WO2017166913A1 - 一种含氟硅环氧树脂耐辐射涂料及其制备方法 - Google Patents

一种含氟硅环氧树脂耐辐射涂料及其制备方法 Download PDF

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WO2017166913A1
WO2017166913A1 PCT/CN2017/072219 CN2017072219W WO2017166913A1 WO 2017166913 A1 WO2017166913 A1 WO 2017166913A1 CN 2017072219 W CN2017072219 W CN 2017072219W WO 2017166913 A1 WO2017166913 A1 WO 2017166913A1
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fluorine
parts
radiation
epoxy resin
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戴李宗
毛杰
袁丛辉
王诗榕
武彤
吴俣哲
许一婷
罗伟昂
王书传
陈国荣
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Xinhe New Materials Co Ltd
Xiamen University
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Xinhe New Materials Co Ltd
Xiamen University
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    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the invention belongs to a functional coating in the field of coatings, in particular to a fluorine-containing silicon epoxy resin radiation-resistant coating and a preparation method thereof.
  • the radiation resistant base materials for nuclear industry coatings are epoxy resin, modified phenolic acid, chlorinated rubber, alkyd, vinyl resin, etc.
  • the amine-cured epoxy resin is particularly suitable for coatings resistant to gamma radiation.
  • Fluorinated epoxy is a type of epoxy resin with a fluorine atom on the main chain or side groups of the polymer.
  • the bond energy of the FC bond formed by the fluorine atom and the carbon atom is large (485 kJ/mol), and the electron cloud of the fluorine atom is CC.
  • the shielding of the bond protects the CC bond from radiation and chemicals, making the fluoropolymer excellent in corrosion resistance and durability.
  • the selection and use of the curing agent and the addition of the auxiliary materials play a vital role in the final performance of the product.
  • Ci-O bond can have high radiation resistance
  • Changshu is equal (a silicone-epoxy radiation-resistant coating and its preparation method, Chinese Patent, Publication No.: CN 104263194A) discloses an epoxy resin. Radiation-resistant coating compounded with silicone resin. Although the coating material is resistant to radiation, the use of silicone resin in a large amount of the main film-forming material will definitely reduce the mechanical properties and corrosion resistance of the coating material.
  • the ⁇ bond on the benzene ring enables the radiant energy received by individual electrons to be uniformly dispersed to all the electrons on the ⁇ bond, reducing the local C-C bond
  • the chain breakage that occurs during excitation enhances the radiation resistance of the material, and the Si-O bond of the high bond energy and the electron cloud of the fluorine atom in the FC bond shield the CC bond, thereby protecting the CC bond, thereby effectively improving the material. Radiation resistance. .
  • the present invention is directed to the deficiencies of the prior art, and based on the use of a fluorine-containing bisphenol AF epoxy, an organic amine and an octaphenylamino polysilsesquioxane (OAPPOSS) compound curing agent are used to participate in the bisphenol AF type.
  • the curing of the fluorine-containing epoxy resin gives a coating material excellent in radiation resistance without sacrificing mechanical properties.
  • the invention aims to provide a fluorine-containing silicon epoxy resin radiation-resistant paint and a preparation method thereof.
  • the formulation of the fluorine-containing silicon epoxy resin radiation-resistant coating is as follows:
  • the preparation method of the bisphenol AF type fluorine-containing epoxy resin refers to the steps provided by the public patent CN201310352654.6:
  • the reactive diluent may be selected from the group consisting of 1,6-hexanediol diacrylate, ⁇ -hydroxyethyl methacrylate, tolyl glycidyl ether, castor oil polyglycidyl ether, and ethylene glycol diglycidyl ether.
  • 1,6-hexanediol diacrylate ⁇ -hydroxyethyl methacrylate
  • tolyl glycidyl ether castor oil polyglycidyl ether
  • ethylene glycol diglycidyl ether ethylene glycol diglycidyl ether
  • the metal oxide nanopowder is one or more of ZnO, Al 2 O 3 , TiO 2 , and Fe 2 O 3 of 50 to 300 nm.
  • the curing agent is an organic compound such as ethylenediamine, diethylenetriamine, m-phenylenediamine or 4,4-diaminodiphenylmethane used in combination with an epoxy resin.
  • the silsesquioxane (OAPPOSS) wherein the ratio of the amine curing agent to the OAPPOSS is from 10:1 to 5.
  • the preparation method of OAPPOSS is described in the literature M. Laine, et al. Octa (aminophenyl) silsesquioxane as a Nanoconstruction Site. J. Am. Steps in Chem. Soc. 2001, 123, 12416-12417.
  • OPS octaphenyl polysilsesquioxane
  • the antifoaming agent is preferably dimethicone.
  • the preparation method of the fluorine-containing silicon epoxy resin radiation-resistant coating is as follows: First, the metal oxide nano powder and the antifoaming agent are sequentially dissolved in the reactive diluent, and stirred for 0.5 to 1 hour to obtain a uniform emulsion, which is under ultrasonic vibration. The epoxy resin was added portionwise to the emulsion in portions, and stirred for 0.5 to 2 hours to uniformly obtain the A component. Next, the amine curing agent and OAPPOSS were added to xylene to be uniformly dispersed to obtain a B component. The fluorine-containing silicon epoxy resin radiation-resistant coating can be obtained by mixing the components A and B.
  • Fluorine-containing epoxy is used as the main film-forming material of the coating. Compared with ordinary epoxy and phenolic modified epoxy, the paint film not only has higher radiation resistance, but also F-C bond in fluorine-containing epoxy resin. The bond energy is large, and the electron cloud of the fluorine atom shields the C-C bond to protect the C-C bond from radiation and chemicals, and gives the coating better antifouling and anti-corrosion properties, so that the coating material has Excellent weather resistance.
  • OAPPOSS organic amine and octaphenylamino polysilsesquioxane
  • OAPPOSS organic amine and octaphenylamino polysilsesquioxane
  • the addition of OAPPOSS improves the thermal stability of the epoxy resin.
  • octaphenylamino polysilsesquioxane contains a plurality of functional groups which can participate in epoxy curing, and can be well dispersed in the epoxy group, and OAPPOSS has eight benzene ring structures and ⁇ on the benzene ring.
  • the bond can uniformly disperse the radiant energy received by the individual electrons to all the electrons on the ⁇ bond, reduce the chain breakage of the local CC bond due to excitation, and improve the radiation resistance of the material.
  • OPS octaphenyl polysilsesquioxane
  • 15g of metal oxide nanopowder and 0.5g of antifoaming agent were sequentially dissolved in 15g of reactive diluent, and stirred for 1 hour to obtain a uniform emulsion.
  • 120g of epoxy resin was added to the emulsion in batches under ultrasonic vibration, and stirred for 1.5 hours until uniform.
  • the component A is obtained.
  • 30 g of the amine curing agent and 10 g of OAPPOSS were added to 10 mL of xylene to be uniformly dispersed to obtain a B component.
  • the components A and B are mixed to obtain a fluorine-containing silicone epoxy radiation-resistant paint.
  • OPS octaphenyl polysilsesquioxane
  • OPS octaphenyl polysilsesquioxane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)

Abstract

一种含氟硅环氧树脂耐辐射涂料及其制备方法，涂料按质量比的组成为双酚AF型含氟环氧树脂80～150份，活性稀释剂10～30份，金属氧化物纳米粉5～20份，复配固化剂30～50份，消泡剂0.2～0.8份。复配固化剂为有机胺和八苯基氨基倍半硅氧烷，参与双酚AF型含氟环氧树脂的固化，得到的涂层材料具有良好的耐辐射性能。

Description

一种含氟硅环氧树脂耐辐射涂料及其制备方法 技术领域
本发明属于涂料领域的一种功能涂料，具体涉及一种含氟硅环氧树脂耐辐射涂料及其制备方法。
技术背景
随着化石能源燃料储量的不断减少与环境污染的日益加剧，越来越多的国家把目光投向清洁能源核电。从2005年开始，我国每年都有新增的核电站建设工程。国家发改委《国家核电发展专题规划(2005-2020)》指出，到2020年国家将建成20多座2组100万千瓦的核电站，发展核电及“核电走出去”均已上升为国家战略。在中国核电事业蓬勃发展之时，核电站机组及相关设备所需耐辐射特种涂料的研发日益受到重视。核电厂的很多设备、设施都需要进行涂装保护，涂装保护所用特种涂料，要求具有高抗辐射和易去污、耐腐蚀性能及其他特殊化学性能，并且能够吸收辐射，以便保护放射源周围的环境。
研究表明，放射性辐照会加速涂层中的主要成膜物质—高分子聚合物的老化降解开裂，或使聚合物经高能辐照后产生自由基和空气中的氧原子发生反应，引起聚合物的交联反应而变脆开裂，影响涂料性能。因此，耐辐射涂料的主要成膜物质的性质对涂料的耐辐射性能影响显著。目前核工业涂料用的抗辐射基料有环氧树脂、改性酚醛、氯化橡胶、醇酸、乙烯基树脂等，胺固化的环氧树脂特别适用于抗γ射线辐射的涂料。
含氟环氧是聚合物主链或侧基上带有氟原子的一类环氧树脂，氟原子与碳原子形成的F-C键的键能大(485kJ/mol)，氟原子的电子云对C-C键的屏蔽作用可以保护C-C键避免受辐射和化学品的危害，使得含氟聚合物具有优异的耐腐蚀性与耐久性。但是仅仅使用含氟环氧很难得到性能最佳的特种涂料产品，固化剂的选择与使用，辅料的添加都对产品的最终性能起着至关重要的作用。众所周知，Si-O键键能高耐辐射能力强，常熟全等(一种有机硅-环氧树脂耐辐射涂料及其制备方法，中国专利，公开号：CN 104263194A)公开了一种环氧树脂和有机硅树脂复合的耐辐射涂料，这种涂层材料虽然耐辐射性尚可，但是主要成膜物质大量使用有机硅树脂必将降低涂层材料力学性能和耐腐蚀性。鉴于苯环上的π键能使个别电子接受的辐射能均匀的分散给π键上的所有电子，减少局部C-C键因受 激发而发生的链断裂，提高材料的耐辐射性能，并且高键能的Si-O键和F-C键中氟原子的电子云对C-C键的屏蔽作用可以保护C-C键，因此均能有效提高材料的耐辐射性能。。因此，本发明针对现有技术不足，在使用含氟双酚AF环氧的基础上，采用有机胺和八苯基氨基聚倍半硅氧烷(OAPPOSS)复配固化剂，参与双酚AF型含氟环氧树脂的固化，得到耐辐射性能优异而又不牺牲力学性能的涂层材料。
发明内容
本发明目的在于提供一种含氟硅环氧树脂耐辐射涂料及其制备方法。
所述一种含氟硅环氧树脂耐辐射涂料的配方如下：
双酚AF型含氟环氧树脂80～150份，活性稀释剂10～30份，金属氧化物纳米粉5～20份，复配固化剂30～50份，消泡剂0.2～0.8份。
所述双酚AF型含氟环氧树脂的制备方法参照公开专利CN201310352654.6所提供的步骤：
(1)将30～40份含氟单体和20～30份环氧氯丙烷加入反应容器中，搅拌溶液，升温65℃。
(2)用5～10份NaOH和15～20份水配成碱液，1～1.5小时加入反应容器中，温度控制依然控制在65℃。
(3)滴加完碱液，将反应物在70℃下回流1.5小时，体系呈现乳黄色。
(4)加入去离子水、甲苯，搅拌均匀后，静置分液，除去水层，重复几次操作除去水层分出有机相，减压下蒸馏除去溶剂甲苯和未反应的环氧氯丙烷，得淡黄色粘稠树脂。
所述活性稀释剂可选1,6-己二醇二丙烯酸酯、甲基丙烯酸-β-羟乙酯、甲苯缩水甘油醚、蓖麻油多缩水甘油醚，乙二醇二缩水甘油醚中的一种。
所述金属氧化物纳米粉为50～300nm的ZnO、Al2O3、TiO2、Fe2O3中的一种或几种。
所述固化剂为与环氧树脂配合使用的胺类如乙二胺、二乙烯三胺、间苯二胺、4,4-二氨基二苯基甲烷中的一种复配八苯基氨基聚倍半硅氧烷(OAPPOSS)，其中胺类固化剂与OAPPOSS的比例为10:1～5。OAPPOSS的制备方法参照文献M.Laine，et al.Octa(aminophenyl)silsesquioxane as aNanoconstruction Site.J.Am. Chem.Soc.2001,123,12416-12417.中的步骤：
(1)冰水浴中将5～10份八苯基聚倍半硅氧烷(OPS)分散于30～60体积份硝酸溶液，均匀搅拌30min。
(2)将OPS硝酸溶液室温下继续反应15～30h，抽滤并水洗3～5次后得到黄色沉淀。
(3)将5～10份(2)中所得黄色沉淀与0.5～2份钯碳催化剂置于圆底烧瓶中，氩气保护下加入10～20体积份四氢呋喃(THF)和10～20体积份三乙胺(TEA)，反应液加热至60℃，加入4～10体积份甲酸，继续反应5～10h。
(4)反应结束后，抽滤后用乙酸乙酯和水分别洗涤3～5次，得淡黄色固体。
所述消泡剂优选二甲基硅油。
所述一种含氟硅环氧树脂耐辐射涂料的制备方法为：首先，金属氧化物纳米粉、消泡剂先后依次溶于活性稀释剂中，搅拌0.5～1小时得到均匀乳液，超声振荡下往乳液中分批逐量加入环氧树脂，搅拌0.5～2小时至均匀得到A组分。其次，将胺类固化剂和OAPPOSS加入二甲苯中分散均匀得到B组分。将A、B组分混合即可得含氟硅环氧树脂耐辐射涂料。
本发明含氟硅环氧树脂耐辐射涂料具有以下特点：
(1)采用含氟环氧作为涂料主要成膜物质，相对于普通环氧和酚醛改性环氧，漆膜不仅具有更高的耐辐射性能，且含氟环氧树脂中F‐C键的键能大，氟原子的电子云对C‐C键的屏蔽作用可以保护C‐C键避免受辐射和化学品的危害，赋予涂料更好的防污性与防腐蚀性能，使涂层材料具备优异的耐候性。
(2)采用有机胺和八苯基氨基聚倍半硅氧烷(OAPPOSS)复配固化剂，OAPPOSS的加入提高了环氧树脂的热稳定性。相对于常规POSS，八苯基氨基聚倍半硅氧烷含有多个可参与环氧固化的官能团，可以在环氧基体中良好分散，且OAPPOSS带有八个苯环结构，苯环上的π键能使个别电子接受的辐射能均匀的分散给π键上的所有电子，减少局部C-C键因受激发而发生的链断裂，提高材料的耐辐射性能。
具体实施方式
下面通过实施例对本发明做进一步说明。
实施例1
金属氧化物纳米粉5g、消泡剂0.2g先后依次溶于10g活性稀释剂中，搅拌0.5小时得到均匀乳液，超声振荡下往乳液中分批逐量加入80g环氧树脂，搅拌0.5小时至均匀得到A组分。将20g胺类固化剂和5gOAPPOSS加入10mL二甲苯中分散均匀得到B组分。将A、B组分混合得到含氟硅环氧树脂耐辐射涂料。
所涉及的含氟树脂的制备参照公开专利CN201310352654.6步骤如下：
(1)将30g2,2-二(羟基苯基)-,1,1,3.3,3-六氟丙烷和28g环氧氯丙烷加入加入带有搅拌棒及控温装置的三口烧瓶中，搅拌溶液，升温65℃。
(2)取6gNaOH和17g去离子水配成碱液，1.5小时内加入反应容器中，温度控制依然控制在65℃。
(3)滴加完碱液，将反应物在70℃下回流1.5小时，体系呈现乳黄色。
(4)加入27mL去离子水、54mL甲苯，搅拌均匀后，静置分液，除去水层，重复几次操作除去水层分出有机相，减压下蒸馏除去溶剂甲苯和未反应的环氧氯丙烷，得淡黄色粘稠含氟树脂。
所涉及的OAPPOSS的制备方法参照文献M.Laine，et al.Octa(aminophenyl)silsesquioxane as aNanoconstruction Site.J.Am.Chem.Soc.2001,123,12416-12417.步骤如下：
(1)冰水浴中将5g八苯基聚倍半硅氧烷(OPS)分散于30mL硝酸溶液，均匀搅拌30min。
(2)将OPS硝酸溶液室温下继续反应15h，抽滤并水洗3次后得到黄色沉淀。
(3)将5g(2)中所得黄色沉淀与0.5g钯碳催化剂置于圆底烧瓶中，氩气保护下加入10mL四氢呋喃(THF)和10mL三乙胺(TEA)，反应液加热至60℃，加入4mL甲酸，继续反应5h。
(4)反应结束后，抽滤后用乙酸乙酯和水分别洗涤3次，得淡黄色固体。
实施例2
金属氧化物纳米粉15g、消泡剂0.5g先后依次溶于15g活性稀释剂中，搅拌1小时得到均匀乳液，超声振荡下往乳液中分批逐量加入120g环氧树脂，搅拌1.5小时至均匀得到A组分。将30g胺类固化剂和10gOAPPOSS加入10mL二甲苯中分散均匀得到B组分。将A、B组分混合得到含氟硅环氧树脂耐辐射涂料。
所涉及的含氟树脂的制备参照公开专利CN201310352654.6步骤如下：
(1)将30g2,2-二(羟基苯基)-,1,1,3.3,3-六氟丙烷和28g环氧氯丙烷加入加入带有搅拌棒及控温装置的三口烧瓶中，搅拌溶液，升温65℃。
(2)取6gNaOH和17g去离子水配成碱液，1.5小时内加入反应容器中，温度控制依然控制在65℃。
(3)滴加完碱液，将反应物在70℃下回流1.5小时，体系呈现乳黄色。
(4)加入27mL去离子水、54mL甲苯，搅拌均匀后，静置分液，除去水层，重复几次操作除去水层分出有机相，减压下蒸馏除去溶剂甲苯和未反应的环氧氯丙烷，得淡黄色粘稠含氟树脂。
所涉及的OAPPOSS的制备方法参照文献M.Laine，et al.Octa(aminophenyl)silsesquioxane as aNanoconstruction Site.J.Am.Chem.Soc.2001,123,12416-12417.步骤如下：
(1)冰水浴中将8g八苯基聚倍半硅氧烷(OPS)分散于30～60mL硝酸溶液，均匀搅拌30min。
(2)将OPS硝酸溶液室温下继续反应20h，抽滤并水洗5次后得到黄色沉淀。
(3)将8g(2)中所得黄色沉淀与1g钯碳催化剂置于圆底烧瓶中，氩气保护下加入15mL四氢呋喃(THF)和15mL三乙胺(TEA)，反应液加热至60℃，加入8mL甲酸，继续反应10h。
(4)反应结束后，抽滤后用乙酸乙酯和水分别洗涤5次，得淡黄色固体。
实施例3
金属氧化物纳米粉20g、消泡剂0.8g先后依次溶于30g活性稀释剂中，搅拌1小时得到均匀乳液，超声振荡下往乳液中分批逐量加入150g环氧树脂，搅拌2小时至均匀得到A组分。将40g胺类固化剂和20gOAPPOSS加入20mL二甲苯中分散均匀得到B组分。将A、B组分混合得到含氟硅环氧树脂耐辐射涂料。
所涉及的含氟树脂的制备参照公开专利CN201310352654.6步骤如下：
(1)将40g2,2-二(羟基苯基)-,1,1,3.3,3-六氟丙烷和30g环氧氯丙烷加入加入带有搅拌棒及控温装置的三口烧瓶中，搅拌溶液，升温65℃。
(2)取10gNaOH和20g去离子水配成碱液，1.5小时内加入反应容器中， 温度控制依然控制在65℃。
(3)滴加完碱液，将反应物在70℃下回流1.5小时，体系呈现乳黄色。
(4)加入27mL去离子水、54mL甲苯，搅拌均匀后，静置分液，除去水层，重复几次操作除去水层分出有机相，减压下蒸馏除去溶剂甲苯和未反应的环氧氯丙烷，得淡黄色粘稠含氟树脂。
所涉及的OAPPOSS的制备方法参照文献M.Laine，et al.Octa(aminophenyl)silsesquioxane as aNanoconstruction Site.J.Am.Chem.Soc.2001,123,12416-12417.步骤如下：
(1)冰水浴中将10g八苯基聚倍半硅氧烷(OPS)分散于40mL硝酸溶液，均匀搅拌30min。
(2)将OPS硝酸溶液室温下继续反应30h，抽滤并水洗5次后得到黄色沉淀。
(3)将10g(2)中所得黄色沉淀与2g钯碳催化剂置于圆底烧瓶中，氩气保护下加入15mL四氢呋喃(THF)和15mL三乙胺(TEA)，反应液加热至60℃，加入10mL甲酸，继续反应10h。
(4)反应结束后，抽滤后用乙酸乙酯和水分别洗涤5次，得淡黄色固体。
表1实施例1至3的耐辐射涂料的性能测试结果
Figure PCTCN2017072219-appb-000001

Claims (10)

  1. 一种含氟硅环氧树脂耐辐射涂料，其特征在于其按质量比的组成如下：双酚AF型含氟环氧树脂80～150份，活性稀释剂10～30份，金属氧化物纳米粉5～20份，复配固化剂30～50份，消泡剂0.2～0.8份。
  2. 如权利要求1所述一种含氟硅环氧树脂耐辐射涂料，其特征在于所述双酚AF型含氟环氧树脂的制备方法如下：
    将含氟单体和环氧氯丙烷加入反应容器中升温反应，将碱液加入反应容器中，将反应物回流，然后加入去离子水和甲苯，静置分液，除去水层，分出有机相，减压蒸馏除去溶剂甲苯和未反应的环氧氯丙烷，得双酚AF型含氟环氧树脂，所得双酚AF型含氟环氧树脂呈淡黄色粘稠树脂。
  3. 如权利要求2所述一种含氟硅环氧树脂耐辐射涂料，其特征在于所述含氟单体、环氧氯丙烷、NaOH、水的质量比为(6～8)∶(4～6)∶(1～2)∶(3～4)；所述升温反应的温度可为65℃，升温反应的时间可为1～1.5h；所述回流温度可为70℃，回流的时间可为1.5h；所述除去水层可重复2～3次。
  4. 如权利要求1或2所述一种含氟硅环氧树脂耐辐射涂料，其特征在于所述活性稀释剂选自1,6-己二醇二丙烯酸酯、甲基丙烯酸-β-羟乙酯、甲苯缩水甘油醚、蓖麻油多缩水甘油醚、乙二醇二缩水甘油醚中的一种。
  5. 如权利要求1所述一种含氟硅环氧树脂耐辐射涂料，其特征在于所述金属氧化物纳米粉选自ZnO、Al2O3、TiO2、Fe2O3中的至少一种；金属氧化物纳米粉的粒径为50～300nm。
  6. 如权利要求1所述一种含氟硅环氧树脂耐辐射涂料，其特征在于所述复配固化剂为胺类固化剂与八苯基氨基聚倍半硅氧烷复配而成，所述胺类固化剂选自乙二胺、二乙烯三胺、间苯二胺、4,4-二氨基二苯基甲烷等中的一种；胺类固化剂与八苯基氨基聚倍半硅氧烷的质量比为10:(1～5)。
  7. 如权利要求6所述一种含氟硅环氧树脂耐辐射涂料，其特征在于所述八苯基氨基聚倍半硅氧烷的制备方法如下：
    1)冰水浴中将5～10份八苯基聚倍半硅氧烷分散于30～60体积份硝酸溶液，均匀搅拌30min；
    2)将OPS硝酸溶液室温下继续反应15～30h，抽滤并水洗3～5次后得到黄 色沉淀；
    3)将5～10份步骤2)中所得黄色沉淀与0.5～2份钯碳催化剂置于反应容器，氩气保护下加入10～20体积份四氢呋喃和10～20体积份三乙胺，反应液加热至60℃，加入4～10体积份甲酸，继续反应5～10h；
    4)反应结束后，抽滤后用乙酸乙酯和水分别洗涤3～5次，得淡黄色固体。
  8. 如权利要求1所述一种含氟硅环氧树脂耐辐射涂料，其特征在于所述消泡剂为二甲基硅油。
  9. 如权利要求1所述一种含氟硅环氧树脂耐辐射涂料的制备方法，其特征在于包括以下步骤：
    1)将金属氧化物纳米粉、消泡剂先后依次溶于活性稀释剂中得乳液，在乳液中加入环氧树脂，得组分A；
    2)将胺类固化剂和八苯基氨基聚倍半硅氧烷加入二甲苯中分散均匀得到组分B；
    3)将组分A和组分B混合，即得含氟硅环氧树脂耐辐射涂料。
  10. 如权利要求9所述一种含氟硅环氧树脂耐辐射涂料的制备方法，其特征在于在步骤1)中，所述在乳液中加入环氧树脂是在超声振荡下往乳液中分批加入环氧树脂。
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