粉末,得率为93%;
(4)聚醚醚酮膜的制备:将500g聚醚醚酮粉末溶于DMF中,加入30gPEG4000,搅拌均匀,制成膜液,在洁净的玻璃板上流延成膜,50℃干燥3h,冷却至室温,浸入水中取下;
(5)功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备:将150g步骤(3)制备的ZrO2@GO/富勒烯复合粉末加入乙醇中,得到分散液;将500g步骤(4)制备的聚醚醚酮膜浸入分散液中,浸泡5h,取出,烘干,得到功能化石墨烯/富勒烯/聚醚醚酮导电复合材料,得率为85%。
实施例3功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备
按照以下步骤进行:
(1)氧化石墨烯的制备:采用改进Hummers法制备氧化石墨烯;
(2)功能化石墨烯的制备:将50g ZrO(NO3)2·xH2O加入去离子水中在水浴70℃下连续搅拌30min配制成含Zr4+浓度为0.4mol/L的水溶液,将Zr4+溶液、氨水溶液和溶有500g氧化石墨烯溶液并流加入至烧杯中,溶液pH值调至10左右,室温下老化6h,沉淀物经过滤、洗涤后在120℃下过夜干燥,随后在500℃下焙烧4h,得到ZrO2@GO,得率为75%;
(3)ZrO2@GO/富勒烯复合粉末的制备:将250g ZrO2@GO和500g C60富勒烯粉末加入乙醇中,600W超声60min均匀分散25min,球磨11h,烘干后过400目筛,置于马弗炉中375℃烧结2h,得到的固体继续用金刚石粉碎分级设备粉碎粉剂,过400目筛,得到ZrO2@GO/富勒烯复合粉末,得率为76%;
(4)聚醚醚酮膜的制备:将500g聚醚醚酮粉末溶于DMF中,加入30gPEG4000,搅拌均匀,制成膜液,在洁净的玻璃板上流延成膜,50℃干燥3h,冷却至室温,浸入水中取下;
(5)功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备:将150g步骤(3)制备的ZrO2@GO/富勒烯复合粉末加入乙醇中,得到分散液;将500g步骤(4)制备的聚醚醚酮膜浸入分散液中,浸泡3-5h,取出,烘干,得到功能化石墨烯/富勒烯/聚醚醚酮导电复合材料,得率为82%。
对比例1聚醚醚酮树脂材料的制备
采用传统专利中提到的制备方法制备聚醚醚树脂。具体包括如下步骤:以4,4-二氟二苯酮与对苯二的钾盐为原料,二苯砜为溶剂,在无水条件下于300-340℃进行溶液缩聚,得到的聚合物经脱溶剂、去盐、水洗,然后于140℃真空干燥,得到高分子量PEK树脂。
试验例1热稳定性实验
将各实施例和对比例例分别进行DSC检测和热稳定性检测,结果见表1,注MI值指熔融指数。
表1
组别 | Tg(℃) | Tm(℃) | 400℃加热5min测MI值 | 400℃加热30min测MI值 |
实施例1 | 146 | 332 | 21.4g/10min | 17.8g/10min |
实施例2 | 145 | 330 | 21.2g/10min | 17.5g/10min |
实施例3 | 146 | 334 | 20.8g/10min | 17.3g/10min |
对比例1 | 147 | 337 | 21.7g/10min | 18.0g/10min |
试验例2性能测试
按照标准:GB/T 1040塑料拉伸性能测试;GB/T9341塑料弯曲性能的测定;GB/T1843塑料悬臂梁冲击试验方法;GB/T 3960塑料摩擦系数的测试;GB/T 15662塑料体积电阻率的测试。
结果见表2。
表2
由上表可知,本发明制备的功能化石墨烯/富勒烯/聚醚醚酮导电复合材料在导电性能上有明显提升,本发明实施例2制备的功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的电阻率降到了4.5*105Ω/cm2,同时,在力学性能的拉伸强度和断裂伸张率相较与传统方法制备的聚醚醚酮有明显提升,在耐磨性能也有改善。
尽管已经示出和描述了本发明的实施例,本领域的普通技术人员可以理解:在不脱离本发明的原理和宗旨的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由权利要求及其等同物限定。
Claims (10)
1.一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备方法,包括以下步骤:
(1)氧化石墨烯的制备:采用改进Hummers法制备氧化石墨烯;
(2)功能化石墨烯的制备:将ZrO(NO3)2·xH2O加入去离子水中在水浴70℃下连续搅拌30min配制成含Zr4+浓度为0.4mol/L的水溶液,将Zr4+溶液、氨水溶液和氧化石墨烯溶液并流加入至烧杯中,溶液pH值调至10左右,室温下老化6h,沉淀物经过滤、洗涤后在120℃下过夜干燥,随后在500℃下焙烧4h,得到ZrO2@GO;
(3)ZrO2@GO/富勒烯复合粉末的制备:将ZrO2@GO和富勒烯粉末加入乙醇中,超声均匀分散200-300min,球磨10-12h,烘干后过400目筛,置于马弗炉中325-400℃烧结1h-3h,得到的固体继续用金刚石粉碎分级设备粉碎粉剂,过400目筛,得到ZrO2@GO/富勒烯复合粉末;
(4)聚醚醚酮膜的制备:将聚醚醚酮粉末溶于DMF中,加入PEG4000,搅拌均匀,制成膜液,在洁净的玻璃板上流延成膜,50℃干燥3h,冷却至室温,浸入水中取下;
(5)功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备:将步骤(3)制备的ZrO2@GO/富勒烯复合粉末加入乙醇中,得到分散液;将步骤(4)制备的聚醚醚酮膜浸入分散液中,浸泡3-5h,取出,烘干,得到功能化石墨烯/富勒烯/聚醚醚酮导电复合材料。
2.根据权利要求1所述一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备方法,其特征在于,所述ZrO(NO3)2·xH2O与氧化石墨烯的重量比为(3-10):100。
3.根据权利要求1所述一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备方法,其特征在于,所述ZrO(NO3)2·xH2O与氧化石墨烯的重量比为(3-5):100。
4.根据权利要求1所述一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备方法,其特征在于,所述ZrO2@GO和富勒烯的重量比为(10-50):100。
5.根据权利要求1所述一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备方法,其特征在于,所述ZrO2@GO和富勒烯的重量比为(20-30):100。
6.根据权利要求1所述一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备方法,其特征在于,所述富勒烯包括C60富勒烯和C70富勒烯。
7.根据权利要求1所述一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备方法,其特征在于,所述超声条件为700W超声2h。
8.根据权利要求1所述一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的制备方法,其特征在于,所述ZrO2@GO/富勒烯复合粉末和聚醚醚酮膜的重量比为(10-30):100。
9.一种根据上述任一权利要求所述制备方法得到的功能化石墨烯/富勒烯/聚醚醚酮导电复合材料。
10.根据权利要求9所述一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810391662.4A CN108641111B (zh) | 2018-04-27 | 2018-04-27 | 一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810391662.4A CN108641111B (zh) | 2018-04-27 | 2018-04-27 | 一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108641111A true CN108641111A (zh) | 2018-10-12 |
CN108641111B CN108641111B (zh) | 2021-01-22 |
Family
ID=63748269
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810391662.4A Active CN108641111B (zh) | 2018-04-27 | 2018-04-27 | 一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108641111B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111037942A (zh) * | 2019-12-24 | 2020-04-21 | 江西昊泽光学膜科技有限公司 | 一种防爆、防辐射双层复合式手机保护膜的制备工艺 |
CN111454057A (zh) * | 2019-06-12 | 2020-07-28 | 南京赛诺特斯材料科技有限公司 | 一种牙科氧化锆全瓷材料及其制备方法 |
CN114709395A (zh) * | 2022-04-14 | 2022-07-05 | 内蒙古欣源石墨烯科技股份有限公司 | 一种石墨烯负载碳包覆锡锑的锂电池负极材料的制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN103108908A (zh) * | 2010-09-09 | 2013-05-15 | 贝克休斯公司 | 生成聚合物纳米复合物的方法 |
CN107880484A (zh) * | 2017-12-05 | 2018-04-06 | 中北大学 | 一种纳米粒子/氧化石墨烯复合改性高分子材料及其制备 |
-
2018
- 2018-04-27 CN CN201810391662.4A patent/CN108641111B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103108908A (zh) * | 2010-09-09 | 2013-05-15 | 贝克休斯公司 | 生成聚合物纳米复合物的方法 |
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 |
CN107880484A (zh) * | 2017-12-05 | 2018-04-06 | 中北大学 | 一种纳米粒子/氧化石墨烯复合改性高分子材料及其制备 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111454057A (zh) * | 2019-06-12 | 2020-07-28 | 南京赛诺特斯材料科技有限公司 | 一种牙科氧化锆全瓷材料及其制备方法 |
CN111037942A (zh) * | 2019-12-24 | 2020-04-21 | 江西昊泽光学膜科技有限公司 | 一种防爆、防辐射双层复合式手机保护膜的制备工艺 |
CN114709395A (zh) * | 2022-04-14 | 2022-07-05 | 内蒙古欣源石墨烯科技股份有限公司 | 一种石墨烯负载碳包覆锡锑的锂电池负极材料的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN108641111B (zh) | 2021-01-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Goh et al. | Directed and on‐demand alignment of carbon nanotube: a review toward 3D printing of electronics | |
Rafique et al. | Epoxy resin composite reinforced with carbon fiber and inorganic filler: Overview on preparation and properties | |
Guiney et al. | Three-dimensional printing of cytocompatible, thermally conductive hexagonal boron nitride nanocomposites | |
Sun et al. | On the rheological properties of multi-walled carbon nano-polyvinylpyrrolidone/silicon-based shear thickening fluid | |
Thakur et al. | Hybrid polymer composite materials: structure and chemistry | |
Alemán et al. | Strong carbon nanotube fibers by drawing inspiration from polymer fiber spinning | |
Liu et al. | Scratch-resistant, highly conductive, and high-strength carbon nanotube-based composite yarns | |
Thostenson et al. | Nanocomposites in context | |
Song et al. | Isotropic− nematic phase transition of dispersions of multiwall carbon nanotubes | |
Moniruzzaman et al. | Polymer nanocomposites containing carbon nanotubes | |
Zhang et al. | Nanocomposites of carbon nanotube fibers prepared by polymer crystallization | |
CN108641111A (zh) | 一种功能化石墨烯/富勒烯/聚醚醚酮导电复合材料及其制备方法 | |
Liu et al. | Preparation of carbon nanofibres through electrospinning and thermal treatment | |
Mahltig et al. | Inorganic and composite fibers: production, properties, and applications | |
Wang et al. | Advanced functional carbon nanotube fibers from preparation to application | |
Zhou et al. | High-strength single-walled carbon nanotube/permalloy nanoparticle/poly (vinyl alcohol) multifunctional nanocomposite fiber | |
Zhong et al. | Review of carbon-based electromagnetic shielding materials: film, composite, foam, textile | |
Xu et al. | The preparation of carbonized silk cocoon-Co-graphene composite and its enhanced electromagnetic interference shielding performance | |
Imaizumi et al. | Top-down process based on electrospinning, twisting, and heating for producing one-dimensional carbon nanotube assembly | |
Choudhary et al. | Contemporary review on carbon nanotube (CNT) composites and their impact on multifarious applications | |
Rahatekar et al. | Length‐Dependent Mechanics of Carbon‐Nanotube Networks | |
Kausar | Emerging trends in poly (methyl methacrylate) containing carbonaceous reinforcements—Carbon nanotube, carbon black, and carbon fiber | |
Khan et al. | A review on properties and fabrication techniques of polymer/carbon nanotube composites and polymer intercalated buckypapers | |
CN108624054A (zh) | 一种磁场调控的透明导电复合物及其制备方法 | |
Fakirov | Polymer nanocomposites: Why their mechanical performance does not justify the expectation and a possible solution to the problem? |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20210519 Address after: 215000 32 Cailian Industrial Zone, Linhu Town, Wuzhong District, Suzhou City, Jiangsu Province Patentee after: SUZHOU JUQI OPTOELECTRONICS TECHNOLOGY Co.,Ltd. Address before: 242000 a3-201, JINDA Garden community, Baocheng Road, Xuanzhou District, Xuancheng City, Anhui Province Patentee before: Sun Yongmei |