CN109056335B - 一种石墨烯/水性聚氨酯吸波涂料及其制备方法和应用 - Google Patents
一种石墨烯/水性聚氨酯吸波涂料及其制备方法和应用 Download PDFInfo
- Publication number
- CN109056335B CN109056335B CN201810798618.5A CN201810798618A CN109056335B CN 109056335 B CN109056335 B CN 109056335B CN 201810798618 A CN201810798618 A CN 201810798618A CN 109056335 B CN109056335 B CN 109056335B
- Authority
- CN
- China
- Prior art keywords
- graphene
- wave
- fabric
- absorbing
- waterborne polyurethane
- 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.)
- Expired - Fee Related
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 70
- 238000000576 coating method Methods 0.000 title claims abstract description 39
- 239000011248 coating agent Substances 0.000 title claims abstract description 37
- 239000004814 polyurethane Substances 0.000 title claims abstract description 29
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 230000004048 modification Effects 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 239000004753 textile Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000006096 absorbing agent Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 4
- 239000004744 fabric Substances 0.000 claims description 59
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000004970 Chain extender Substances 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 238000012650 click reaction Methods 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 239000000675 fabric finishing Substances 0.000 claims description 3
- 238000009962 finishing (textile) Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- WYZDCUGWXKHESN-UHFFFAOYSA-N n-benzyl-n-methyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(C)CC1=CC=CC=C1 WYZDCUGWXKHESN-UHFFFAOYSA-N 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims 1
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明涉及一种石墨烯/水性聚氨酯吸波涂料及其制备方法和应用。该涂料是以石墨烯为吸波剂,通过硅烷偶联剂改性使其以化学键合方式均匀分散在水性聚氨酯中。制备方法包括:石墨烯分散液制备,聚氨酯预聚体制备,石墨烯/水性聚氨酯吸波涂料制备。本发明制备条件温和,得到的吸波纺织品轻薄柔软,具有较好的柔韧性和形状适应性等,可裁剪加工成雷达或电子设备等的屏蔽层、特殊场合的防护服等,具有广阔的应用前景。
Description
技术领域
本发明属于吸波涂料及其制备方法和应用领域,特别涉及一种石墨烯/水性聚氨酯吸波涂料及其制备方法和应用。
背景技术
随着现代科学技术的发展,大量电子、电器产品逐渐进入人们生活中,在给人们日常生活带来极大便利的同时,也产生了严重的电磁辐射,这不仅会影响电子设备的正常运转,还直接威胁到人体健康和环境卫生。此外,在现代战争中,为提高军事目标的生存能力和武器系统的突防能力,电磁屏蔽技术的重要性日益凸显。鉴于电磁屏蔽材料在民用和军用领域均具有广阔的应用前景,其制备技术已成为当前研究热点。
近年来,织物型电磁屏蔽材料不仅具有良好的电磁屏蔽性能,亦可保持纺织品本身的柔软、柔韧、可折叠和易加工等特性,可根据需要将其裁剪制成屏蔽窗帘、屏蔽帐篷和遮盖布等纺织产品,是一种新兴的、应用广泛的电磁兼容性材料。目前,根据电磁屏蔽原理不同,电磁屏蔽织物主要可分为反射型和吸收型两类。其中,反射型电磁屏蔽织物主要通过金属纤维混纺、表面涂镀层及填充法制成,该类织物均具有优异的导电性和电磁屏蔽特性,但其主要通过表面金属层的反射损耗衰减电磁能,不能有效减少局部空间电磁波,易造成二次污染;吸收型电磁屏蔽织物又称吸波织物,主要通过涂层技术将吸波剂与织物复合制得,然而现有的吸波剂均为纳微级粉末,主要通过涂层方法应用在纺织品上,由于其极易在粘合剂中发生团聚、沉降现象,从而难以构成连续吸波层,会产生漏波现象;此外吸波剂填充密度大、涂层织物手感僵硬及粘附牢度差等问题也限制了该类吸波织物的进一步发展。
发明内容
本发明所要解决的技术问题是提供一种石墨烯/水性聚氨酯吸波涂料及其制备方法和应用,以克服现有技术中吸波剂在水性聚氨酯中易团聚和重叠,吸波层与纤维间结合牢度差,吸波纺织品手感僵硬的缺陷。
本发明的一种石墨烯/水性聚氨酯吸波涂料,所述涂料是以石墨烯为吸波剂,通过硅烷偶联剂改性使其以化学键合方式均匀分散在水性聚氨酯中,从而制得性能稳定的石墨烯/水性聚氨酯吸波涂料。
本发明的一种石墨烯/水性聚氨酯吸波涂料的制备方法,包括:
(1)采用硅烷偶联剂对氧化石墨烯进行表面改性,然后用还原剂还原,离心并分散,得到石墨烯分散液,其中硅烷偶联剂与氧化石墨烯的质量比为5~20:1,还原剂与氧化石墨烯的质量比为5~10:1,石墨烯分散液质量浓度为0.1~0.5wt%;
(2)将异氟尔酮二异氰酸酯IPDI、聚乙二醇PEG400和二月桂酸二丁基锡DBTDL以质量比为10~20:10~20:0.05~0.1与溶剂混合,在氮气下搅拌反应,得到聚氨酯预聚体,加入扩链剂和步骤(1)中石墨烯分散液继续反应,加入甲基丙烯酸-2-羟基乙酯HEMA进行封端反应,加入碱中和反应,乳化,得到石墨烯/水性聚氨酯吸波涂料,其中IPDI与溶剂的比例为10~20g:10~20mL,IPDI、扩链剂、石墨烯、HEMA与碱的质量比为10~20:1.5~5:0.15~0.3:2~4:1.5~3。
所述步骤(1)中硅烷偶联剂为KH580或3-氨丙基三乙氧基硅烷APTES。
所述步骤(1)中还原剂为二乙醇胺;还原时间为12~24h。
所述步骤(1)中表面改性的工艺参数为:温度为室温,溶剂为体积比为2~4:1的无水乙醇和蒸馏水混合溶剂,时间为12~24h。
所述步骤(1)中石墨烯分散液溶剂为丙酮。
所述步骤(2)中搅拌反应温度为60~70℃,搅拌反应时间为1~1.5h。
所述步骤(2)中继续反应温度为80~90℃,继续反应时间为2~4h。
所述步骤(2)中封端反应温度为60~80℃,封端反应时间为4~6h。
所述步骤(2)中扩链剂为2,2-二羟甲基丁酸DBMA或2,2-二羟甲基丙酸DMPA。
所述步骤(2)中碱为三乙胺;中和反应时间为0.5~1h;乳化是加入去离子水剪切乳化。
本发明的一种石墨烯/水性聚氨酯吸波涂料在织物整理中的应用。
所述在织物整理中的应用具体为:采用3-巯丙基三乙氧基硅烷KH580对织物进行表面改性,然后利用巯基-烯点击反应将石墨烯/水性聚氨酯吸波涂料整理在巯基改性的织物表面,得到石墨烯/水性聚氨酯吸波纺织品,其中石墨烯/水性聚氨酯吸波涂料固含量为40~60%。
所述织物为棉织物、碱减量涤纶织物等;表面改性具体为:在室温搅拌条件下将织物浸入含5~10wt%KH580的无水乙醇和蒸馏水混合溶剂中,反应1~5h,其中浴比为50~100:1,无水乙醇和蒸馏水的体积比为2~4:1。
所述巯基-烯点击反应具体为:将织物浸入石墨烯/水性聚氨酯吸波涂料中,浴比为50~100:1,加入热引发剂三(2-羧乙基)膦TCEP,在25~60℃下反应2~10h,其中TCEP占石墨烯/水性聚氨酯吸波涂料的质量含量为0.5~2wt%。
本发明首先通过硅烷偶联剂表面改性GO,将其还原后采用化学键合结构均匀分散在WPU中制得石墨烯/WPU吸波涂料(反应机理如图1所示);然后利用巯基-烯点击反应将其整理在巯基改性的纺织品表面(工艺流程如图2所示),从而制得石墨烯/WPU吸波纺织品。
有益效果
与现有技术相比,本发明的吸波纺织品以轻质、高导电性、高导热性和高比表面积的石墨烯为吸波剂所制备,具有质量轻、厚度薄的优点;与反射型电磁屏蔽织物相比,本发明的吸波织物主要利用介电损耗方式衰减电磁能,其具有高的表面阻抗匹配,有利于电磁波进入材料内部,减少材料的表面反射作用,解决了电磁波二次污染的问题;尤其是与常规涂层类吸波织物相比,采用化学改性的方式使石墨烯材料均匀分散在WPU中,解决了石墨烯吸波剂在WPU中易团聚和重叠等技术问题,有利于减少吸波漏洞,可有效提高吸波性能;此外,本发明中采用巯基-烯点击反应将WPU整理在巯基改性的纺织品表面,取代了传统的物理沉积或涂层等方式,提高了石墨烯吸波层与织物的结合牢度,且制备条件温和。所得的吸波织物轻薄柔软,具有较好的柔韧性和形状适应性等,可裁剪加工成雷达或电子设备等的屏蔽层、特殊场合的防护服等,具有广阔的应用前景。
附图说明
图1为本发明合成石墨烯/WPU吸波涂料的反应机理图;
图2为本发明中石墨烯/WPU吸波织物的制备工艺流程图;
图3为本发明中实施例1(a)、实施例2(b)、实施例3(c)、实施例4(d)、实施例5(e)和实施例6(f)制备的吸波织物的吸波效果示意图。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
本发明实施例中,所用的氧化石墨烯购自苏州碳丰科技有限公司,所使用的织物基材均由三元控股集团有限公司提供,IPDI、PEG400、DBTDL和HEMA试剂购自西格玛奥德里奇(上海)贸易有限公司,所有试剂均为分析纯,在使用过程中无需进一步提纯。
实施例1
采用棉织物为基材制备rGO/WPU/棉吸波织物,具体步骤如下:
(1)取200mg GO均匀分散在250mL无水乙醇/蒸馏水=2:1(V/V)溶液中,然后依次加入0.1mL TEA、2g APTES和0.2mL盐酸,室温搅拌24h;离心,无水乙醇洗涤后再离心,然后将其均匀分散在200mL蒸馏水中,缓慢加入1g二乙醇胺,在室温、搅拌条件下反应24h,产物经离心后均匀分散在200mL丙酮中,得到石墨烯丙酮分散液备用。
(2)14.63g IPDI、12g PEG400、50mg DBTDL和10mL丙酮置于四口烧瓶中,在65℃油浴、氮气、冷凝回流、机械搅拌下反应1h;升温至85℃,加入2.435g扩链剂DMPA和20mL上述石墨烯丙酮分散液,反应3h,反应结束,降温至80℃;然后加入3.664g封端剂HEMA,反应时间为4h,反应结束后,降至室温,并加入1.64g TEA进行中和反应,反应时间为45min;加入蒸馏水进行乳化,固含量控制在50%,从而制得石墨烯/WPU吸波涂料。
(3)将清洗的棉织物(18×18cm2)浸入含5wt%KH580的无水乙醇/蒸馏水=4:1(V/V)溶液中,浴比为50:1,在室温搅拌条件下进行表面改性,反应时间为2h;将改性织物浸入石墨烯/WPU吸波涂料中,浴比为50:1,加入1wt%热引发剂TCEP,室温搅拌条件反应6h,取出织物,烘干,制得rGO/WPU/棉吸波织物,记为样品1。
实施例2
以棉织物为基材,采用实施例1工艺,仅调节石墨烯丙酮分散液浓度,将其分散在100mL丙酮中。制得rGO/WPU/棉吸波织物,记为样品2。
实施例3
以棉织物为基材,采用实施例1工艺,仅调节石墨烯丙酮分散液浓度,将其分散在50mL丙酮中。制得rGO/WPU/棉吸波织物,记为样品3。
实施例4
采用涤纶(PET)织物为基材制备rGO/WPU/PET吸波织物,具体步骤如下:
(1)取200mg GO均匀分散在250mL无水乙醇/蒸馏水=2:1(V/V)溶液中,然后依次加入0.1mL TEA、2g APTES和0.2mL盐酸,室温搅拌24h;离心,无水乙醇洗涤后再离心,然后将其均匀分散在200mL蒸馏水中,缓慢加入1g二乙醇胺,在室温、搅拌条件下反应24h,产物经离心后均匀分散在200mL丙酮中,得到石墨烯丙酮分散液备用。
(2)14.63g IPDI、12g PEG400、50mg DBTDL和10mL丙酮置于四口烧瓶中,在65℃油浴、氮气、冷凝回流、机械搅拌下反应1h;升温至85℃,加入2.435g扩链剂DMPA和20mL上述石墨烯丙酮分散液,反应3h,反应结束,降温至80℃;然后加入3.664g封端剂HEMA,反应时间为4h,反应结束后,降至室温,并加入1.64g TEA进行中和反应,反应时间为45min;加入蒸馏水进行乳化,固含量控制在50%,从而制得石墨烯/WPU吸波涂料。
(3)将碱减量处理的PET织物(18×18cm2)浸入含5wt%KH580的无水乙醇/蒸馏水=4:1(V/V)溶液中,浴比为50:1,在室温搅拌条件下进行表面改性,反应时间为2h;将改性织物浸入石墨烯/WPU吸波涂料中,浴比为50:1,加入1wt%热引发剂TCEP,室温搅拌条件反应6h,取出织物,烘干,制得rGO/WPU/PET吸波织物,记为样品4。
实施例5
以PET织物为基材,采用实施例4工艺,仅调节石墨烯丙酮分散液浓度,将其分散在100mL丙酮中。制得rGO/WPU/PET吸波织物,记为样品5。
实施例6
以PET织物为基材,采用实施例4工艺,仅调节石墨烯丙酮分散液浓度,将其分散在50mL丙酮中。制得rGO/WPU/PET吸波织物,记为样品6。
本发明根据传输线理论,通过测试计算织物样品1-6的反射损耗(Reflectionloss,RL)值来表征其微波吸收性能,其吸波效能如图3和表1所示。测试结果表明样品1-6的反射率最小值均低于-20.1dB,吸收率高达99%以上,吸波性能较好;样品1-3的有效吸波带宽(RL≤-10dB)均在3.21GHz以上,吸波带宽较大;与实施例1-3相比,采用PET织物为基材制得吸波织物的反射损耗值较小,有效吸收频带较窄。但与专利CN 106288961A相比,本发明采用石墨烯等碳基新材料为吸波剂,产品质轻且易加工;而与CN 102493204A等涂覆型吸波织物相比,本发明通过硅烷偶联剂改性GO使其以化学键合方式均匀分散在WPU中,有利于提高石墨烯材料在粘结剂中的均匀分散性,此外本发明采用点击反应将吸波涂料接枝在纺织品表面,改善了吸波层与纤维基间的粘附牢度,有更好的使用性能。
此外,在本发明中,实施例1中所制得的吸波织物有效吸波带宽为4.40GHz,其反射损耗最小值达-20.1dB,转化为微波吸收率可达99%,可满足雷达隐身的要求;此外由于样品1中加入石墨烯的量最少,成本最低,其实用性较强。
表1
Claims (10)
1.一种石墨烯/水性聚氨酯吸波涂料,其特征在于,所述涂料是以石墨烯为吸波剂,通过硅烷偶联剂改性使其以化学键合方式均匀分散在水性聚氨酯中;
所述涂料的制备方法,包括:
(1)采用硅烷偶联剂对氧化石墨烯进行表面改性,然后用还原剂还原,离心并分散,得到石墨烯分散液,其中硅烷偶联剂与氧化石墨烯的质量比为5~20:1,还原剂与氧化石墨烯的质量比为5~10:1,石墨烯分散液质量浓度为0.1~0.5wt%;
(2)将异氟尔酮二异氰酸酯IPDI、聚乙二醇PEG400和二月桂酸二丁基锡DBTDL以质量比为10~20:10~20:0.05~0.1与溶剂混合,在氮气下搅拌反应,得到聚氨酯预聚体,加入扩链剂和步骤(1)中石墨烯分散液继续反应,加入甲基丙烯酸-2-羟基乙酯HEMA进行封端反应,加入碱中和反应,乳化,得到石墨烯/水性聚氨酯吸波涂料,其中IPDI与溶剂的比例为10~20g:10~20mL,IPDI、扩链剂、石墨烯、HEMA与碱的质量比为10~20:1.5~5:0.15~0.3:2~4:1.5~3。
2.一种石墨烯/水性聚氨酯吸波涂料的制备方法,包括:
(1)采用硅烷偶联剂对氧化石墨烯进行表面改性,然后用还原剂还原,离心并分散,得到石墨烯分散液,其中硅烷偶联剂与氧化石墨烯的质量比为5~20:1,还原剂与氧化石墨烯的质量比为5~10:1,石墨烯分散液质量浓度为0.1~0.5wt%;
(2)将异氟尔酮二异氰酸酯IPDI、聚乙二醇PEG400和二月桂酸二丁基锡DBTDL以质量比为10~20:10~20:0.05~0.1与溶剂混合,在氮气下搅拌反应,得到聚氨酯预聚体,加入扩链剂和步骤(1)中石墨烯分散液继续反应,加入甲基丙烯酸-2-羟基乙酯HEMA进行封端反应,加入碱中和反应,乳化,得到石墨烯/水性聚氨酯吸波涂料,其中IPDI与溶剂的比例为10~20g:10~20mL,IPDI、扩链剂、石墨烯、HEMA与碱的质量比为10~20:1.5~5:0.15~0.3:2~4:1.5~3。
3.根据权利要求2所述的制备方法,其特征在于,所述步骤(1)中硅烷偶联剂为KH580或3-氨丙基三乙氧基硅烷APTES;还原剂为二乙醇胺;还原时间为12~24h。
4.根据权利要求2所述的制备方法,其特征在于,所述步骤(1)中表面改性的工艺参数为:温度为室温,氧化石墨烯的溶剂为体积比为2~4:1的无水乙醇和蒸馏水混合溶剂,时间为12~24h;石墨烯分散液溶剂为丙酮。
5.根据权利要求2所述的制备方法,其特征在于,所述步骤(2)中搅拌反应温度为60~70℃,搅拌反应时间为1~1.5h;继续反应温度为80~90℃,继续反应时间为2~4h;封端反应温度为60~80℃,封端反应时间为4~6h。
6.根据权利要求2所述的制备方法,其特征在于,所述步骤(2)中扩链剂为2,2-二羟甲基丁酸DBMA或2,2-二羟甲基丙酸DMPA;碱为三乙胺;中和反应时间为0.5~1h;乳化是用去离子水。
7.一种如权利要求1所述的石墨烯/水性聚氨酯吸波涂料在织物整理中的应用。
8.按照权利要求7所述的应用,其特征在于,所述在织物整理中的应用具体为:采用3-巯丙基三乙氧基硅烷KH580对织物进行表面改性,然后利用巯基-烯点击反应将石墨烯/水性聚氨酯吸波涂料整理在巯基改性的织物表面,得到石墨烯/水性聚氨酯吸波纺织品,其中石墨烯/水性聚氨酯吸波涂料固含量为40~60%。
9.根据权利要求8所述的应用,其特征在于,所述织物为棉织物或碱减量涤纶织物;表面改性具体为:在室温搅拌条件下将织物浸入含5~10wt%KH580的无水乙醇和蒸馏水混合溶剂中,反应1~5h,其中浴比为50~100:1,无水乙醇和蒸馏水的体积比为2~4:1。
10.根据权利要求8所述的应用,其特征在于,所述巯基-烯点击反应具体为:将织物浸入石墨烯/水性聚氨酯吸波涂料中,浴比为50~100:1,加入热引发剂三(2-羧乙基)膦TCEP,在25~60℃下反应2~10h,其中TCEP占石墨烯/水性聚氨酯吸波涂料的质量含量为0.5~2wt%。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810798618.5A CN109056335B (zh) | 2018-07-19 | 2018-07-19 | 一种石墨烯/水性聚氨酯吸波涂料及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810798618.5A CN109056335B (zh) | 2018-07-19 | 2018-07-19 | 一种石墨烯/水性聚氨酯吸波涂料及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109056335A CN109056335A (zh) | 2018-12-21 |
CN109056335B true CN109056335B (zh) | 2021-04-02 |
Family
ID=64817517
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810798618.5A Expired - Fee Related CN109056335B (zh) | 2018-07-19 | 2018-07-19 | 一种石墨烯/水性聚氨酯吸波涂料及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109056335B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109629247B (zh) * | 2019-01-24 | 2021-09-17 | 大连东信微波技术有限公司 | 多普勒伪装网及其制作方法 |
CN109870429B (zh) * | 2019-03-11 | 2021-07-13 | 黔南民族师范学院 | 一种多层石墨烯传感生物芯片的制备方法 |
CN115339189B (zh) * | 2022-07-21 | 2024-07-16 | 东华大学 | 一种柔性宽频吸波织物及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103254400A (zh) * | 2013-05-20 | 2013-08-21 | 常州大学 | 一种氧化石墨烯/水性聚氨酯纳米复合材料的制备方法 |
CN105949986A (zh) * | 2016-05-31 | 2016-09-21 | 无锡伊佩克科技有限公司 | 一种改性石墨烯/水性聚氨酯复合纳米涂料的制备方法 |
CN108264755A (zh) * | 2018-04-03 | 2018-07-10 | 安徽大学 | 一种石墨烯-碳纳米管/水性聚氨酯复合材料的制备方法 |
-
2018
- 2018-07-19 CN CN201810798618.5A patent/CN109056335B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103254400A (zh) * | 2013-05-20 | 2013-08-21 | 常州大学 | 一种氧化石墨烯/水性聚氨酯纳米复合材料的制备方法 |
CN105949986A (zh) * | 2016-05-31 | 2016-09-21 | 无锡伊佩克科技有限公司 | 一种改性石墨烯/水性聚氨酯复合纳米涂料的制备方法 |
CN108264755A (zh) * | 2018-04-03 | 2018-07-10 | 安徽大学 | 一种石墨烯-碳纳米管/水性聚氨酯复合材料的制备方法 |
Non-Patent Citations (1)
Title |
---|
石墨烯/聚氨酯复合功能材料研究进展;罗晓民等;《功能材料》;20151231;第46卷(第16期);第16044-16051页 * |
Also Published As
Publication number | Publication date |
---|---|
CN109056335A (zh) | 2018-12-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109056335B (zh) | 一种石墨烯/水性聚氨酯吸波涂料及其制备方法和应用 | |
CN110845844A (zh) | 一种PANI/MXene/碳布复合吸波材料的制备方法 | |
CN110846881B (zh) | 一种Co3O4/PANI/MXene/PI电磁屏蔽织物的制备方法 | |
CN108570163B (zh) | 一种基于纳米纤维素的高效电磁屏蔽多孔材料的制备方法 | |
CN110982421B (zh) | 一种耐高温吸波涂料及其制备方法 | |
CN109423636B (zh) | 一种二次镀银高导电填料的制备方法 | |
CN115262231B (zh) | 一种自修复型自清洁电磁屏蔽织物涂层及其制备方法和应用 | |
CN110819220A (zh) | 一种石墨烯/镀银空心玻璃微珠电磁屏蔽涂料及其制备方法 | |
CN114364244A (zh) | 一种SiCnw/Co复合吸波材料的制备方法 | |
CN103920436A (zh) | 一种改性空心微球及其应用 | |
CN105131901A (zh) | 均匀核壳复合材料PPy@PANI及其制备方法 | |
CN108951192B (zh) | 一种磁性吸波织物及其制备方法和应用 | |
CN108530100A (zh) | 一种碳基吸波膜及制备方法 | |
CN116575229A (zh) | 一种uhmwpe纤维及织物表面改性与电磁屏蔽功能化的方法 | |
CN110713661A (zh) | 一种低频p波段吸波材料及其制备方法 | |
CN113402920B (zh) | 一种FeSiAl基有机-无机双层核壳结构的制备方法 | |
CN102766376B (zh) | 一种疏水型涂料及其制备方法、天线罩及天线系统 | |
CN108503869A (zh) | 低频电磁波吸收材料的制备方法 | |
CN106589363A (zh) | 一种聚苯胺/w型锶铁氧体复合材料的制备方法及其应用 | |
CN113173715A (zh) | 一种增强聚氯乙烯用玻璃纤维浸润剂及其制备方法和应用 | |
CN100485005C (zh) | 能吸收太阳能的纳米硫化锡涂层材料的制备方法 | |
CN110684438A (zh) | 一种水性防腐蚀耐老化吸波涂层及其制备方法 | |
CN107011917B (zh) | 一种聚硅氧烷超疏水膨胀土改良剂及其使用方法 | |
CN114517015A (zh) | 吸波组合物、吸波材料及其制备方法 | |
CN110541162A (zh) | 一种在吸波材料表面包覆磁性金属薄膜的方法 |
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 | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210402 |