WO2018095361A1 - 一种钢结构用环氧树脂膨胀型防火涂料及其制备方法 - Google Patents

一种钢结构用环氧树脂膨胀型防火涂料及其制备方法 Download PDF

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WO2018095361A1
WO2018095361A1 PCT/CN2017/112583 CN2017112583W WO2018095361A1 WO 2018095361 A1 WO2018095361 A1 WO 2018095361A1 CN 2017112583 W CN2017112583 W CN 2017112583W WO 2018095361 A1 WO2018095361 A1 WO 2018095361A1
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parts
agent
epoxy resin
fire
component
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French (fr)
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戴李宗
邵志恒
柳超
黄陈
曾碧榕
许一婷
罗伟昂
袁丛辉
陈国荣
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厦门大学
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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
    • 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
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/70—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
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention belongs to the field of fireproof coatings, and relates to an epoxy resin fireproof coating, in particular to an epoxy resin expansion type fireproof coating for steel structures and a preparation method thereof.
  • Intumescent fireproof coatings are widely used as fireproofing for steel structure buildings. Intumescent fireproof coatings expand and foam after fire, which acts as a flame retardant and heat insulation. When foaming, it will never release toxic gases and protect the human body from poison.
  • the intumescent fireproof coating base resin can be divided into two types: thermoplastic type and thermosetting type.
  • the thermosetting type fireproof coating adopts a two-component system, and the film-forming materials are mostly epoxy resin or polyurethane resin.
  • the two components generally have good chemical resistance, heat resistance, acid and alkali resistance, and sealing properties.
  • the flame retardant system is also not easy to migrate to the surface of the coating, and the fireproof performance is relatively stable, which is not susceptible to time and environment.
  • the two-component fire retardant coating has a high strength of the expanded carbon layer and provides effective fire protection.
  • Chinese patent CN105585931A is synthesized by modifying epoxy resin with diethanolamine, and then reacting with phosphoric acid-phosphorus pentoxide-urea, phosphoric acid-urea, ammonium polyphosphate-urea and modified epoxy resin respectively. Water-soluble ammonium polyphosphate flame retardant, and made into a new high-performance transparent fire retardant coating, its flame resistance time can reach 60min.
  • Chinese patent CN104845490A has prepared a fire retardant coating with a new flame retardant, including antimony trioxide, ammonium sulfate, magnesium hydroxide, citric acid and diatomaceous earth.
  • Chinese patent CN104804594A has prepared a steel structure fireproof coating using additive type expandable graphite, chlorinated paraffin and titanium white powder. When the coating thickness is 2.2mm, the fire resistance limit can reach 100min.
  • the fire-fighting aids added are all additive types, and the fire-retardant additives are easily lost over time, which may result in a decrease in fire resistance.
  • the fireproof coating has poor water resistance, heat resistance and corrosion resistance, and the added fireproofing agent is easy to settle, which will affect the fireproof performance.
  • the invention aims to solve the deficiencies of the existing steel structure fireproof coatings, and proposes an epoxy resin expansion type fireproof coating for steel structures and a preparation method thereof.
  • Table 1 Composition and mass fraction of epoxy resin intumescent fireproof coating for steel structure of the present invention
  • Component A Content (wt%)
  • Component B Content (wt%)
  • Expandable graphite 2 to 3 Additive 0 to 6
  • the epoxy resin is a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, and the epoxy value is between 0.1 and 0.56.
  • the dehydrated carbon catalyst includes ammonium polyphosphate and melamine phosphate in a mass ratio of 2 to 3:1.
  • the blowing agent includes melamine and urea in a mass ratio of 1.9 to 3:1.
  • the char forming agent includes pentaerythritol and mannitol in a mass ratio of 1.4 to 2:1.
  • the pigment filler comprises titanium dioxide, zinc borate and aluminum hydroxide in a mass ratio of 0.9 to 1.1:0.9 to 1.1:0.9 to 1.1.
  • the expandable graphite has a mesh number of 80 to 200 mesh.
  • the auxiliary agent comprises, in parts by mass, 0 to 1.0 parts of a dispersing agent, 0 to 1.0 part of an antifoaming agent, 0 to 1.0 part of a leveling agent, and 0 to 0.6 parts of an anti-settling agent;
  • the dispersing agent is a German Becker A solution of low molecular weight unsaturated polycarboxylic acid polymer BYK-P104, defoaming agent is BYK-066N of German Beck broken foaming polysiloxane solution, and the leveling agent is polyether modified polydimethylsiloxane copolymer.
  • BYK-333 anti-settling agent is Germany BYK modified urea solution BYK-410.
  • the solvent is a mixture of xylene, n-butanol and butyl acetate, wherein the mass ratio of xylene, n-butanol and butyl acetate is from 2.9 to 3.1:1.9 to 2.1:1.
  • the curing agent has low viscosity, high toughness and moderate curing speed.
  • the curing agent is at least one selected from the group consisting of polyamide, diethylenetriamine and triethylenetetramine.
  • PEI-DEPP modified polyethyleneimine
  • the modified polyethyleneimine is prepared by mixing polyethyleneimine, diethyl phosphite and dichloromethane, and adding carbon tetrachloride and triethylamine at 0 to 5 ° C;
  • the polyethyleneimine has a molecular weight of 600 to 70,000, and the molar ratio of the amine group to the polyethylene phosphite (amine value 18 to 20 mmol/g) to diethyl phosphite, carbon tetrachloride, and triethylamine is 1.8 to 2.
  • the amount of the dichloromethane is 1.3 to 1.5 times the mass of the polyethyleneimine; the reaction is 10 to After 24 h, the solvent is removed to give a crude product; the crude product is removed from impurities and lyophilized to give a modified polyethyleneimine.
  • the preparation method of the epoxy resin intumescent fireproof coating for steel structure the steps are as follows:
  • the epoxy resin is dissolved in a solvent, and then dehydrated into a carbon catalyst, a carbon forming agent, a foaming agent, an expandable graphite, a pigment filler, and uniformly mixed, and an auxiliary agent is added. , fully ground, that is, the A component;
  • the curing agent and the modified polyethyleneimine are dissolved in a solvent, and then the pigment filler and the auxiliary agent are added, uniformly mixed, and fully ground to obtain a B component.
  • the steel structure is an epoxy resin intumescent fireproof coating. Before use, the components A and B are mixed and stirred at a mass ratio of 2 to 5:1, and may be applied by spraying, brushing or smearing.
  • the modified polyethyleneimine synthesized is a branched macromolecular fireproofing agent which is halogen-free and has a high phosphorus-nitrogen content.
  • the fire retardant contains a plurality of active amine sites, which can be used as a reactive fire retardant and as an epoxy resin toughener, which not only enhances the fire performance of the paint, but also does not affect its mechanical properties. .
  • the fire-retardant additive collects the “three sources of one” from the acid source, gas source and carbon source: the high nitrogen content of polyethyleneimine acts as a gas source, and the “phosphorous acid” in the diethyl phosphite
  • the structure "acts as an acid source", and the "diethyl ester group” on the diethyl phosphite acts as a carbon source.
  • the reaction type fire-retardant auxiliary has high fire prevention efficiency, simple preparation method, low raw material and high yield. Commercial industrialization can be carried out.
  • the component A is made of epoxy resin as a main film-forming substance, and an expansion system composed of polyammonium phosphate, melamine phosphate, melamine, urea, pentaerythritol or mannitol is added, and then Adding expandable graphite and titanium dioxide to improve the quality of the carbon layer, adding zinc borate and aluminum hydroxide as flame retardants and smoke suppressing agents, improving the storage stability of the coating by dispersing agents, anti-settling agents, antifoaming agents and leveling agents;
  • the B component mainly has a curing agent, a modified polyethyleneimine fireproofing auxiliary, a pigment filler, a solvent and various auxiliary agents. When the two components A and B are mixed, they can produce excellent fireproof performance and physical and chemical properties, and are suitable for fire protection of offshore equipment and steel structures with harsh environments.
  • Example 1 is a 1H NMR nuclear magnetic spectrum of the fireproofing assistant PEI-DEPP synthesized in Example 1.
  • Figure 2 is a 1H NMR nuclear magnetic spectrum of polyethyleneimine PEI.
  • Figure 3 is a 1H NMR nuclear magnetic spectrum of diethyl phosphite.
  • Example 4 is a comparative photograph of the fireproof coating obtained in Example 1 before and after combustion.
  • Step 1 Preparation of modified polyethylene imine fire retardant
  • PEI polyethyleneimine
  • dichloromethane 100 g
  • Triethylamine after reacting for 24 h, was rotary evaporated to give a crude product.
  • the product was dissolved in 500 ml of distilled water, dialysis was carried out to remove impurities, and then lyophilized to obtain a final product modified polyethyleneimine (PEI-DEPP).
  • Step 2 Dissolve 480 g of epoxy resin in a solvent mixture of 130 g of xylene, 87 g of n-butanol, and 43 g of butyl acetate, and then add dehydration to a carbon catalyst, that is, 380 g of ammonium polyphosphate and 190 g of melamine phosphate, and a blowing agent of 217 g of melamine.
  • a carbon catalyst that is, 380 g of ammonium polyphosphate and 190 g of melamine phosphate, and a blowing agent of 217 g of melamine.
  • urea a carbon-forming agent, that is, 122 g of pentaerythritol and 82 g of mannitol, 41 g of expandable graphite, a pigment filler, that is, 40 g of titanium dioxide, 40 g of zinc borate and 40 g of aluminum hydroxide, are mixed, and then added to a batching tank, and dispersed and dispersed uniformly by a high-speed disperser.
  • auxiliaries (20g dispersant BYK-P104, 15g defoamer BYK-066N, 15g leveling agent BYK-333, 10g anti-settling agent BYK-410), and then use a three-roll mill (or ball mill or sanding) Machine) is fully ground for 2h, and after sifting, the A component is obtained.
  • Step 3 Dissolve 350 g of the curing agent polyamide and 200 g of the modified polyethyleneimine obtained in the step 1 in a solvent mixed with 45 g of xylene, 30 g of n-butanol, and 15 g of butyl acetate, and then add a pigment filler, that is, 10 g.
  • Titanium dioxide, 10g zinc borate, 10g aluminum hydroxide and additives (6g dispersant BYK-P104, 5g defoamer BYK-066N, 5g leveling agent BYK-333, 4g anti-settling agent BYK-410), then high-speed dispersion stirring After 30 min, it was fully ground for 1 h with a three-roll mill (or ball mill or sand mill), and sieved after discharge to obtain component B.
  • Step 4 When the two components A and B are mixed at a mass ratio of 4.5:1, a fireproof coating can be obtained, which can be sprayed, brushed or smeared.
  • Step 1 Preparation of modified polyethylene imine fire retardant
  • Step 2 Dissolve 450 g of epoxy resin in a solvent mixed with 120 g of xylene, 80 g of n-butanol, and 40 g of butyl acetate, and then add dehydration to a carbon catalyst, that is, 340 g of ammonium polyphosphate and 170 g of melamine phosphate, and a blowing agent of 190 g of melamine.
  • a carbon catalyst that is, 340 g of ammonium polyphosphate and 170 g of melamine phosphate, and a blowing agent of 190 g of melamine.
  • urea a carbon-forming agent, that is, 120g of pentaerythritol and 60g of mannitol, 41g of expandable graphite, a pigment filler, that is, 30g of titanium dioxide, 30g of zinc borate and 30g of aluminum hydroxide, are mixed, and then added to the batching tank, and dispersed and dispersed uniformly by a high-speed disperser.
  • a carbon-forming agent that is, 120g of pentaerythritol and 60g of mannitol
  • 41g of expandable graphite a pigment filler, that is, 30g of titanium dioxide, 30g of zinc borate and 30g of aluminum hydroxide
  • auxiliaries 15g dispersant BYK-P104, 15g defoamer BYK-066N, 12g leveling agent BYK-333, 6g anti-settling agent BYK-410
  • a three-roll mill (or ball mill or sanding) Machine is fully ground for 2h, and after sifting, the A component is obtained.
  • Step 3 Dissolve 380 g of the curing agent polyamide and 180 g of the modified polyethyleneimine obtained in the step 1 in a solvent mixed with 39 g of xylene, 26 g of n-butanol and 13 g of butyl acetate, and then add a pigment filler, ie, 30 g of titanium dioxide, 30 g.
  • Zinc borate 30g aluminum hydroxide and additives (8g dispersant BYK-P104, 15g defoamer BYK-066N, 12g leveling agent BYK-333, 10g anti-settling agent BYK-410), then stir at high speed for 30min, then It is fully ground for 1 hour with a three-roll mill (or ball mill or sand mill), and sieved after discharge to obtain component B.
  • additives 8g dispersant BYK-P104, 15g defoamer BYK-066N, 12g leveling agent BYK-333, 10g anti-settling agent BYK-410
  • Step 4 When the two components A and B are mixed at a mass ratio of 4:1, the fireproof coating can be obtained, and the coating can be sprayed, brushed or smeared.
  • Step 1 Preparation of modified polyethylene imine fire retardant
  • Step 2 600 g of epoxy resin was dissolved in a solvent of 141 g of xylene, 94 g of n-butanol, and 47 g of butyl acetate, and then dehydrated to a carbon catalyst, that is, 420 g of ammonium polyphosphate and 210 g of melamine phosphate, and a foaming agent, 180 g of melamine.
  • a carbon catalyst that is, 420 g of ammonium polyphosphate and 210 g of melamine phosphate, and a foaming agent, 180 g of melamine.
  • Step 3 Dissolve 150 g of the curing agent polyamide and 180 g of the modified polyethyleneimine obtained in the step 1 in a solvent mixture of 30 g of xylene, 20 g of n-butanol and 10 g of butyl acetate, and then add a pigment filler, that is, 15 g of titanium dioxide, 15 g. Zinc borate, 15g aluminum hydroxide and additives (5g dispersant BYK-P104, 5g defoamer BYK-066N, 5g leveling agent BYK-333, 5g anti-settling agent BYK-410), then disperse and stir for 30min at high speed, and then fully grind for 1h with three-roll mill (or ball mill or sand mill). Sieve, that is, the B component.
  • a pigment filler that is, 15 g of titanium dioxide, 15 g.
  • Zinc borate, 15g aluminum hydroxide and additives 5g dispersant BYK-P104, 5g def
  • Step 4 When the two components A and B are mixed at a mass ratio of 2.5:1, the fireproof coating can be obtained, and the coating can be sprayed, brushed or smeared.

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Abstract

一种钢结构用环氧树脂膨胀型防火涂料及其制备方法，属于功能性涂料。本膨胀型防火涂料由A、B两组分组成，其中A组分主要包括成膜物质、脱水成炭催化剂、发泡剂、成炭剂、助剂、溶剂、颜填料，B组分主要包括固化剂、改性聚乙烯亚胺、溶剂、助剂。该防火涂料采用亚磷酸二乙酯改性聚乙烯亚胺为防火助剂(PEI-DEPP)及复配技术，有效提高防火涂料燃烧后炭层膨胀倍数及炭层质量。该涂料具有优异的防火性能、粘结力、耐水性、耐热性能、耐腐蚀性和耐酸碱性，不仅可用于高层钢结构建筑，还适用于海工装备和石化产业等处于恶劣环境的钢结构的防火保护。

Description

一种钢结构用环氧树脂膨胀型防火涂料及其制备方法 技术领域
本发明属于防火涂料领域，涉及一种环氧树脂防火涂料，具体是涉及一种钢结构用环氧树脂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，人类所用的建筑材料不断更新换代。钢结构建筑相比于砖混结构建筑在环保、节能、高效、工厂化生产等方面具有明显优势，因而逐步取代钢筋混凝土成为主要的建筑形式。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。膨胀型防火涂料目前广泛被用来作为钢结构建筑的防火，膨胀型防火涂料遇火后膨胀发泡，起到阻燃隔热作用，发泡时绝不释放有毒气体，保护人体不受毒害。
膨胀型防火涂料基体树脂可分为热塑型和热固型两种，热固型防火涂料采用双组份体系，成膜物多为环氧树脂或聚氨酯树脂。双组份一般具有较好的耐化学腐蚀性、耐热性、耐酸碱性和封闭性。阻燃体系也不易迁移到涂层表面，防火性能较为稳定，不易受时间和环境的影响。双组份防火涂料膨胀炭层强度高，能提供有效防火保护。
近年来对钢结构防火涂料的报道很多，但对于反应型自膨胀防火助剂的研究、专利报道并不多。中国专利CN102634264A合成了一种水性磷酸苯酯二缩水甘油酯，然后将这种化合物用来制备水性含磷环氧树脂防火涂料，当固化后涂层厚度为1.0mm时，涂有防火涂料的三合板耐穿烧时间可达一小时，其LOI也可达42。中国专利CN105585931A通过用二乙醇胺对环氧树脂改性，然后分别采用磷酸-五氧化二磷-尿素、磷酸-尿素、多聚磷酸铵-尿素与改性后的环氧树脂反应，合成出一种水溶性聚磷酸铵酯阻燃剂，并制成新型的高性能透明防火涂料，其耐燃时间可达60min。中国专利CN104845490A制备了添加新型阻燃剂的防火涂料，阻燃剂包括三氧化二锑、硫酸铵、氢氧化镁、柠檬酸和硅藻土。 中国专利CN104804594A制备了一种钢结构防火涂料，使用了添加型可膨胀石墨、氯化石蜡和钛白粉，当涂层厚度2.2mm其耐火极限可达100min。
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)加入的防火助剂都是添加型，随着时间推移，防火助剂易流失，因而会导致防火性能下降。
2)防火助剂添加量较大，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，且添加型防火助剂容易沉降，会影响防火性能。
发明内容
本发明旨在解决现有钢结构防火涂料的不足，提出了一种钢结构用环氧树脂膨胀型防火涂料及其制备方法。
本发明所述的钢结构用环氧树脂膨胀型防火涂料的具体配方如表1：
表1 本发明的钢结构用环氧树脂膨胀型防火涂料的组分与质量分数
A组分 含量(wt％) B组分 含量(wt％)
环氧树脂 21～28 固化剂 35～53
脱水成炭催化剂 26～30 改性聚乙烯亚胺 20～40
发泡剂 14～16 助剂 0～4
成炭剂 8～10 颜填料 0～15
颜填料 2～7 溶剂 5～15
可膨胀石墨 2～3
助剂 0～6
溶剂 12～18
所述的环氧树脂为双酚A型环氧树脂或双酚F型环氧树脂，环氧值为0.1～0.56之间。
所述脱水成炭催化剂包括质量比为2～3:1的聚磷酸铵和磷酸三聚氰胺。
所述发泡剂包括质量比为1.9～3:1的三聚氰胺和脲。
所述成炭剂包括质量比为1.4～2:1的季戊四醇和甘露醇。
所述颜填料包括质量比为0.9～1.1:0.9～1.1:0.9～1.1的二氧化钛、硼酸锌和氢氧化铝。
所述的可膨胀石墨目数为80～200目。
所述助剂按质量份数计，包括分散剂0～1.0份、消泡剂0～1.0份、流平剂0～1.0份、防沉剂0～0.6份；所述分散剂为德国毕克低分子量不饱和多元羧酸聚合物的溶液BYK-P104，消泡剂为德国毕克破泡聚硅氧烷溶液BYK-066N，流平剂为聚醚改性聚二甲基硅氧烷共聚体BYK-333，防沉剂为德国毕克改性脲溶液BYK-410。
所述溶剂为二甲苯、正丁醇和乙酸丁酯的混合，其中二甲苯、正丁醇和乙酸丁酯的质量比为2.9～3.1:1.9～2.1:1。
所述固化剂粘度低、韧性高、固化速度适中，例如固化剂选用聚酰胺、二乙烯三胺、三乙烯四胺中的至少一种。
所述改性聚乙烯亚胺(PEI-DEPP)作为其中的防火助剂，其化学结构式如下：
Figure PCTCN2017112583-appb-000001
其中n为聚合度，n＝1～140。
所述改性聚乙烯亚胺的制备方法为：将聚乙烯亚胺、亚磷酸二乙酯和二氯甲烷混合，在0～5℃下，滴加四氯化碳和三乙胺；所述聚乙烯亚胺分子量为600～70000，且聚乙烯亚胺(胺值18～20mmol/g)中的胺基与亚磷酸二乙酯、四氯化碳、三乙胺的摩尔比为1.8～2:0.8～1.2:1～1.4:1～1.4，优选为1.8～2:1:1.2:1.2；所述二氯甲烷的用量按质量比为聚乙烯亚胺质量的1.3～1.5倍；反应10～24h后，除去溶剂，得到粗产物；将粗产物除去杂质，冻干，即得改性聚乙烯亚胺。
所述钢结构用环氧树脂膨胀型防火涂料的制备方法，其步骤如下：
1)按所述A组分中的配比，将环氧树脂溶解于溶剂中，再加入脱水成炭催化剂、成炭剂、发泡剂、可膨胀石墨、颜填料，混合均匀，加入助剂，充分研磨，即得A组分；
2)按所述B组分中的配比，将固化剂和改性聚乙烯亚胺溶解于溶剂中，再加入颜填料和助剂，混合均匀，充分研磨，即得B组分。
所述钢结构用环氧树脂膨胀型防火涂料，在使用前，将A、B组分按质量比2～5:1混合搅拌，可以采用喷涂、刷涂、镘涂的方法进行施工。
与现有技术相比本发明具有以下优点：
1)所合成的改性聚乙烯亚胺是一种无卤且有较高磷氮含量的支链型大分子防火助剂。
2)该防火助剂(PEI-DEPP)含有多个活性胺基位点，可作为反应型防火助剂，又可作为环氧树脂增韧剂，既增强涂料防火性能，又不影响其机械性能。
3)该防火助剂(PEI-DEPP)集酸源、气源、碳源“三源一体”：其中聚乙烯亚胺高含氮量起到气源作用，亚磷酸二乙酯中“亚磷酸结构”起到酸源作用，亚磷酸二乙酯上的“二乙酯基团”起到碳源作用，该反应型防火助剂防火效率高，制备方法简便，原料廉价，产率较高，可以进行商业产业化。
4)本发明的环氧树脂膨胀型防火涂料中，A组分以环氧树脂为主要成膜物质，添加多聚磷酸铵、磷酸三聚氰胺、三聚氰胺、脲和季戊四醇、甘露醇组成的膨胀体系，再添加可膨胀石墨和二氧化钛以提高炭层质量，加入硼酸锌和氢氧化铝作为阻燃剂和抑烟剂，通过分散剂、防沉剂、消泡剂和流平剂提高涂料的贮存稳定性；B组分主要有固化剂、改性聚乙烯亚胺防火助剂、颜填料、溶剂和各种助剂。A、B两组分混合使用时，能够产生优异的防火性能和理化性能，适用于环境较为恶劣的海工装备和钢结构的防火保护。
附图说明
下面结合附图和实施例对本发明作进一步说明。
图1为实施例1中合成的防火助剂PEI-DEPP的1HNMR核磁谱图。
图2为聚乙烯亚胺PEI的1HNMR核磁谱图。
图3为亚磷酸二乙酯的1HNMR核磁谱图。
图4为实施例1得到的防火涂料燃烧前后的对比照片。
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：制备改性聚乙烯亚胺防火助剂
在反应釜中加入100g分子量为600～70000的聚乙烯亚胺(PEI)、138g亚磷酸二乙酯以及100ml二氯甲烷，在冰浴条件下，在6h内滴加185g四氯化碳和122g三乙胺，反应24h后，旋蒸得到粗产物。将产物溶解在500ml蒸馏水中，透析除去杂质，然后冻干得到最终产物改性聚乙烯亚胺(PEI-DEPP)。
由图1的1HNMR核磁谱图和图2、图3对比可见在2～3ppm出现了聚乙烯亚胺PEI的胺基质子峰，7.66ppm和5.93ppm却没有亚磷酸二乙酯的P-H质子峰，且分别在1.23ppm和3.91ppm处出现了亚磷酸二乙酯的甲基和亚甲基的峰。说明防火助剂PEI-DEPP的成功合成。
步骤2：将480g环氧树脂溶解于130g二甲苯、87g正丁醇、43g乙酸丁酯混合的溶剂中，再加入脱水成炭催化剂即380g聚磷酸铵和190g磷酸三聚氰胺，发泡剂即217g三聚氰胺和109g脲，成炭剂即122g季戊四醇和82g甘露醇，41g可膨胀石墨，颜填料即40g二氧化钛、40g硼酸锌和40g氢氧化铝，混合，然后加入配料罐中，用高速分散机分散搅拌均匀30min，加入助剂(20g分散剂BYK-P104，15g消泡剂BYK-066N，15g流平剂BYK-333，10g防沉剂BYK-410)，再用三辊研磨机(或球磨机或砂磨机)进行充分研磨2h，出料后过筛，即得A组分。
步骤3：将350g固化剂聚酰胺和200g步骤1得到的改性聚乙烯亚胺溶解于45g二甲苯、30g正丁醇、15g乙酸丁酯混合的溶剂中，再加入颜填料即10g 二氧化钛、10g硼酸锌、10g氢氧化铝和助剂(6g分散剂BYK-P104，5g消泡剂BYK-066N，5g流平剂BYK-333，4g防沉剂BYK-410)，然后高速分散搅拌30min，再用三辊研磨机(或球磨机或砂磨机)进行充分研磨1h，出料后过筛，即得B组分。
步骤4：用时A、B两组分按质量比4.5:1的比例混合，即得防火涂料，喷涂、刷涂或镘涂均可。
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1.92mm(图4右)，膨胀后炭层高度为4.32cm(图4左)，耐火极限143.3min；其余结果见表2。
表2 实施例1的环氧树脂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 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 0.43
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1.92mm，耐火极限143.3min
实施例2：
步骤1：制备改性聚乙烯亚胺防火助剂
在反应釜中加入100g分子量为600～70000的聚乙烯亚胺、125g亚磷酸二乙酯以及100ml二氯甲烷，在冰浴条件下，在6h内滴加185g四氯化碳和122g三乙胺，反应24h后，旋蒸得到粗产物。将产物溶解在500ml蒸馏水中，透析除去杂质，然后冻干得到最终产物改性聚乙烯亚胺。
步骤2：将450g环氧树脂溶解于120g二甲苯、80g正丁醇、40g乙酸丁酯混合的溶剂中，再加入脱水成炭催化剂即340g聚磷酸铵和170g磷酸三聚氰胺，发泡剂即190g三聚氰胺和95g脲，成炭剂即120g季戊四醇和60g甘露醇，41g可膨胀石墨，颜填料即30g二氧化钛、30g硼酸锌和30g氢氧化铝，混合，然后加入配料罐中，用高速分散机分散搅拌均匀30min，加入助剂(15g分散剂BYK-P104，15g消泡剂BYK-066N，12g流平剂BYK-333，6g防沉剂BYK-410)，再用三辊研磨机(或球磨机或砂磨机)进行充分研磨2h，出料后过筛，即得A组分。
步骤3：将380g固化剂聚酰胺和180g步骤1得到的改性聚乙烯亚胺溶解于39g二甲苯、26g正丁醇、13g乙酸丁酯混合的溶剂中，再加入颜填料即30g二氧化钛、30g硼酸锌、30g氢氧化铝和助剂(8g分散剂BYK-P104，15g消泡剂BYK-066N，12g流平剂BYK-333，10g防沉剂BYK-410)，然后高速分散搅拌30min，再用三辊研磨机(或球磨机或砂磨机)进行充分研磨1h，出料后过筛，即得B组分。
步骤4：用时A、B两组分按质量比4:1的比例混合，即得防火涂料，喷涂、刷涂或镘涂均可。
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1.89mm，耐火极限110.2min；其余结果见表3。
表3 实施例2的环氧树脂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 4.5
初期干燥抗裂性 无裂纹
外观与颜色 符合要求
粘结强度/MPa 0.52
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1.89mm，耐火极限110.2min
实施例3：
步骤1：制备改性聚乙烯亚胺防火助剂
在反应釜中加入100g分子量为600～70000的聚乙烯亚胺和138g亚磷酸二乙酯以及100ml二氯甲烷，在冰浴条件下，在6h内滴加185g四氯化碳和122g三乙胺，反应24h后，旋蒸得到粗产物。将产物溶解在500ml蒸馏水中，透析除去杂质，然后冻干得到最终产物改性聚乙烯亚胺。
步骤2：将600g环氧树脂溶解于141g二甲苯、94g正丁醇、47g乙酸丁酯混合的溶剂中，再加入脱水成炭催化剂即420g聚磷酸铵和210g磷酸三聚氰胺，发泡剂即180g三聚氰胺和90g脲，成炭剂及140g季戊四醇和70g甘露醇，50g可膨胀石墨，颜填料即45g二氧化钛、45g硼酸锌和45g氢氧化铝，混合，然后加入配料罐中，用高速分散机分散搅拌均匀30min，加入助剂(25g分散剂BYK-P104，18g消泡剂BYK-066N，18g流平剂BYK-333，14g防沉剂BYK-410)，再用三辊研磨机(或球磨机或砂磨机)进行充分研磨2h，出料后过筛，即得A组分。
步骤3：将150g固化剂聚酰胺和180g步骤1得到的改性聚乙烯亚胺溶解于30g二甲苯、20g正丁醇、10g乙酸丁酯混合的溶剂中，再加入颜填料即15g二氧化钛、15g硼酸锌、15g氢氧化铝和助剂(5g分散剂BYK-P104，5g消泡剂 BYK-066N，5g流平剂BYK-333，5g防沉剂BYK-410)，然后高速分散搅拌30min，再用三辊研磨机(或球磨机或砂磨机)进行充分研磨1h，出料后过筛，即得B组分。
步骤4：用时A、B两组分按质量比2.5:1的比例混合，即得防火涂料，喷涂、刷涂或镘涂均可。
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2.04mm，耐火极限120.8min；其余结果见表4。
表4 实施例3的环氧树脂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 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 0.65
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2.04mm，耐火极限120.8min
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. 一种钢结构用环氧树脂膨胀型防火涂料，其特征在于：包括A组分和B组分，其中，A组分按质量份数计，包括：环氧树脂21～28份，脱水成炭催化剂25～30份，发泡剂11～17份，成炭剂8～11份，颜填料2～7份，可膨胀石墨2～3份，助剂0～6份，溶剂11～18份；B组分按质量份数计，包括：固化剂35～53份，改性聚乙烯亚胺18～54份，助剂0～6份，颜填料0～15份，溶剂5～18份，所述改性聚乙烯亚胺化学结构式如下：
    Figure PCTCN2017112583-appb-100001
    其中，n为聚合度，n＝1～140；
    用时A、B两组分按质量比2～5:1的比例混合使用。
  2. 如权利要求1所述的钢结构用环氧树脂膨胀型防火涂料，其特征在于：所述环氧树脂为双酚A型环氧树脂或双酚F型环氧树脂，环氧值为0.1～0.56之间。
  3. 如权利要求1所述的钢结构用环氧树脂膨胀型防火涂料，其特征在于所述脱水成炭催化剂包括质量比为2～3:1的聚磷酸铵和磷酸三聚氰胺；所述发泡剂包括质量比为1.9～3:1的三聚氰胺和脲；所述成炭剂包括质量比为1.4～2:1的季戊四醇和甘露醇；所述颜填料包括质量比为0.9～1.1:0.9～ 1.1:0.9～1.1的二氧化钛、硼酸锌和氢氧化铝；所述可膨胀石墨目数为80～200目。
  4. 如权利要求1所述的钢结构用环氧树脂膨胀型防火涂料，其特征在于：所述助剂按质量份数计，包括分散剂0～1.0份、消泡剂0～1.0份、流平剂0～1.0份、防沉剂0～0.6份；所述分散剂为低分子量不饱和多元羧酸聚合物的溶液，消泡剂为破泡聚硅氧烷溶液，流平剂为聚醚改性聚二甲基硅氧烷共聚体，防沉剂为改性脲溶液。
  5. 如权利要求1所述的钢结构用环氧树脂膨胀型防火涂料，其特征在于：所述溶剂为二甲苯、正丁醇和乙酸丁酯的混合，其中二甲苯、正丁醇和乙酸丁酯的质量比为2.9～3.1:1.9～2.1:1。
  6. 如权利要求1所述的钢结构用环氧树脂膨胀型防火涂料，其特征在于：所述固化剂为聚酰胺、二乙烯三胺、三乙烯四胺中的至少一种。
  7. 一种权利要求1所述的钢结构用环氧树脂膨胀型防火涂料的制备方法，其特征在于：包括：
    1)按所述A组分中的配比，将环氧树脂溶解于溶剂中，再加入脱水成炭催化剂、成炭剂、发泡剂、可膨胀石墨、颜填料，混合均匀，加入助剂，充分研磨，即得A组分；
    2)按所述B组分中的配比，将固化剂和改性聚乙烯亚胺溶解于溶剂中，再加入颜填料和助剂，混合均匀，充分研磨，即得B组分。
  8. 根据权利要求7所述的钢结构用环氧树脂膨胀型防火涂料的制备方法，其特征在于：所述改性聚乙烯亚胺的制备方法为：将胺值18～20mmol/g的聚乙烯亚胺、亚磷酸二乙酯和二氯甲烷混合，在0～5℃下，滴加四氯化碳和三乙胺；所述聚乙烯亚胺分子量为600～70000，且聚乙烯亚胺中的胺基与亚磷酸二乙酯、四氯化碳、三乙胺的摩尔比为1.8～2:0.8～1.2:1～1.4:1～1.4；所 述二氯甲烷的用量按质量比为聚乙烯亚胺质量的1.3～1.5倍；反应10～24h后，除去溶剂，得到粗产物；将粗产物除去杂质，冻干，即得改性聚乙烯亚胺。
  9. 一种环氧树脂膨胀型防火涂料用防火助剂，其特征在于：该防火助剂为改性聚乙烯亚胺，其化学结构式如下：
    Figure PCTCN2017112583-appb-100002
    其中，n为聚合度，n＝1～140。
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3712218A1 (de) * 2019-03-22 2020-09-23 Hilti Aktiengesellschaft Brandschutzzusammensetzung und deren verwendung
EP3712219A1 (de) * 2019-03-22 2020-09-23 Hilti Aktiengesellschaft Brandschutzzusammensetzung und deren verwendung
CN113217077A (zh) * 2021-05-07 2021-08-06 湖南红森科技有限公司 一种隧道防火涂层的施工方法
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CN116925497A (zh) * 2023-07-21 2023-10-24 广州润泰新材料科技有限公司 一种新型防火材料及其制备方法和应用
CN116970325A (zh) * 2023-09-22 2023-10-31 潍坊市兴源防水材料股份有限公司 一种建筑防火涂料及其制备方法
CN117467332A (zh) * 2023-11-24 2024-01-30 上海中南建筑材料有限公司 一种耐水型气凝胶防火涂料及其制备方法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN108559359B (zh) * 2018-04-25 2020-07-31 中南林业科技大学 一种相变吸热、膨胀阻燃的钢结构防火涂料及其制备方法
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086385A (en) * 1975-11-05 1978-04-25 The United States Of America As Represented By The Secretary Of Agriculture Flame retarded textiles via deposition of polymers from oligomeric vinylphosphonate and polyamino compounds
CN103045037A (zh) * 2012-12-14 2013-04-17 中盈长江国际新能源投资有限公司 水性膨胀型钢结构防火涂料及制备方法
CN103740231A (zh) * 2013-12-26 2014-04-23 中盈长江国际新能源投资有限公司 一种水性膨胀型电缆用纳米防火涂料及其制备方法
CN105368166A (zh) * 2015-11-27 2016-03-02 沈阳顺风新城建筑材料有限公司 一种膨胀型氯化橡胶防火涂料及其制备方法
US20160168393A1 (en) * 2014-12-12 2016-06-16 United States Mineral Products Company Intumescent Coating
CN106752682A (zh) * 2016-11-23 2017-05-31 厦门大学 一种钢结构用环氧树脂膨胀型防火涂料及其制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103805033A (zh) * 2014-02-25 2014-05-21 绵阳惠利环氧工程有限公司 一种超薄膨胀型钢结构防火涂料及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086385A (en) * 1975-11-05 1978-04-25 The United States Of America As Represented By The Secretary Of Agriculture Flame retarded textiles via deposition of polymers from oligomeric vinylphosphonate and polyamino compounds
CN103045037A (zh) * 2012-12-14 2013-04-17 中盈长江国际新能源投资有限公司 水性膨胀型钢结构防火涂料及制备方法
CN103740231A (zh) * 2013-12-26 2014-04-23 中盈长江国际新能源投资有限公司 一种水性膨胀型电缆用纳米防火涂料及其制备方法
US20160168393A1 (en) * 2014-12-12 2016-06-16 United States Mineral Products Company Intumescent Coating
CN105368166A (zh) * 2015-11-27 2016-03-02 沈阳顺风新城建筑材料有限公司 一种膨胀型氯化橡胶防火涂料及其制备方法
CN106752682A (zh) * 2016-11-23 2017-05-31 厦门大学 一种钢结构用环氧树脂膨胀型防火涂料及其制备方法

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3712218A1 (de) * 2019-03-22 2020-09-23 Hilti Aktiengesellschaft Brandschutzzusammensetzung und deren verwendung
EP3712219A1 (de) * 2019-03-22 2020-09-23 Hilti Aktiengesellschaft Brandschutzzusammensetzung und deren verwendung
CN113217077A (zh) * 2021-05-07 2021-08-06 湖南红森科技有限公司 一种隧道防火涂层的施工方法
CN113217077B (zh) * 2021-05-07 2024-03-29 湖南红森科技有限公司 一种隧道防火涂层的施工方法
CN114904739A (zh) * 2022-06-16 2022-08-16 广东百安环保新材料有限公司 一种用于钢结构的水性防火涂料及其制备方法
CN114904739B (zh) * 2022-06-16 2023-04-14 广东百安环保新材料有限公司 一种用于钢结构的水性防火涂料及其制备方法
CN114922066A (zh) * 2022-07-08 2022-08-19 上海岐海防腐工程技术有限公司 一种防腐防火的桥梁缆索
CN116925497A (zh) * 2023-07-21 2023-10-24 广州润泰新材料科技有限公司 一种新型防火材料及其制备方法和应用
CN116970325A (zh) * 2023-09-22 2023-10-31 潍坊市兴源防水材料股份有限公司 一种建筑防火涂料及其制备方法
CN116970325B (zh) * 2023-09-22 2023-11-24 潍坊市兴源防水材料股份有限公司 一种建筑防火涂料及其制备方法
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