WO2018095360A1 - 一种基于改性氧化石墨烯的水性膨胀型防火涂料及其制备方法 - Google Patents

一种基于改性氧化石墨烯的水性膨胀型防火涂料及其制备方法 Download PDF

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WO2018095360A1
WO2018095360A1 PCT/CN2017/112582 CN2017112582W WO2018095360A1 WO 2018095360 A1 WO2018095360 A1 WO 2018095360A1 CN 2017112582 W CN2017112582 W CN 2017112582W WO 2018095360 A1 WO2018095360 A1 WO 2018095360A1
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graphene oxide
modified graphene
parts
water
agent
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French (fr)
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戴李宗
邵志恒
陈国荣
王世成
袁丛辉
许一婷
曾碧榕
罗伟昂
刘新瑜
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厦门大学
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    • 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
    • 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
    • C09D5/185—Intumescent 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • the invention belongs to the field of flame retardant coatings, and particularly relates to an aqueous expansion type fireproof coating based on modified graphene oxide and a preparation method thereof.
  • Intumescent fire retardant coatings are classified into dispersing media and can be classified into solvent-based fire retardant coatings and waterborne fire retardant coatings. Obviously, water-based fire retardant coatings are much more environmentally friendly than solvent-based fire retardant coatings. The organic volatiles (VOC) of waterborne fire retardant coatings are lower than solvent-based fireproof coatings, which is more in line with the development needs of ecological civilization construction. The research, development and use of waterborne fire retardant coatings is one of the development trends of fire retardant coatings.
  • the traditional intumescent flame retardant system is mainly composed of acid source, carbon source and gas source “three sources”. Due to their advantages of no halogen, no antimony, low smoke, low toxicity and no corrosive gas, it has been widely used in intumescent type. Fireproof coating.
  • these typical intumescent flame retardants still have some problems: most of the intumescent flame retardants have poor compatibility, and this problem often leads to a decrease in the mechanical properties of the polymer, which makes it impossible to apply it in engineering; some intumescent flame retardants It is easy to absorb moisture. Because of the certain water absorption of ammonium polyphosphate (APP) and pentaerythritol (PER), the water resistance of the polymer will eventually decrease. Most of the intumescent flame retardants are low molecular weight, which not only leads to poor thermal stability of the polymer. It is also easy to seep; the optimization of the ratio of the intumescent flame retardant requires a lot of experiment and experience to obtain.
  • APP am
  • Chinese patent CN105153850A synthesizes a phosphorus-nitrogen flame retardant through diphenyl chlorophosphate and diaminopyridine, and applies it to fireproof coatings.
  • the coating has good corrosion resistance, water resistance, fire resistance and weather resistance.
  • Chinese patent CN104130671A modified epoxy emulsion by DOPO to improve corrosion protection Corrosion resistance, adhesion, weather resistance, and fire resistance.
  • the flame retardant is further improved by the DOPO type silane coupling agent to further improve the dispersibility and fire retardant property of the flame retardant.
  • Chinese patent CN101712840A is an intumescent flame retardant system composed of epoxy resin, modified ammonium polyphosphate and foaming agent triazine macromolecule, which overcomes the poor water resistance of traditional intumescent flame retardant system.
  • Chinese patent CN101255305A has prepared a steel structure fireproof coating, which uses an aqueous bromine carbon epoxy resin. The fire retardant coating can reduce the flame retardant auxiliary system by using an intrinsic type flame retardant polymer resin as a base material. The fireproof coating has the characteristics of strong adhesion, good film forming performance, excellent combustion expansion and high hardness of the carbon layer.
  • the intumescent flame retardant system has a large amount of addition and poor compatibility with the matrix, which reduces the strength and other physical and chemical properties of the coating.
  • Fireproof coatings have poor water resistance, heat resistance and corrosion resistance, and the additive type intumescent flame retardant system is easy to settle, which may affect fireproof performance.
  • the invention aims to solve the deficiencies of the existing fireproof coatings, and proposes an aqueous expansion type fireproof coating based on modified graphene oxide and a preparation method thereof.
  • the water-based epoxy resin emulsion-based water-based intumescent fire-retardant coating of the invention is mainly composed of water-based epoxy emulsion, silicone-acrylic emulsion and acrylate compound emulsion, and water, ammonium polyphosphate, melamine phosphate, melamine, urea, Pentaerythritol, mannitol, expandable graphite and zinc phosphate, aluminum hydroxide, titanium dioxide, modified graphene oxide (GO-KHTD), additives, aqueous curing agent.
  • the coating has good physical and chemical properties and fire resistance.
  • Table 1 Composition and mass fraction of water-based intumescent fire retardant coating based on modified graphene oxide
  • the film-forming substance includes an aqueous epoxy emulsion, a silicone-acrylic emulsion, and an acrylate emulsion in a mass ratio of 1.5 to 2.5:1.5 to 2:0.5 to 1.
  • the aqueous epoxy emulsion is a bisphenol A epoxy emulsion or a bisphenol F epoxy emulsion, and the epoxy value is 0.1 to 0.56.
  • the dehydrated carbon catalyst includes a high degree of polymerization of ammonium polyphosphate and melamine phosphate in a mass ratio of 1.9 to 3:1.
  • the blowing agent includes melamine and urea in a mass ratio of 2 to 3:1.
  • the char forming agent includes pentaerythritol and mannitol in a mass ratio of 1.5 to 2:1.
  • the pigment filler and the flame retardant include titanium oxide, zinc phosphate and aluminum hydroxide in a mass ratio of 0.5 to 1.5:1.5 to 2:0.5 to 1.5.
  • the expandable graphite has a mesh number of 80 to 200 mesh.
  • the aqueous curing agent is one of polyether diamine, hexamethylene diamine, diamine methylcyclohexane, and diamine methylcyclohexylmethane.
  • the auxiliary agent includes 0 to 1.0 parts of the dispersing aid, 0 to 1.0 part of the defoaming aid, 0 to 1.0 part of the thickening aid, and 0 to 0.7 parts of the multifunctional auxiliary agent.
  • a film forming aid such as an alcohol ester-12 or the like is 0.9 to 1.2 parts.
  • the modified graphene oxide (GO-KHTD) is used as a reactive expansion flame retardant therein, and its chemical structural formula is as follows:
  • the modified graphene oxide (GO-KHTD) is prepared by ultrasonically dispersing graphene oxide (GO) in solvent A under stirring, condensing reflux and nitrogen protection, and adding aminopropyltriethoxy group.
  • the silane is heated to 60 to 80 ° C for 6 to 15 hours, and then washed by filtration to obtain aminopropyltriethoxysilane-modified graphene oxide (GO-APTMS).
  • the aminopropyltriethoxysilane-modified graphene oxide (GO-APTMS) is ultrasonically dispersed in solvent B, and then added triglycidyl isocyanurate, and the temperature is raised.
  • DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is added, and the temperature is raised to 125-135 ° C for 6-8 h. Filtering and washing to obtain the modified graphene oxide; the mass ratio of the graphene oxide to the aminopropyltriethoxysilane is 1:4.4 to 4.6; the aminopropyltriethyl group The mass ratio of the oxysilane-modified graphene oxide to the triglycidyl isocyanurate and DOPO is 1:2.5-5:2.1-2.2; the solvent A is a mixture of water and ethanol in a volume ratio of 1:15-20.
  • the solvent B is N,N-dimethylformamide or dioxane.
  • the preparation method of the modified graphene oxide-based aqueous intumescent fireproof coating has the following steps:
  • Modified graphene oxide (GO-KHTD) has good water dispersibility and solves the problem of poor compatibility between the traditional intumescent flame retardant system and the polymer.
  • Modified graphene oxide contains reactive epoxy functional groups and can be used as a reactive flame retardant, which not only solves the problem of the loss of the traditional expansion system, but also enhances the mechanical properties, water resistance, weather resistance, etc. of the coating. Physical and chemical properties.
  • the water-based ultra-thin intumescent fireproof coating has excellent fire resistance and physical and chemical properties, and is very environmentally friendly.
  • Example 1 is a graph of X-ray photoelectron spectroscopy analysis of modified graphene oxide (GO-KHTD) in Example 1.
  • Example 2 is a scanning electron micrograph of modified graphene oxide (GO-KHTD) in Example 1.
  • Fig. 3 is a picture showing the post-combustion expansion foaming of the fireproof coating laboratory in Example 1.
  • GO-APTMS GO-APTMS
  • 216 g of DOPO reaction was added, and the temperature was raised to 130 ° C for 6 h.
  • the X-ray photoelectron spectroscopy analysis of the modified graphene oxide (GO-KHTD) is shown in Fig. 1, corresponding to peaks of C, O, P, Si, and N.
  • the scanning electron micrograph of the modified graphene oxide (GO-KHTD) is shown in Fig. 2.
  • Step 2 Dehydration to a carbon catalyst, namely 533 g ammonium polyphosphate and 267 g melamine phosphate, blowing agent 267 g melamine and 133 g urea, carbon forming agent 300 g pentaerythritol and 150 g mannitol, 40 g expandable graphite, pigment filler and flame retardant That is, 50g of titanium dioxide, 80g of zinc phosphate and 60g of aluminum hydroxide, 200g of modified graphene oxide (GO-KHTD) prepared in step 1, mixed into 1000g of deionized water, then added to the batching tank, dispersed and stirred by high-speed disperser Uniformly 30min, and then fully grinded with a three-roll mill (or ball mill or sander) for 2h, slowly adding additives (25g dispersing aid polyacrylic acid sodium salt SN-Dispersant-5040, 25g defoaming aid F111, more than 15g
  • the functional additive AMP-95
  • Step 3 Mix 690 g of epoxy emulsion and 200 g of aqueous curing agent polyether diamine uniformly, add 550 g of silicone-acrylic emulsion, 140 g of acrylate emulsion to obtain a mixed emulsion; add the mixed emulsion to the slurry obtained in step 2, while stirring 50 g of the film-forming auxiliary alcohol ester-12 was added dropwise, and the mixture was uniformly mixed. Then, 10 g of a thickening aid polyurethane type DSX3116 was added to adjust the viscosity to 98 KU, and the finished product was sieved after discharging.
  • GO-APTMS was placed in a vessel equipped with a stirring device, condensed reflux and nitrogen protection, ultrasonically dispersed in 600 ml of dioxane, and 305 g of triglycidyl isocyanurate was added thereto, and the mixture was heated to 85 ° C for 13 hours, and then added. 218 g of DOPO reaction, the temperature was raised to 130 ° C, and the reaction was carried out for 7 h. After filtration, it was washed with absolute ethanol and dried to obtain modified graphene oxide (GO-KHTD).
  • GO-KHTD modified graphene oxide
  • Step 2 Dehydration to carbon catalyst 540g ammonium polyphosphate and 270g melamine phosphate, foaming agent 280g melamine and 140g urea, charcoal agent 320g pentaerythritol and 160g mannitol, 35g expandable stone Ink, pigment and filler and flame retardant, namely 45g titanium dioxide, 65g zinc phosphate and 48g aluminum hydroxide, 150g of modified graphene oxide (GO-KHTD) prepared in step 1, added to 1050g deionized water, and then added to the batching tank Disperse and stir evenly for 30 minutes with a high-speed disperser, then fully grind with a three-roll mill (or ball mill or sand mill) for 2 h, slowly add auxiliary agent (25 g dispersing aid polyacrylic acid sodium salt SN-Dispersant-5040, 25g Defoaming aid F111, 15g multi-functional auxiliary agent AMP-95), and stirring was continued for another 30 minutes to obtain a slurry
  • Step 3 680 g of the epoxy emulsion and 210 g of the aqueous curing agent hexamethylenediamine are uniformly mixed, and 540 g of a silicone-acrylic emulsion and 130 g of an acrylate emulsion are added to obtain a mixed emulsion; and the mixed emulsion is added to the slurry obtained in the step 2 while stirring. 50 g of film-forming auxiliary alcohol ester-12 was added dropwise, and the mixture was uniformly mixed. Then, 12 g of a thickening auxiliary polyurethane type DSX3116 was added to adjust the viscosity to 96 KU. After discharging, the finished product was obtained by sieving.
  • GO-APTMS was placed in a vessel equipped with a stirring device, condensed reflux and nitrogen atmosphere, ultrasonically dispersed in 600 ml of N,N-dimethylformamide, 320 g of triglycidyl isocyanurate was added, and the temperature was raised to 80 ° C. After reacting for 15 hours, 220 g of DOPO reaction was added, and the temperature was raised to 130 ° C, and the reaction was carried out for 8 hours. After filtration, it was washed with N,N-dimethylformamide and dried to give modified graphene oxide (GO-KHTD).
  • GO-KHTD modified graphene oxide
  • Step 2 Dehydration to a carbon catalyst, namely 533 g ammonium polyphosphate and 267 g melamine phosphate, blowing agent 267 g melamine and 133 g urea, carbon forming agent 300 g pentaerythritol and 150 g mannitol, 40 g expandable graphite, pigment filler and flame retardant That is, 45g of titanium dioxide, 90g of zinc phosphate and 45g of aluminum hydroxide, 250g of modified graphene oxide (GO-KHTD) prepared in step 1, mixed into 1250g of deionized water, then added to the batching tank, dispersed and stirred by high-speed disperser Uniform for 30min, and then fully grinded with a three-roll mill (or ball mill or sand mill) for 2h, slowly adding additives (30g dispersing aid polyacrylic acid sodium salt SN-Dispersant-5040, 30g defoaming aid F111, more than 20g The functional additive AMP-95)
  • Step 3 720 g of the epoxy emulsion and 210 g of the aqueous curing agent diaminomethylcyclohexane are uniformly mixed, and 560 g of a silicone-acrylic emulsion and 150 g of an acrylate emulsion are added to obtain a mixed emulsion; and the mixed emulsion is added to the slurry obtained in the step 2.
  • the film-forming auxiliary alcohol ester-12 60g was added dropwise while stirring, and the mixture was uniformly mixed.
  • 15 g of a thickening aid polyurethane type DSX3116 was added to adjust the viscosity to 98 KU, and the finished product was sieved after discharging.

Abstract

一种基于改性氧化石墨烯的水性膨胀型防火涂料及其制备方法，该防水涂料包括水、成膜物质、脱水成炭催化剂、发泡剂、成炭剂、颜填料和阻燃剂、可膨胀石墨、改性氧化石墨烯、助剂、水性固化剂和水。该改性氧化石墨烯由氧化石墨烯、氨丙基三乙氧基硅烷、异氰脲酸三缩水甘油酯和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）反应制备得到。该防火涂料由组分均匀混合制备得到。

Description

一种基于改性氧化石墨烯的水性膨胀型防火涂料及其制备方法 技术领域
本发明属于阻燃涂料领域，具体涉及一种基于改性氧化石墨烯的水性膨胀型防火涂料及其制备方法。
背景技术
随着经济社会以及科技不断发展，人们对安全和环保问题更加重视。根据国家标准《建筑设计防火规范》GB 50016-2014的要求，必须对钢结构建筑进行防火保护。
膨胀型防火涂料按分散介质分类，可分为溶剂型防火涂料和水性防火涂料。显而易见，水性防火涂料较溶剂型防火涂料环保得多，水性防火涂料的有机挥发物(VOC)低于溶剂型防火涂料，更加符合生态文明建设的发展需求。对于水性防火涂料的研究、发展和使用是防火涂料的发展趋势之一。
传统膨胀阻燃体系主要由酸源、碳源、气源“三源”组成，由于它们无卤、无锑、低烟、低毒、无腐蚀性气体的优势，所以一直被广泛应用在膨胀型防火涂料。但是这些典型的膨胀型阻燃剂仍然存在一些问题：大部分膨胀型阻燃剂相容性较差，这个问题往往导致聚合物力学性能降低，从而无法在工程上应用；一些膨胀型阻燃剂容易吸潮，由于聚磷酸铵(APP)和季戊四醇(PER)有一定吸水性，最终会导致聚合物耐水性下降；大部分膨胀型阻燃剂为低分子物，不仅导致聚合物热稳定性差，还易渗出；膨胀型阻燃剂的配比优化需要大量实验和经验来获得。
近年来对钢结构防火涂料的报道很多，但对于活性膨胀阻燃剂的研究、专利报道并不多。中国专利CN105153850A通过氯代磷酸二苯酯和二氨基吡啶合成磷氮阻燃剂，并将其应用到防火涂料，该涂料具有较好的防腐蚀性能，耐水性和防火性能、耐候性能。中国专利CN104130671A通过DOPO对环氧乳液改性，提高了防腐 蚀性能、附着力、耐候性，也提高了防火性能。又以DOPO型硅烷偶联剂改性阻燃剂进一步提高阻燃剂的分散性和防火阻燃性能。中国专利CN101712840A以环氧树脂、改性聚磷酸铵、发泡剂三嗪大分子组成膨胀型阻燃体系，克服了传统膨胀型阻燃体系耐水性差的特点。中国专利CN101255305A制备了一种钢结构防火涂料，使用了水性溴碳环氧树脂，该防火涂料由于使用了本征型阻燃高分子树脂为基料，可以减少阻燃助剂体系，由此制备的防火涂料具有附着力强、成膜性能好、燃烧膨胀优、碳层硬度高的特点。
现有的专利、文献报道的钢结构防火涂料主要存在以下问题：
1)加入的膨胀阻燃剂大都属于添加型，随着时间推移，膨胀型阻燃体系易渗出流失，因而会导致防火性能下降。
2)膨胀型阻燃体系添加量较大且与基体相容性较差，降低了涂层的强度及其它理化性能。
3)防火涂料耐水性和耐热性、耐腐蚀性能较差，且添加型膨胀型阻燃体系容易沉降，会影响防火性能。
发明内容
本发明旨在解决现有防火涂料的不足，提出了一种基于改性氧化石墨烯的水性膨胀型防火涂料及其制备方法。
本发明的基于改性氧化石墨烯的水性膨胀型防火涂料以水性环氧乳液、硅丙乳液、丙烯酸酯复配乳液为主要成膜物质，添加水、聚磷酸铵、磷酸三聚氰胺、三聚氰胺、脲、季戊四醇、甘露醇、可膨胀石墨和磷酸锌、氢氧化铝、二氧化钛、改性氧化石墨烯(GO-KHTD)、助剂、水性固化剂组成。该涂料具有较好的理化性能和防火性能。
本发明所述的基于改性氧化石墨烯的水性膨胀型防火涂料的具体配方设计如表1：
表1 基于改性氧化石墨烯的水性膨胀型防火涂料的组分与质量分数
组分 含量(wt％)
成膜物质 25-31
脱水成炭催化剂 12-22
发泡剂 4-10
成炭剂 7-12
颜填料和阻燃剂 2-5
可膨胀石墨 2-4
改性氧化石墨烯 0.7-15
助剂 1-5
水性固化剂 4-10
水 15-28
所述成膜物质包括质量比为1.5～2.5∶1.5～2∶0.5～1的水性环氧乳液、硅丙乳液和丙烯酸酯乳液。
所述水性环氧乳液为双酚A型环氧乳液或双酚F型环氧乳液，环氧值为0.1～0.56。
所述脱水成炭催化剂包括质量比为1.9～3∶1的高聚合度的聚磷酸铵和磷酸三聚氰胺。
所述发泡剂包括质量比为2～3∶1的三聚氰胺和脲。
所述成炭剂包括质量比为1.5～2∶1的季戊四醇和甘露醇。
所述颜填料和阻燃剂包括质量比为0.5～1.5∶1.5～2∶0.5～1.5的二氧化钛、磷酸锌和氢氧化铝。
所述可膨胀石墨目数为80～200目。
所述水性固化剂为聚醚二胺、己二胺、二胺甲基环己烷、二胺甲基环己基甲烷中的一种。
所述助剂按质量份数计，包括分散助剂0～1.0份、消泡助剂0～1.0份、增稠助剂0～1.0份、多功能助剂0～0.7份。成膜助剂例如醇酯-12等0.9～1.2份。
所述改性氧化石墨烯(GO-KHTD)作为其中的活性膨胀阻燃剂，其化学结构式如下：
Figure PCTCN2017112582-appb-000001
所述改性氧化石墨烯(GO-KHTD)的制备方法为：在搅拌、冷凝回流和氮气保护下，将氧化石墨烯(GO)在溶剂A中超声分散后，加入氨丙基三乙氧基硅烷，升温至60～80℃反应6～15h后，过滤洗涤，得到氨丙基三乙氧基硅烷改性的氧化石墨烯(GO-APTMS)。；然后在搅拌、冷凝回流和氮气保护下，将氨丙基三乙氧基硅烷改性的氧化石墨烯(GO-APTMS)在溶剂B中超声分散后，加入异氰尿酸三缩水甘油酯，升温至80～90℃反应10～15h，再加入DOPO(9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物)，升温至125～135℃反应6～8h后，过滤洗涤，得到所述改性氧化石墨烯；所述氧化石墨烯和氨丙基三乙氧基硅烷的质量比为1∶4.4～4.6；所述氨丙基三乙 氧基硅烷改性的氧化石墨烯与异氰尿酸三缩水甘油酯、DOPO的质量比为1∶2.5～5∶2.1～2.2；所述溶剂A为体积比1∶15～20的水和乙醇混合液，溶剂B为N，N-二甲基甲酰胺或二氧六环。
所述基于改性氧化石墨烯的水性膨胀型防火涂料的制备方法，其步骤如下：
1)按所述各组分配比，将脱水成炭催化剂、成炭剂、发泡剂、可膨胀石墨、颜填料和阻燃剂、改性氧化石墨烯、水混合均匀，充分研磨；然后向其中加入分散助剂、消泡助剂和多功能助剂，搅拌均匀，得到浆料；
2)将成膜物质的水性环氧乳液与水性固化剂混合，然后加入其余成膜物质，得到混合乳液；将混合乳液加入至步骤1)得到的浆料中，搅拌下向其中滴加成膜助剂，混合均匀，再加入增稠助剂调节至粘度95～100KU，即得。
与现有技术相比本发明具有以下优点：
1)改性氧化石墨烯(GO-KHTD)水分散性较好，解决了传统膨胀阻燃体系与聚合物相容性差的问题。
2)改性氧化石墨烯(GO-KHTD)含有活性环氧官能团，可作为反应型阻燃剂，不仅解决了传统膨胀体系易流失的问题，又可增强涂料机械性能、耐水性、耐候性等理化性能。
3)改性氧化石墨烯(GO-KHTD)一方面氮硅协同阻燃，另一方面石墨烯结构可起到凝聚相的防火阻燃作用，该阻燃剂防火效果好，制备方法简便，原料廉价，产率较高，可以进行商业产业化。
4)该水性超薄膨胀型防火涂料具有优异的防火性能和理化性能，并且十分环保。
附图说明
图1为实例1中改性氧化石墨烯(GO-KHTD)X射线光电子能谱分析图。
图2为实例1中改性氧化石墨烯(GO-KHTD)扫描电镜图。
图3为实例1中防火涂料实验室模拟燃烧后膨胀发泡图片。
具体实施方式
下面通过实施例具体说明本发明的内容：
实施例1：
步骤1：制备改性氧化石墨烯(GO-KHTD)
在装有搅拌装置、冷凝回流和氮气保护的容器中依次加入50g氧化石墨烯(GO)、50ml去离子水和800ml乙醇，待超声30min后，加入223g氨丙基三乙氧基硅烷，升温至60℃，反应8h后，过滤后用丙酮洗涤，得到氨丙基三乙氧基硅烷改性的氧化石墨烯(GO-APTMS)。然后将100g GO-APTMS加入装有搅拌装置、冷凝回流和氮气保护的容器中，在600ml N，N-二甲基甲酰胺中超声分散，加入298g异氰尿酸三缩水甘油酯，升温至90℃反应12h后，加入216g DOPO反应，升温至130℃，反应6h。过滤后用无水乙醇洗涤，干燥后得到改性氧化石墨烯(GO-KHTD)。所述改性氧化石墨烯(GO-KHTD)X射线光电子能谱分析如图1所示，对应出现C、O、P、Si、N的峰。改性氧化石墨烯(GO-KHTD)扫描电镜图如2所示。
步骤2：将脱水成炭催化剂即533g聚磷酸铵和267g磷酸三聚氰胺，发泡剂即267g三聚氰胺和133g脲，成炭剂即300g季戊四醇和150g甘露醇，40g可膨胀石墨，颜填料和阻燃剂即50g二氧化钛、80g磷酸锌和60g氢氧化铝，200g步骤1制得的改性氧化石墨烯(GO-KHTD)混合，加入到1000g去离子水中，然后加入配料罐中，用高速分散机分散搅拌均匀30min，再用三辊研磨机(或球磨机或砂磨机)进行充分研磨2h，缓慢加入助剂(25g分散助剂聚丙烯酸钠盐SN-Dispersant-5040，25g消泡助剂F111，15g多功能助剂AMP-95)，再继续搅拌30min，得到浆料。
步骤3：将690g环氧乳液和200g水性固化剂聚醚二胺混合均匀，加入550g硅丙乳液，140g丙烯酸酯乳液，得到混合乳液；将混合乳液加入至步骤2得到的浆料中，边搅拌边滴加成膜助剂醇酯-12 50g，混合均匀，再加入10g增稠助剂聚氨酯型DSX3116，调节至粘度为98KU，出料后过筛即得涂料成品。
所得防火涂料各项技术指标按国家标准GB14907-2002《钢结构防火涂料》的要求进行测试，防火性能：涂层厚度0.82mm(图3左)，和膨胀后炭层高度为4.35cm(图3右)，耐火极限96min；其余结果见表2。
表2 实施例1的基于改性氧化石墨烯的水性超薄膨胀型防火涂料的主要性能指标
检验项目 检验结果
在容器中的状态 符合要求
干燥时间(表干)/h 2.5
初期干燥抗裂性 无裂纹
外观与颜色 符合要求
粘结强度/MPa 0.75
抗振性 符合要求
抗弯性 符合要求
耐曝热性/h ≥720涂层无起层、脱落、空鼓、开裂现象
耐湿热性/h ≥504涂层无起层、脱落现象
耐冻融循环性/次 ≥15涂层无开裂、脱落、起泡现象
耐水性/h ≥24涂层无起层、发泡、脱落现象
耐酸性/h(3％HCl溶液) ≥360涂层无起层、脱落、开裂现象
耐碱性/h(3％氨水溶液) ≥360涂层无起层、脱落、开裂现象
耐盐雾腐蚀性/次 ≥30涂层无起泡，明显的变质、软化现象
耐火性能 涂层厚度0.82mm，耐火极限96min
实施例2：
步骤1：制备改性氧化石墨烯(GO-KHTD)
在装有搅拌装置、冷凝回流和氮气保护的容器中依次加入50g氧化石墨烯(GO)、50ml去离子水和800ml乙醇，待超声30min后，加入225g氨丙基三乙氧基硅烷，升温至60℃，反应8h后，过滤后用丙酮洗涤，得到氨丙基三乙氧基硅烷改性的氧化石墨烯(GO-APTMS)。然后将100g GO-APTMS加入装有搅拌装置、冷凝回流和氮气保护的容器中，在600ml二氧六环中超声分散，加入305g异氰尿酸三缩水甘油酯，升温至85℃反应13h后，加入218g DOPO反应，升温至130℃，反应7h。过滤后用无水乙醇洗涤，干燥后得到改性氧化石墨烯(GO-KHTD)。
步骤2：将脱水成炭催化剂即540g聚磷酸铵和270g磷酸三聚氰胺，发泡剂即280g三聚氰胺和140g脲，成炭剂即320g季戊四醇和160g甘露醇，35g可膨胀石 墨，颜填料和阻燃剂即45g二氧化钛、65g磷酸锌和48g氢氧化铝，150g步骤1制得的改性氧化石墨烯(GO-KHTD)混合，加入到1050g去离子水中，然后加入配料罐中，用高速分散机分散搅拌均匀30min，再用三辊研磨机(或球磨机或砂磨机)进行充分研磨2h，缓慢加入助剂(25g分散助剂聚丙烯酸钠盐SN-Dispersant-5040，25g消泡助剂F111，15g多功能助剂AMP-95)，再继续搅拌30min，得到浆料。
步骤3：将680g环氧乳液和210g水性固化剂己二胺混合均匀，加入540g硅丙乳液，130g丙烯酸酯乳液，得到混合乳液；将混合乳液加入至步骤2得到的浆料中，边搅拌边滴加成膜助剂醇酯-12 50g，混合均匀，再加入12g增稠助剂聚氨酯型DSX3116，调节至粘度为96KU，出料后过筛即得涂料成品。
所得防火涂料各项技术指标按国家标准GB14907-2002《钢结构防火涂料》的要求进行测试，防火性能：涂层厚度0.97mm，耐火极限101min；其余结果见表3。
表3 实施例2的基于改性氧化石墨烯的水性超薄膨胀型防火涂料的主要性能指标
检验项目 检验结果
在容器中的状态 符合要求
干燥时间(表干)/h 3
初期干燥抗裂性 无裂纹
外观与颜色 符合要求
粘结强度/MPa 0.63
抗振性 符合要求
抗弯性 符合要求
耐曝热性/h ≥720涂层无起层、脱落、空鼓、开裂现象
耐湿热性/h ≥504涂层无起层、脱落现象
耐冻融循环性/次 ≥15涂层无开裂、脱落、起泡现象
耐水性/h ≥24涂层无起层、发泡、脱落现象
耐酸性/h(3％HCl溶液) ≥360涂层无起层、脱落、开裂现象
耐碱性/h(3％氨水溶液) ≥360涂层无起层、脱落、开裂现象
耐盐雾腐蚀性/次 ≥30涂层无起泡，明显的变质、软化现象
耐火性能 涂层厚度0.97mm，耐火极限101min
实施例3：
步骤1：制备改性氧化石墨烯(GO-KHTD)
在装有搅拌装置、冷凝回流和氮气保护的容器中依次加入50g氧化石墨烯(GO)、50ml去离子水和800ml乙醇，待超声30min后，加入230g氨丙基三乙氧基硅烷，升温至60℃，反应8h后，过滤后用丙酮洗涤，得到氨丙基三乙氧基硅烷改性的氧化石墨烯(GO-APTMS)。然后将100g GO-APTMS加入装有搅拌装置、冷凝回流和氮气保护的容器中，在600ml N，N-二甲基甲酰胺中超声分散，加入320g异氰尿酸三缩水甘油酯，升温至80℃反应15h后，加入220g DOPO反应，升温至130℃，反应8h。过滤后用N，N-二甲基甲酰胺洗涤，干燥后得到改性氧化石墨烯(GO-KHTD)。
步骤2：将脱水成炭催化剂即533g聚磷酸铵和267g磷酸三聚氰胺，发泡剂即267g三聚氰胺和133g脲，成炭剂即300g季戊四醇和150g甘露醇，40g可膨胀石墨，颜填料和阻燃剂即45g二氧化钛、90g磷酸锌和45g氢氧化铝，250g步骤1制得的改性氧化石墨烯(GO-KHTD)混合，加入到1250g去离子水中，然后加入配料罐中，用高速分散机分散搅拌均匀30min，再用三辊研磨机(或球磨机或砂磨机)进行充分研磨2h，缓慢加入助剂(30g分散助剂聚丙烯酸钠盐SN-Dispersant-5040，30g消泡助剂F111，20g多功能助剂AMP-95)，再继续搅拌30min，得到浆料。
步骤3：将720g环氧乳液和210g水性固化剂二氨甲基环己烷混合均匀，加入560g硅丙乳液，150g丙烯酸酯乳液，得到混合乳液；将混合乳液加入至步骤2得到的浆料中，边搅拌边滴加成膜助剂醇酯-12 60g，混合均匀，再加入15g增稠助剂聚氨酯型DSX3116，调节至粘度为98KU，出料后过筛即得涂料成品。
所得防火涂料各项技术指标按国家标准GB14907-2002《钢结构防火涂料》的要求进行测试，防火性能：涂层厚度1.02mm，耐火极限109min；其余结果见表4。
表4 实施例3的基于改性氧化石墨烯的水性超薄膨胀型防火涂料的主要性能指标
检验项目 检验结果
在容器中的状态 符合要求
干燥时间(表干)/h 3.5
初期干燥抗裂性 无裂纹
外观与颜色 符合要求
粘结强度/MPa 0.56
抗振性 符合要求
抗弯性 符合要求
耐曝热性/h ≥720涂层无起层、脱落、空鼓、开裂现象
耐湿热性/h ≥504涂层无起层、脱落现象
耐冻融循环性/次 ≥15涂层无开裂、脱落、起泡现象
耐水性/h ≥24涂层无起层、发泡、脱落现象
耐酸性/h(3％HCl溶液) ≥360涂层无起层、脱落、开裂现象
耐碱性/h(3％氨水溶液) ≥360涂层无起层、脱落、开裂现象
耐盐雾腐蚀性/次 ≥30涂层无起泡，明显的变质、软化现象
耐火性能 涂层厚度0.97mm，耐火极限109min
以上所述，仅为本发明较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (9)

  1. 一种基于改性氧化石墨烯的水性膨胀型防火涂料，其特征在于：所述涂料按质量份数计，包括成膜物质25～31份，脱水成炭催化剂12～22份，发泡剂4～10份，成炭剂7～12份，颜填料和阻燃剂2～5份，可膨胀石墨2～4份，改性氧化石墨烯0.7～15份，助剂1～5份，水性固化剂4～10份，水15～28份；
    其中，所述成膜物质包括质量比为1.5～2.5∶1.5～2∶0.5～1的水性环氧乳液、硅丙乳液和丙烯酸酯乳液，且水性环氧乳液与所述水性固化剂的质量比为1∶0.25～0.75；所述助剂包括分散助剂、消泡助剂、增稠助剂、多功能助剂和成膜助剂；所述改性氧化石墨烯化学结构式如下：
    Figure PCTCN2017112582-appb-100001
  2. 如权利要求1所述的基于改性氧化石墨烯的水性膨胀型防火涂料，其特征在于：所述水性环氧乳液为双酚A型环氧乳液或双酚F型环氧乳液，环氧值为0.1～0.56。
  3. 如权利要求1所述的基于改性氧化石墨烯的水性膨胀型防火涂料，其特征在于：所述脱水成炭催化剂包括质量比为1.9～3∶1的聚磷酸铵和磷酸三聚氰胺；所述发泡剂包括质量比为2～3∶1的三聚氰胺和脲。
  4. 如权利要求1所述的基于改性氧化石墨烯的水性膨胀型防火涂料，其特征在于：所述成炭剂包括质量比为1.5～2∶1的季戊四醇和甘露醇；所述颜填料和阻燃剂包括质量比为0.5～1.5∶1.5～2∶0.5～1.5的二氧化钛、磷酸锌和氢氧化铝。
  5. 如权利要求1所述的基于改性氧化石墨烯的水性膨胀型防火涂料，其特征在于：所述可膨胀石墨目数为80～200目；所述水性固化剂为聚醚二胺、己二胺、二胺甲基环己烷、二胺甲基环己基甲烷中的一种。
  6. 如权利要求1所述的基于改性氧化石墨烯的水性膨胀型防火涂料，其特征在于：所述助剂按质量份数计，包括分散助剂0～1.0份，消泡助剂0～1.0份，增稠助剂0～1.0份，多功能助剂0～0.7份，成膜助剂0.9～2份。
  7. 一种权利要求1所述的基于改性氧化石墨烯的水性膨胀型防火涂料的制备方法，其特征在于：包括如下步骤：
    1)按所述各组分配比，将脱水成炭催化剂、成炭剂、发泡剂、可膨胀石墨、颜填料和阻燃剂、改性氧化石墨烯、水混合均匀，充分研磨；然后向其中加入分散助剂、消泡助剂和多功能助剂，搅拌均匀，得到浆料；
    2)将成膜物质的水性环氧乳液与水性固化剂混合，然后加入其余成膜物质，得到混合乳液；将混合乳液加入至步骤1)得到的浆料中，搅拌下向其中滴加成膜助剂，混合均匀，再加入增稠助剂调节至粘度95～100KU，即得。
  8. 如权利要求7所述的基于改性氧化石墨烯的水性膨胀型防火涂料的制备方法，其特征在于：所述改性氧化石墨烯的制备方法为：在搅拌、冷凝回流和氮气保护下，将氧化石墨烯在溶剂A中超声分散后，加入氨丙基三乙氧基硅烷，升温至60～80℃反应6～15h后，过滤洗涤，得到氨丙基三乙氧基硅烷改性的氧化石墨烯；然后在搅拌、冷凝回流和氮气保护下，将氨丙基三乙氧基硅烷改性的氧化石墨烯在溶剂B中超声分散后，加入异氰尿酸三缩水甘油酯，升温至80～90℃反应10～15h，再 加入DOPO，升温至125～135℃反应6～8h后，过滤洗涤，得到所述改性氧化石墨烯；所述氧化石墨烯和氨丙基三乙氧基硅烷的质量比为1∶4.4～4.6；所述氨丙基三乙氧基硅烷改性的氧化石墨烯与异氰尿酸三缩水甘油酯、DOPO的质量比为1∶2.5～5∶2.1～2.2；所述溶剂A为体积比1∶15～20的水和乙醇混合液，溶剂B为N，N-二甲基甲酰胺或二氧六环。
  9. 一种用于水性膨胀型防火涂料的膨胀阻燃剂，其特征在于：所述膨胀阻燃剂为改性氧化石墨烯，其化学结构式如下：
    Figure PCTCN2017112582-appb-100002
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