WO2018036429A1 - 一种改性白石墨烯复合抗氧化涂料及其制备 - Google Patents

一种改性白石墨烯复合抗氧化涂料及其制备 Download PDF

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WO2018036429A1
WO2018036429A1 PCT/CN2017/098072 CN2017098072W WO2018036429A1 WO 2018036429 A1 WO2018036429 A1 WO 2018036429A1 CN 2017098072 W CN2017098072 W CN 2017098072W WO 2018036429 A1 WO2018036429 A1 WO 2018036429A1
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white graphene
modified white
oxidation
graphene composite
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French (fr)
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段曦东
李晓丰
毛志浩
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广东纳路纳米科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition

Definitions

  • the invention relates to the technical field of high-temperature anti-oxidation coatings, in particular to a modified white graphene composite anti-oxidation coating and preparation thereof.
  • vacuum methods are commonly used to prevent high-temperature oxidation of metals.
  • the vacuum method is to heat-treat the metal material in a vacuum environment, thereby reducing the contact of the metal product with oxygen and preventing the oxidation of the metal surface.
  • the vacuum equipment used in this method is very expensive, and the product size requirements and operator requirements are very high, which limits its application; the protective atmosphere method is carried out in a low-oxygen non-vacuum atmosphere, specifically by charging nitrogen, methane, and hydrogen.
  • the high-temperature anti-oxidation coating is generally used for high-temperature oxidation protection of metal materials during heat treatment.
  • the principle is that high-temperature anti-oxidation coating is applied to the metal surface before heat treatment, and the coating softens to a molten state during high-temperature heat treatment.
  • a dense protective film is formed on the surface of the metal to prevent high temperature gas from penetrating into the substrate to achieve a high temperature oxidation preventing effect.
  • the present invention adopts the following technical solutions:
  • the modified white graphene composite antioxidant coating of the present invention comprises: a liquid phase and an inorganic solid phase;
  • the liquid phase comprises, by weight: 20-50 parts of matrix resin, 5-30 parts of silica sol, 5-30 parts of coupling agent, 20-60 parts of deionized water;
  • the inorganic solid phase comprises, by weight, 0.1 to 10 parts of modified white graphene, 5 to 20 parts of glass powder, 10 to 40 parts of spherical alumina, and 5 to 30 parts of fumed silica.
  • the matrix resin comprises at least one of an acrylic resin, an aqueous polyurethane, and an acrylic-silicone resin;
  • the coupling agent includes one of a silane coupling agent KH-570, KH-590, and n-butyl titanate.
  • the modified white graphene is 5 to 10 layers of white graphene
  • the spherical alumina has a diameter of 50 to 200 nm;
  • the fumed silica has a diameter of 10 to 100 nm.
  • the preparation of the modified white graphene composite anti-oxidation coating comprises: adding a certain amount of matrix resin, silica sol, coupling agent and deionized water according to the parts by weight, and then sequentially adding to a high-speed mixer and mixing at room temperature. And weigh a certain amount of spherical alumina, fumed silica, glass powder and modified white graphene, and then added to a high-speed mixer for temperature mixing and stirring, and then ball milled by a planetary ball mill for 30-240 minutes to obtain the final product;
  • the high speed mixer has an operating temperature of 40 to 100 ° C and a stirring time of 10 to 60 minutes.
  • the surface modification method of the white graphene is: selecting 5-10 layers of white graphene with 0.3% aqueous oleylamine solution, long-chain borane, sodium dodecylbenzenesulfonate solution, and hexa bromide The solution is immersed in an alkylpyridine ethanol solution or a polyethylene oxide alkyl alcohol amide solution for 24 hours, and is subjected to centrifugation and vacuum drying to obtain a modified white graphene.
  • modified white graphene because it is a single layer or a small layer of hexagonal boron nitride, has a layer structure similar to graphite, oxidation temperature 900 ° C, high temperature resistance 2000 ° C, and good gas barrier properties .
  • the atomic layer is less than ten layers, the layer arrangement is compact and uniform, and the number of barrier sheets is large, the gas bypasses the coating, the path becomes long, and a small amount of addition can well block the passage of gas;
  • the surface modified white graphene In the environment, compared with the traditional boron nitride high temperature oxidation resistant coating, the surface modified white graphene has better affinity with the matrix, densely dispersed in the coating, and the white graphene sheet under the same weight.
  • the number of layers is more, and the ability of the layers to be more closely combined with oxygen is stronger. Therefore, the high-temperature anti-oxidation coating modified by white graphene has stronger oxidation resistance.
  • the modified white graphene composite anti-oxidation coating of the invention can withstand high temperature of 1800 ° C, has strong anti-oxidation ability, and has good adhesion and weather resistance, which greatly prolongs the service life of the material to be protected, and has a large Value.
  • Step 1) Surface modification of white graphene use 5-10 layers of white graphene with 0.3% aqueous oleylamine solution Soaking for 24 hours, after centrifugation, vacuum drying to obtain modified white graphene;
  • Step 2) Preparation of modified white graphene composite anti-oxidation coating: weigh 30 parts of acrylic resin, 10 parts of silica sol, 10 parts of KH-570 silane coupling agent and 50 parts of deionized water by weight, and then add sequentially Mix and stir for 5 min at room temperature in a high speed mixer. Weigh 10 parts of spherical alumina, 20 parts of fumed silica, 10 parts of glass powder and 0.5 parts of modified white graphene. Then add to the high-speed mixer and mix and stir. The temperature is controlled at 80 ° C for 15 min. After the end, the product is taken out. After being ground by a planetary grinder for 120 min, a composite anti-oxidation coating was obtained.
  • Step 1) Surface modification of white graphene 5-10 layers of white graphene are selected by soaking in a 0.3% aqueous solution of oleylamine for 24 hours, and the modified white graphene is obtained by centrifugation and vacuum drying;
  • Step 2) Preparation of modified white graphene composite anti-oxidation coating: 20 parts of acrylic resin, 10 parts of silica sol, 5 parts of KH-570 silane coupling agent and 40 parts of deionized water are weighed in parts by weight, and then sequentially added. Mix and stir for 5 min at room temperature in a high speed mixer. Weigh 15 parts of spherical alumina, 10 parts of fumed silica, 7 parts of glass powder and 2.5 parts of modified white graphene. Then add to the high-speed mixer and mix and stir. The temperature is controlled at 60 ° C for 30 min. After the end, the product is taken out. After being ground by a planetary grinder for 60 minutes, a composite anti-oxidation coating was obtained.
  • Step 1) Surface modification of white graphene 5-10 layers of white graphene are selected by soaking in a 0.3% aqueous solution of oleylamine for 24 hours, and the modified white graphene is obtained by centrifugation and vacuum drying;
  • Step 2) Preparation of modified white graphene composite anti-oxidation coating: weigh 30 parts of water-based polyurethane, 10 parts of silica sol, 8 parts of KH-570 silane coupling agent and 50 parts of deionized water by weight, and then add sequentially Mix and stir for 5 min at room temperature in a high speed mixer. Weigh 10 parts of spherical alumina, 20 parts of fumed silica, 10 parts of glass powder and 0.5 parts of modified white graphene. Then add to the high-speed mixer and mix and stir. The temperature is controlled at 80 ° C for 15 min. After the end, the product is taken out. Grinded by a planetary grinder for 120 min, A composite antioxidant coating is obtained.
  • Step 1) Surface modification of white graphene 5-10 layers of white graphene are selected by soaking in a 0.3% aqueous solution of oleylamine for 24 hours, and the modified white graphene is obtained by centrifugation and vacuum drying;
  • Step 2) Preparation of modified white graphene composite anti-oxidation coating: 20 parts of water-based polyurethane, 8 parts of silica sol, 5 parts of KH-570 silane coupling agent and 40 parts of deionized water are weighed separately according to the parts by weight, and then sequentially added. Mix and stir for 5 min at room temperature in a high speed mixer. Weigh 15 parts of spherical alumina, 10 parts of fumed silica, 7 parts of glass powder and 2.5 parts of modified white graphene. Then add to the high-speed mixer and mix and stir. The temperature is controlled at 60 ° C for 30 min. After the end, the product is taken out. After being ground by a planetary grinder for 60 minutes, a composite anti-oxidation coating was obtained.
  • Step 1) Surface modification of white graphene 5-10 layers of white graphene are selected by soaking in a 0.3% aqueous solution of oleylamine for 24 hours, and the modified white graphene is obtained by centrifugation and vacuum drying;
  • Step 2) Preparation of modified white graphene composite anti-oxidation coating: after weighing 30 parts of acrylic-silicone resin, 5 parts of silica sol, 7 parts of KH-570 silane coupling agent and 50 parts of deionized water, respectively, by weight parts , and then added to a high-speed mixer and mixed at room temperature for 5 minutes. Weigh 10 parts of spherical alumina, 20 parts of fumed silica, 10 parts of glass powder and 0.5 parts of modified white graphene. Then add to the high-speed mixer and mix and stir. The temperature is controlled at 80 ° C for 15 min. After the end, the product is taken out. After being ground by a planetary grinder for 120 min, a composite anti-oxidation coating was obtained.
  • Step 1) Surface modification of white graphene 5-10 layers of white graphene are selected by soaking in a 0.3% aqueous solution of oleylamine for 24 hours, and after centrifugation and vacuum drying, a white graphene modified additive is obtained;
  • Step 2) Preparation of modified white graphene composite anti-oxidation coating: 20 parts of acrylic-silicone resin, 5 parts of silica sol, 7 parts of KH-570 silane coupling agent and 40 parts of deionized water are weighed separately by weight , The mixture was sequentially added to a high-speed mixer and mixed at room temperature for 5 minutes. Weigh 15 parts of spherical alumina, 10 parts of fumed silica, 7 parts of glass powder and 2.5 parts of modified white graphene. Then add to the high-speed mixer and mix and stir. The temperature is controlled at 60 ° C for 30 min. After the end, the product is taken out. After being ground by a planetary grinder for 60 minutes, a composite anti-oxidation coating was obtained.
  • Preparation of composite anti-oxidation coating weigh 30 parts of acrylic resin, 10 parts of silica sol, 8 parts of KH-570 silane coupling agent and 50 parts of deionized water by weight, then add to high speed mixer and mix at room temperature for 5min. . Weigh 20 parts of spherical alumina, 20 parts of fumed silica and 10 parts of glass powder, and then add them to a high-speed mixer and mix and stir. The temperature is controlled at 80 ° C for 40 min. After the end, the product is taken out and ground by a planetary grinder for 90 min. A composite antioxidant coating is obtained.
  • Preparation of composite anti-oxidation coating weigh 30 parts of water-based polyurethane, 10 parts of silica sol, 8 parts of KH-570 silane coupling agent and 50 parts of deionized water by weight, then add to high-speed mixer and mix at room temperature for 5min. . Weigh 20 parts of spherical alumina, 20 parts of fumed silica and 10 parts of glass powder, and then add them to a high-speed mixer and mix and stir. The temperature is controlled at 80 ° C for 40 min. After the end, the product is taken out and ground by a planetary grinder for 90 min. A composite antioxidant coating is obtained.
  • Preparation of composite anti-oxidation coating weigh 30 parts of acrylic-silicone resin, 8 parts of silica sol, 5 parts of KH-570 silane coupling agent and 50 parts of deionized water by weight, and then add to high speed mixer at room temperature. Mix and stir for 5 min. Weigh 20 parts of spherical alumina, 20 parts of fumed silica and 10 parts of glass powder, and then add them to a high-speed mixer and mix and stir. The temperature is controlled at 80 ° C for 40 min. After the end, the product is taken out and ground by a planetary grinder for 90 min. A composite antioxidant coating is obtained.
  • Table 1 is used to determine the performance indexes of the composite antioxidant coatings after curing in various examples:
  • the modified white graphene composite anti-oxidation coating of the invention can withstand high temperature of 1800 ° C, has strong oxidation resistance, and has good adhesion and weather resistance, which greatly prolongs the service life of the material to be protected. Has great application value.

Abstract

一种改性白石墨烯复合抗氧化涂料，包括：液体相和无机固体相；按重量份数，液体相包括：20～50份基体树脂，5～30份硅溶胶，5～30份偶联剂，20～60份去离子水；无机固体相包括0.1～10份改性白石墨烯，5-20份玻璃粉，10～40份球形氧化铝，5-30份气相二氧化硅。该抗氧化涂料能承受1800℃高温、抗氧化能力强，同时具有较好的附着力和耐候性。

Description

一种改性白石墨烯复合抗氧化涂料及其制备 技术领域
本发明涉及高温抗氧化涂料技术领域，具体涉及一种改性白石墨烯复合抗氧化涂料及其制备。
背景技术
钢铁产品在进行一系列的热处理过程中，在大气环境中高温条件下钢铁表面容易产生氧化现象，同时伴随钢铁结构中合金元素的氧化，这给钢铁产品带来一系列的如使用性能降低、能耗增大等问题，严重影响钢铁产品质量和使用寿命。到目前为止，全世界钢铁产业在热处理工艺过程中因钢铁氧化导致产品损耗已增加到15％，造成巨大的资源浪费。因此采取措施减少钢铁产品在高温环境下的表面氧化已是人们迫切解决的问题。
目前，普遍采用的有真空法、保护气氛法、高温抗氧化涂料等防止金属高温氧化。真空法是将金属材料在真空环境中进行热加工处理，减少了金属产品与氧气的接触，防止金属表面氧化的进行。但此法使用的真空设备很昂贵，对产品尺寸要求和作业人员要求很高，限制了其应用；保护气氛法是在少氧非真空气氛中进行的，具体是通过充入氮气、甲烷、氢气以及惰性气体等保护性气体赶走环境中的氧气，减少钢铁表面与氧气接触从而达到防氧化的目的，但该工艺复杂，设备也很昂贵，同时保护性气氛会污染环境，不适合大规模使用。因此目前普遍采用的为高温防氧化涂料对金属材料在热处理过程中进行高温抗氧化保护，其原理为在热处理前，将高温抗氧化涂料涂覆在金属表面，高温热处理时涂层软化达到熔融状态，在金属表面形成致密保护膜，阻止高温气体向基体渗透从而达到高温防氧化效果。目前市场上应用较多的是添加碳化硼、氮化硼高温抗氧化涂料，但局限温度为1000℃，温度超过1000℃时，碳化硼或氮 化硼会形成较高的蒸汽压，挥发速度快，导致抗氧化时间有限。因此开发一种能在更苛刻温度环境下稳定的高温抗氧化涂料以扩大市场应用是行业人员始终追求的目标。
发明内容
有鉴于此，有必要针对上述问题，提供一种改性白石墨烯复合抗氧化涂料及其制备。
为实现上述目的，本发明采取以下技术方案：
本发明的改性白石墨烯复合抗氧化涂料，包括：液体相和无机固体相；
所述液体相按重量份数包括：20～50份基体树脂，5～30份硅溶胶，5～30份偶联剂，20～60份去离子水；
所述无机固体相按重量份数包括：0.1～10份改性白石墨烯，5-20份玻璃粉，10～40份球形氧化铝，5-30份气相二氧化硅。
进一步的，所述液体相中，基体树脂包括丙烯酸树脂、水性聚氨酯、丙烯酸-有机硅树脂中的至少一种；
所述偶联剂包括硅烷偶联剂KH-570、KH-590、钛酸正丁酯中的一种。
进一步的，所述无机固体相中，改性白石墨烯为5～10层白石墨烯；
所述球形氧化铝的直径为50～200nm；
所述气相二氧化硅直径为10～100nm。
本发明改性白石墨烯复合抗氧化涂料的制备，包括：按重量份数分别称取一定量的基体树脂、硅溶胶、偶联剂和去离子水后，依次加入到高速搅拌机中常温混合搅拌，再称取一定量的球形氧化铝、气相二氧化硅、玻璃粉和改性白石墨烯，并依次加入到高速搅拌机中升温混合搅拌后，再经行星球磨机球磨30～240min得到最终产品；
所述高速搅拌机作业温度为40～100℃、搅拌时间为10～60min。
进一步的，所述白石墨烯表面改性方法为：选用5-10层的白石墨烯用0.3％油胺水溶液、长链硼烷、十二烷基苯磺酸钠乙醇溶液、溴化十六烷基吡啶乙醇溶液或聚环氧乙烷烷基醇酰胺水溶液浸泡24小时，经离心、真空干燥后得改性白石墨烯。
与现有技术相比，本发明的有益效果为：
5～10层的改性白石墨烯，因其为单层或者少层六方氮化硼，具有类似石墨的层状结构，抗氧化温度900℃，耐高温2000℃，并有良好的隔离气体性能。当原子层少于十层时，片层排列紧凑、均匀，且阻挡片层数目较多，气体在涂层中绕行，路径变长，少量添加就能很好的阻挡气体通过；在高温苛刻环境中，与传统的氮化硼耐高温抗氧化涂料相比，经表面修饰的白石墨烯与基体有更好的亲和性，致密分散于涂层中，而且同样重量下的白石墨烯片层数更多，层与层之间会结合得更紧密隔离氧气的能力更强，因此经白石墨烯改性的高温抗氧化涂料的抗氧化能力更强。
本发明的改性白石墨烯复合抗氧化涂料，能承受1800℃高温、抗氧化能力强，同时具有较好的附着力和耐候性，这大大延长了被保护材料的使用寿命，具有很大的应用价值。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明的技术方案作进一步清楚、完整地描述。需要说明的是，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，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所有其他实施例，都属于本发明保护的范围。
实施例1
步骤1)白石墨烯表面改性：选用5-10层的白石墨烯用0.3％油胺水溶液 浸泡24小时，经离心、真空干燥后得改性白石墨烯；
步骤2)改性白石墨烯复合抗氧化涂料制备：按重量份数分别称取30份丙烯酸树脂、10份硅溶胶、10份KH-570硅烷偶联剂和50份去离子水后，依次加入到高速搅拌机中常温混合搅拌5min。再称取10份球形氧化铝、20份气相二氧化硅、10份玻璃粉和0.5份改性白石墨烯依次加入到高速搅拌机中混合搅拌，温度控制80℃，时间为15min；结束后取出产物再经行星研磨机研磨120min，得到复合抗氧化涂料。
实施例2
步骤1)白石墨烯表面改性：选用5-10层的白石墨烯用0.3％油胺水溶液浸泡24小时，经离心、真空干燥后得改性白石墨烯；
步骤2)改性白石墨烯复合抗氧化涂料制备：按重量份数分别称取20份丙烯酸树脂、10份硅溶胶、5份KH-570硅烷偶联剂和40份去离子水后，依次加入到高速搅拌机中常温混合搅拌5min。再称取15份球形氧化铝、10份气相二氧化硅、7份玻璃粉和2.5份改性白石墨烯依次加入到高速搅拌机中混合搅拌，温度控制60℃，时间为30min；结束后取出产物再经行星研磨机研磨60min，得到复合抗氧化涂料。
实施例3
步骤1)白石墨烯表面改性：选用5-10层的白石墨烯用0.3％油胺水溶液浸泡24小时，经离心、真空干燥后得改性白石墨烯；
步骤2)改性白石墨烯复合抗氧化涂料制备：按重量份数分别称取30份水性聚氨酯、10份硅溶胶、8份KH-570硅烷偶联剂和50份去离子水后，依次加入到高速搅拌机中常温混合搅拌5min。再称取10份球形氧化铝、20份气相二氧化硅、10份玻璃粉和0.5份改性白石墨烯依次加入到高速搅拌机中混合搅拌，温度控制80℃，时间为15min；结束后取出产物再经行星研磨机研磨120min， 得到复合抗氧化涂料。
实施例4
步骤1)白石墨烯表面改性：选用5-10层的白石墨烯用0.3％油胺水溶液浸泡24小时，经离心、真空干燥后得改性白石墨烯；
步骤2)改性白石墨烯复合抗氧化涂料制备：按重量份数分别称取20份水性聚氨酯、8份硅溶胶、5份KH-570硅烷偶联剂和40份去离子水后，依次加入到高速搅拌机中常温混合搅拌5min。再称取15份球形氧化铝、10份气相二氧化硅、7份玻璃粉和2.5份改性白石墨烯依次加入到高速搅拌机中混合搅拌，温度控制60℃，时间为30min；结束后取出产物再经行星研磨机研磨60min，得到复合抗防氧化涂料。
实施例5
步骤1)白石墨烯表面改性：选用5-10层的白石墨烯用0.3％油胺水溶液浸泡24小时，经离心、真空干燥后得改性白石墨烯；
步骤2)改性白石墨烯复合抗氧化涂料制备：按重量份数分别称取30份丙烯酸-有机硅树脂、5份硅溶胶、7份KH-570硅烷偶联剂和50份去离子水后，依次加入到高速搅拌机中常温混合搅拌5min。再称取10份球形氧化铝、20份气相二氧化硅、10份玻璃粉和0.5份改性白石墨烯依次加入到高速搅拌机中混合搅拌，温度控制80℃，时间为15min；结束后取出产物再经行星研磨机研磨120min，得到复合抗氧化涂料。
实施例6
步骤1)白石墨烯表面改性：选用5-10层的白石墨烯用0.3％油胺水溶液浸泡24小时，经离心、真空干燥后得白石墨烯改性添加剂；
步骤2)改性白石墨烯复合抗氧化涂料制备：按重量份数分别称取20份丙烯酸-有机硅树脂、5份硅溶胶、7份KH-570硅烷偶联剂和40份去离子水后， 依次加入到高速搅拌机中常温混合搅拌5min。再称取15份球形氧化铝、10份气相二氧化硅、7份玻璃粉和2.5份改性白石墨烯依次加入到高速搅拌机中混合搅拌，温度控制60℃，时间为30min；结束后取出产物再经行星研磨机研磨60min，得到复合抗氧化涂料。
对比实施例1
复合抗氧化涂料制备：按重量份数分别称取30份丙烯酸树脂、10份硅溶胶、8份KH-570硅烷偶联剂和50份去离子水后，依次加入到高速搅拌机中常温混合搅拌5min。再称取20份球形氧化铝、20份气相二氧化硅和10份玻璃粉依次加入到高速搅拌机中混合搅拌，温度控制80℃，时间为40min；结束后取出产物再经行星研磨机研磨90min，得到复合抗氧化涂料。
对比实施例2
复合抗氧化涂料制备：按重量份数分别称取30份水性聚氨酯、10份硅溶胶、8份KH-570硅烷偶联剂和50份去离子水后，依次加入到高速搅拌机中常温混合搅拌5min。再称取20份球形氧化铝、20份气相二氧化硅和10份玻璃粉依次加入到高速搅拌机中混合搅拌，温度控制80℃，时间为40min；结束后取出产物再经行星研磨机研磨90min，得到复合抗氧化涂料。
对比实施例3
复合抗氧化涂料制备：按重量份数分别称取30份丙烯酸-有机硅树脂、8份硅溶胶、5份KH-570硅烷偶联剂和50份去离子水后，依次加入到高速搅拌机中常温混合搅拌5min。再称取20份球形氧化铝、20份气相二氧化硅和10份玻璃粉依次加入到高速搅拌机中混合搅拌，温度控制80℃，时间为40min；结束后取出产物再经行星研磨机研磨90min，得到复合抗氧化涂料。
表1中为测定各实施例复合抗氧化涂料固化成膜后的各项性能指标：
表1复合抗氧化涂料的各项性能数据
Figure PCTCN2017098072-appb-000001
从上表可知，本发明的改性白石墨烯复合抗氧化涂料能承受1800℃高温、抗氧化能力强，同时具有较好的附着力和耐候性，这大大延长了被保护材料的使用寿命，具有很大的应用价值。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细， 但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (5)

  1. 一种改性白石墨烯复合抗氧化涂料，其特征在于，包括：液体相和无机固体相；
    所述液体相按重量份数包括：20～50份基体树脂，5～30份硅溶胶，5～30份偶联剂，20～60份去离子水；
    所述无机固体相按重量份数包括0.1～10份改性白石墨烯，5-20份玻璃粉，10～40份球形氧化铝，5-30份气相二氧化硅。
  2. 根据权利要求1所述的改性白石墨烯复合抗氧化涂料，其特征在于，所述液体相中，基体树脂包括丙烯酸树脂、水性聚氨酯、丙烯酸-有机硅树脂中的至少一种；
    所述偶联剂包括硅烷偶联剂KH-570、KH-590、钛酸正丁酯中的一种；
  3. 根据权利要求1所述的改性白石墨烯复合抗氧化涂料，其特征在于，所述无机固体相中，改性白石墨烯为5～10层白石墨烯；
    所述球形氧化铝的直径为50～200nm；
    所述气相二氧化硅直径为10～100nm。
  4. 一种权利要求1-3任意一项所述的改性白石墨烯复合抗氧化涂料的制备方法，其特征在于，包括：按重量份数分别称取一定量的基体树脂、硅溶胶、偶联剂和去离子水后，依次加入到高速搅拌机中常温混合搅拌，再称取一定量的球形氧化铝、气相二氧化硅、玻璃粉和改性白石墨烯，并依次加入到高速搅拌机中升温混合搅拌后，再经行星球磨机球磨30～240min得到最终产品；
    所述高速搅拌机作业温度为40～100℃、搅拌时间为10～60min。
  5. 根据权利要求4所述的改性白石墨烯复合抗氧化涂料的制备方法，其特征在于，所述白石墨烯表面改性方法为：选用5-10层的白石墨烯用0.3％油胺水 溶液、长链硼烷、十二烷基苯磺酸钠乙醇溶液、溴化十六烷基吡啶乙醇溶液或聚环氧乙烷烷基醇酰胺水溶液浸泡24小时，经离心、真空干燥后得改性白石墨烯。
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