CN110885440A - 一种涂料用羧基改性含氟聚芳醚树脂及其制备方法 - Google Patents
一种涂料用羧基改性含氟聚芳醚树脂及其制备方法 Download PDFInfo
- Publication number
- CN110885440A CN110885440A CN201911292113.2A CN201911292113A CN110885440A CN 110885440 A CN110885440 A CN 110885440A CN 201911292113 A CN201911292113 A CN 201911292113A CN 110885440 A CN110885440 A CN 110885440A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- containing polyarylether
- polyarylether resin
- molar amount
- coating
- 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
- 229920000090 poly(aryl ether) Polymers 0.000 title claims abstract description 49
- 239000011347 resin Substances 0.000 title claims abstract description 44
- 229920005989 resin Polymers 0.000 title claims abstract description 44
- 238000000576 coating method Methods 0.000 title claims abstract description 21
- 239000011248 coating agent Substances 0.000 title claims abstract description 20
- -1 Carboxyl modified fluorine Chemical class 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 24
- 239000011737 fluorine Substances 0.000 claims abstract description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 23
- ONUFSRWQCKNVSL-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F ONUFSRWQCKNVSL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- QRFMXBKGNQEADL-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 QRFMXBKGNQEADL-UHFFFAOYSA-N 0.000 claims abstract description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 239000003973 paint Substances 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000005028 tinplate Substances 0.000 abstract description 3
- 239000011157 advanced composite material Substances 0.000 abstract description 2
- 238000004100 electronic packaging Methods 0.000 abstract description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 150000002221 fluorine Chemical class 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
- C09D5/08—Anti-corrosive paints
-
- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种涂料用羧基改性含氟聚芳醚树脂及其制备方法。本发明先利用四烯丙基联苯二酚，2,2'‑双（4'‑羟基苯基）丙烷和十氟联苯，进行缩聚反应来制备含氟聚芳醚树脂，再通过3‑巯基‑1‑丙酸的烯‑巯点击化学反应，制得所述涂料用羧基改性含氟聚芳醚树脂，其侧链为羧基封端的5个亚甲基和1个硫醚键组成的长线性结构，所得羧基改性含氟聚芳醚树脂在极性非质子溶剂中具有良好的溶解性，可以用溶液浇铸在马口铁上制得涂层，所制得的涂层具有高硬度、高附着力、耐高温、耐腐蚀性和疏水性等特点，在电子封装，精密仪器，航空航天，耐高温涂料和先进复合材料等领域具有广泛的用途。
Description
技术领域
本发明是关于一种涂料用羧基改性含氟聚芳醚树脂及其制备方法，属于溶剂型功能树脂领域。
背景技术
聚芳醚是一种性能优良的工程塑料，具有优良的热学性能、高的机械强度和良好的化学稳定性等优点，使它在电子电器、交通运输、电子通信、精密仪器和航空航天领域具有广泛的应用空间。聚芳醚类聚合物能够以薄膜、纤维和涂层等多种形态使用。作为涂层使用，具有耐高温、耐磨损、耐腐蚀等性能。
含氟聚芳醚是将氟原子引入到聚芳醚分子链中，以提高或增加原有聚芳醚材料的性能。氟原子的引入降低了聚芳醚结构的刚性，提高了聚合物的热性能。由于C-F键键能较低，降低表面自由能，使材料具有很好的疏水疏油特性。Allied Signal等人通过十氟联苯和双酚单体合成了第一代含氟聚芳醚材料，该材料具有良好的疏水介电性能和热性能，Cassidy等人报道的一系列由十氟联苯制备的含氟聚芳醚材料都表现出低吸湿率和良好的热稳定性。此外，含氟高分子还具有超强的耐候性、介电性和耐污性能，说明含氟聚芳醚在电子封装，精密仪器，航空航天，耐高温涂料和先进复合材料等领域前景广阔。
但是含氟聚芳醚聚合物作为涂层应用在金属表面，存在附着力低的问题，那么提高涂层附着力是目前需要解决的问题。目前粘接机理主要有：机械理论、吸附理论、化学键形成理论、静电理论、弱边界层理论。所以目前，找到一种使涂层与金属基材间形成化学键，是一种可以有效提高涂层的附着力的方式。
发明内容
本发明的目的在于提供一种涂料用羧基改性含氟聚芳醚树脂及其制备方法，其利用四烯丙基联苯二酚，2,2'-双（4'-羟基苯基）丙烷和十氟联苯进行缩聚反应得到含氟聚芳醚树脂，再通过烯巯加成反应接入羧基，最终得到一种羧基改性含氟聚芳醚树脂；该树脂由于具有柔软的羧基封端的长侧链，以及刚性的含氟芳香主链，因此具有较好的粘附性、韧性和较高的硬度。
为实现上述目的，本发明采用如下技术方案：
一种涂料用羧基改性含氟聚芳醚树脂，其结构式如下：
式中m=10~200，n=0~200。
上述涂料用羧基改性含氟聚芳醚树脂的制备方法包括以下步骤：
（1）将四烯丙基联苯二酚，2,2'-双（4'-羟基苯基）丙烷和十氟联苯溶解于极性非质子溶剂中，以氟化铯为催化剂，在惰性气体氩气的保护下，0-80℃聚合10-60小时；反应结束后将反应物缓慢倒入去离子水中析出，沉淀干燥后在二氯甲烷溶剂中溶解后在甲醇中析出提纯，过滤并收集沉淀，再在60~120℃真空干燥10~40小时，制得含氟聚芳醚树脂；反应流程如下：
（2）将步骤（1）得到的含氟聚芳醚树脂和3-巯基-1-丙酸溶解在N-甲基吡咯烷酮中，在氩气的保护下，以偶氮二异丁腈为引发剂，冠醚为催化剂，在60-150℃下反应10-100小时，然后冷却到室温，缓慢倒入去离子水中析出，过滤后用去离子水洗涤2-10次后，在60~120℃真空干燥10~40小时，得到羧基改性含氟聚芳醚树脂；反应流程如下：
进一步地，步骤（1）所述十氟联苯的摩尔量为四烯丙基联苯二酚和2,2'-双（4'-羟基苯基）丙烷的摩尔量之和；所用氟化铯的摩尔量为十氟联苯摩尔量的2-10倍。
进一步地，步骤（1）所述极性非质子溶剂为N,N-二甲基乙酰胺，N,N-二甲基甲酰胺，N-甲基吡咯烷酮，二甲基亚砜中的任意一种。
进一步地，步骤（2）中偶氮二异丁腈的摩尔量为含氟聚芳醚树脂中双键摩尔量的0.5-2倍。
本发明所述的羧基改性含氟聚芳醚树脂的制备方法可用于涂料。
与现有技术相比，本发明具有如下有益效果：
（1）本发明所采用的原料为常见的化工原料，操作方便，易于产业化，且由于联苯二酚具有刚性共轭苯环，易于进行双键功能化，且产物易分离提纯。
（2）本发明在低温下进行聚合，操作简单，副反应极少，且分子量高
（3）本发明采用十氟联苯作为聚合单体，可显著提高产物的疏水性。
（4）本发明所得到的含氟聚芳醚树脂的双键在侧链末端，反应活性高。
（5）本发明通过烯巯加成反应，得到羧基封端、具有5个亚甲基和1个硫醚键的长线性侧链，羧基与金属基材之间形成氢键，显著提高产物的粘附性和韧性。
（6）采用本发明羧基改性含氟聚芳醚树脂所制得的涂层具有高硬度、高附着力、耐高温、耐腐蚀性和疏水性等特点。
附图说明
图1是实施例1制得的含氟聚芳醚树脂的核磁共振氢谱；
图2是实施例1制得的含氟聚芳醚树脂的红外光谱图；
图3是实施例4制得的羧基改性含氟聚芳醚树脂的核磁共振氢谱；
图4是实施例4制得的羧基改性含氟聚芳醚树脂的红外光谱图。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例1 含氟聚芳醚树脂的制备
将0.4573 g（1.32mmol）四烯丙基联苯二酚、1.2054 g（5.28mmol）2,2'-双（4'-羟基苯基）丙烷、2.2052 g（6.6mmol）十氟联苯和13mL N-甲基吡咯烷酮加入到三口烧瓶中，溶解后，再加入5.0000 g氟化铯、0.10 g氢化钙，在氩气的保护下，室温反应24 h，得到的含氟聚芳醚树脂在去离子水中析出沉淀，用二氯甲烷溶解后再在甲醇中析出沉淀，过滤，收集沉淀在80 ℃烘箱中干燥得到含氟聚芳醚树脂，产率为92%。该树脂的核磁共振氢谱的数据为：1HNMR (400 MHz，CDCl3, ppm)，1.70 (d, 6H), 3.49 (s, 2H), 5.00 (s, 2H), 5.94 (s,1H), 6.98 (d, 4H), 7.24 (d, 4H), 7.34 (d, 1H); 红外数据为：FT-IR (cm-1) υ 3037,2973, 2937, 1649, 1603, 1487, 1410, 1365, 1330, 1280, 1209, 1173, 1070, 1002,979, 982, 918, 869, 830, 725, 659, 552。
实施例2含氟聚芳醚树脂的制备
将实施例1中四烯丙基联苯二酚的投料量改为0.1143 g（0.33mmol）、1.4342 g（6.27mmol）2,2'-双（4'-羟基苯基）丙烷、2.2052 g（6.6mmol）十氟联苯投料，其余操作按实施例1，产率为93%。
实施例3 羧基改性含氟聚芳醚树脂的制备
取实施例1中所得的含氟聚芳醚树脂中1.00 g（1.83 mmol）和15 mL NMP加入到50 mL的三口烧瓶中，完全溶解后加入0.52 mL（5.86 mmol）3-巯基-1-丙酸，再取0.12g（0.73mmol）AIBN溶解在6 mL NMP中，待温度升高至80 ℃时，缓慢滴加AIBN的NMP溶液，在氩气的保护下反应96小时，然后冷却至室温，边搅拌边倒入去离子水中析出沉淀，过滤后用去离子水洗涤5次后，在鼓风烘箱中干燥12小时再在真空干燥12小时，产率为80%。该化合物的核磁共振氢谱的数据为：1H NMR (400 MHz，CDCl3, ppm)，1.70 (d, 6H), 2.20 (d, 6H), 2.61(m, 2H), 2.79 (m, 2H)， 6.98(m, 4H), 7.23(m, 4H), 7.29(m, 1H)；红外数据为：FT-IR(cm-1) υ 3043, 2968, 2931, 1712, 1649, 1603, 1487, 1409, 1365, 1330, 1284,1209, 1174, 1105, 1001, 982, 874, 831, 724, 660, 564。
实施例4 羧基改性含氟聚芳醚树脂的制备
取实施例2中所得的含氟聚芳醚树脂中1.00 g（1.91 mmol）和15 mL NMP加入到50 mL的三口烧瓶中，完全溶解后加入0.14 mL（1.52 mmol）3-巯基-1-丙酸，再取0.03g（0.19mmol）AIBN溶解在4 mL NMP中，其余操作按实施例3，产率为82%。
实施例5 羧基改性含氟聚芳醚树脂涂层的制备
将马口铁用砂纸打磨后，用去离子水、乙醇和丙酮洗净 烘干。实施例3和4中所得的羧基改性含氟聚芳醚树脂各取0.2 g溶解在10 mL NMP中，得到2 wt.%的溶液，将1 mL溶液在准备好的马口铁上铺膜，在80 oC的烘箱中烘干12小时，再在100 oC真空烘箱中干燥12小时，得到制备好的涂层，经测试，得到的羧基改性含氟聚芳醚树脂涂层硬度分别为2H和5H，附着力都为0级，韧性都为0.5，水接触角分别为84.36°和102.20°。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (9)
1.一种涂料用羧基改性含氟聚芳醚树脂，其特征在于，结构式如下：
式中m=10~200，n=0~200。
2.一种如权利要求1所述的涂料用羧基改性含氟聚芳醚树脂，其特征在于，包括以下步骤：
（1）将四烯丙基联苯二酚，2,2'-双（4'-羟基苯基）丙烷和十氟联苯溶解于极性非质子溶剂中，以氟化铯为催化剂，在惰性气体氩气的保护下进行聚合反应，反应结束后将反应物缓慢倒入去离子水中，过滤并收集沉淀，然后在二氯甲烷溶剂中溶解后，在甲醇中析出提纯，过滤并收集沉淀，然后进行真空干燥，制得含氟聚芳醚树脂；
（2）将步骤（1）得到的含氟聚芳醚树脂和3-巯基-1-丙酸溶解在N-甲基咯烷酮中，在氩气的保护下，以偶氮二异丁腈、冠醚分别为引发剂和催化剂，进行反应，然后冷却到室温，缓慢倒入去离子水中析出，过滤后用去离子水洗涤后，进行干燥，得到羧基改性含氟聚芳醚树脂。
3.根据权利要求2所述的制备方法，其特征在于，步骤（1）所述十氟联苯的摩尔量为四烯丙基联苯二酚和2,2'-双（4'-羟基苯基）丙烷的摩尔量之和；所用氟化铯的摩尔量为十氟联苯摩尔量的2-10倍。
4.根据按权利要求2所述的制备方法，其特征在于，步骤（1）所述聚合反应的温度为0-80℃，聚合时间为10-60小时。
5.根据按权利要求2所述的制备方法，其特征在于，步骤（1）和（2）所述真空干燥温度为60~120℃，真空干燥时间为10~40小时。
6.根据权利要求2所述的制备方法，其特征在于，步骤（1）所述极性非质子溶剂为N,N-二甲基乙酰胺，N,N-二甲基甲酰胺，N-甲基吡咯烷酮，二甲基亚砜中的任意一种。
7.根据按权利要求2所述的制备方法，其特征在于，步骤（2）中所述的3-巯基-1-丙酸的摩尔量为含氟聚芳醚树脂中双键摩尔量的1-10倍。
8.根据权利要求2所述的制备方法，其特征在于，步骤（2）中偶氮二异丁腈的摩尔量为含氟聚芳醚树脂中双键摩尔量的0.5-2倍。
9.根据权利要求2所述的制备方法，其特征在于，步骤（2）所述反应温度为60-150℃，反应时间为10-100小时。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911292113.2A CN110885440B (zh) | 2019-12-12 | 2019-12-12 | 一种涂料用羧基改性含氟聚芳醚树脂及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911292113.2A CN110885440B (zh) | 2019-12-12 | 2019-12-12 | 一种涂料用羧基改性含氟聚芳醚树脂及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110885440A true CN110885440A (zh) | 2020-03-17 |
| CN110885440B CN110885440B (zh) | 2021-09-28 |
Family
ID=69751988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911292113.2A Expired - Fee Related CN110885440B (zh) | 2019-12-12 | 2019-12-12 | 一种涂料用羧基改性含氟聚芳醚树脂及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110885440B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113913046A (zh) * | 2021-09-28 | 2022-01-11 | 武汉纺织大学 | 一种生物基抗菌紫外荧光涂料及其制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008978A (zh) * | 2016-06-30 | 2016-10-12 | 吉林大学 | 一种含羧基侧基聚芳醚类共聚物、制备方法及其在超滤膜亲水改性方面的应用 |
| CN109320715A (zh) * | 2018-11-02 | 2019-02-12 | 福州大学 | 一种密集侧链型含氟磺化聚芳醚化合物及其制备方法与应用 |
-
2019
- 2019-12-12 CN CN201911292113.2A patent/CN110885440B/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008978A (zh) * | 2016-06-30 | 2016-10-12 | 吉林大学 | 一种含羧基侧基聚芳醚类共聚物、制备方法及其在超滤膜亲水改性方面的应用 |
| CN109320715A (zh) * | 2018-11-02 | 2019-02-12 | 福州大学 | 一种密集侧链型含氟磺化聚芳醚化合物及其制备方法与应用 |
Non-Patent Citations (1)
| Title |
|---|
| MIYAKE MUNEHARU，ET AL.: "A novel water-soluble cyclophane as a host for cationic, anionic, and neutral aromatic guests", 《CHEMICAL & PHARMACEUTICAL BULLETIN》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113913046A (zh) * | 2021-09-28 | 2022-01-11 | 武汉纺织大学 | 一种生物基抗菌紫外荧光涂料及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110885440B (zh) | 2021-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100734458B1 (ko) | 전자 흡인성기 및 전자 공여성기를 포함하는 단량체, 이를이용한 공중합체, 및 양성자 전도막 | |
| KR101953369B1 (ko) | 중합성 조성물 | |
| CN109971151B (zh) | 含三芳基均三嗪结构的双邻苯二甲腈树脂纤维增强材料及其制备方法 | |
| WO2000020484A1 (en) | Hydroxy-functionalized poly(amino ether) salts | |
| EP2880079B1 (en) | Synthesis of and curing additives for phthalonitriles | |
| US8981036B2 (en) | Synthesis of and curing additives for phthalonitriles | |
| CN109320715B (zh) | 一种密集侧链型含氟磺化聚芳醚化合物及其制备方法与应用 | |
| CN109320521A (zh) | 环氧单体及其制备方法、环氧树脂 | |
| WO2012088759A1 (zh) | 一种可熔性聚酰亚胺模塑料及其制备方法 | |
| CN102040737A (zh) | 一种利用聚醚醚酮改性的酚醛树脂及其制备方法 | |
| US8859712B2 (en) | Synthesis of and curing additives for phthalonitriles | |
| CN115403764B (zh) | 一种含有环氧基团的聚芳醚酮化合物及其制备方法 | |
| CN110885440B (zh) | 一种涂料用羧基改性含氟聚芳醚树脂及其制备方法 | |
| CN114605640A (zh) | 一种高性能聚砜树脂及其制备方法和应用 | |
| CN114891218A (zh) | 一种高性能聚醚砜树脂及其制备方法和应用 | |
| CN1673254A (zh) | 电活性聚芳醚酮（砜）系列聚合物及其制备方法 | |
| KR101798499B1 (ko) | 이온 전도성을 갖는 가지형 술폰화 폴리페닐렌 고분자 및 이를 포함하는 연료전지용 전해질막 | |
| CN115304764B (zh) | 一种环氧化含氟聚芳醚化合物及其制备方法 | |
| KR101395843B1 (ko) | 그라핀-폴리아미드 복합체 및 그의 제조방법 | |
| CN103613764A (zh) | 主链含笼型倍半硅氧烷双甲板结构的聚芳醚砜树脂及其制备方法 | |
| CN109880098B (zh) | 一种以氨基作为交联基团的聚芳醚砜树脂及其交联产物 | |
| Chen et al. | Tetrafluorophenylene-Containing Vinylbenzyl Ether-Terminated Oligo (2, 6-dimethyl-1, 4-phenylene ether) with Better Thermal, Dielectric, and Flame-Retardant Properties for Application in High-Frequency Communication | |
| WO2015183518A1 (en) | Synthesis of and curing additives for phthalonitriles | |
| CN114634698B (zh) | 一种聚芳醚腈复合材料及其制备方法与应用 | |
| CN114479063B (zh) | 一种含萘结构的聚芳醚腈及其制备方法和应用 |
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: 20210928 |