WO2023050315A1 - 一种超支化型含磷硅脂肪胺阻燃固化剂及其制备方法和在防火涂料中的应用 - Google Patents

一种超支化型含磷硅脂肪胺阻燃固化剂及其制备方法和在防火涂料中的应用 Download PDF

Info

Publication number
WO2023050315A1
WO2023050315A1 PCT/CN2021/122191 CN2021122191W WO2023050315A1 WO 2023050315 A1 WO2023050315 A1 WO 2023050315A1 CN 2021122191 W CN2021122191 W CN 2021122191W WO 2023050315 A1 WO2023050315 A1 WO 2023050315A1
Authority
WO
WIPO (PCT)
Prior art keywords
preparation
curing agent
triethylenetetramine
hyperbranched
phosphorus
Prior art date
Application number
PCT/CN2021/122191
Other languages
English (en)
French (fr)
Inventor
刘治田
石遒
王成
Original Assignee
武汉工程大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 武汉工程大学 filed Critical 武汉工程大学
Publication of WO2023050315A1 publication Critical patent/WO2023050315A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4085—Curing agents not provided for by the groups C08G59/42 - C08G59/66 silicon containing compounds
    • 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

Definitions

  • the invention belongs to the technical field of fireproof coatings, and in particular relates to a hyperbranched phosphorus-containing silicon fatty amine flame-retardant curing agent, a preparation method thereof and an application in fireproof coatings.
  • Intumescent fire retardant coatings are usually composed of binders, intumescent flame retardant systems and filler additives.
  • the binder melts, and the acid source in the intumescent flame retardant system decomposes to release acidic substances, which promote the binder and
  • the carbon source is dehydrated and carbonized to decompose the gas source, release non-combustible gas and generate viscous coke.
  • the combination of the two forms a honeycomb carbon layer, thereby isolating air and heat transfer, so as to achieve excellent fire and heat insulation effects.
  • Epoxy resin is the most widely used thermosetting material at present. Epoxy resin with aliphatic amines as curing agent has good adhesion due to its low glass transition temperature and curing temperature, fast response and insulation. Adhesion, often used as a binder for adhesives and coatings. Among them, triethylenetetramine (triethylenetetramine), as a water-soluble aliphatic amine curing agent, has the advantages of less volatility and lower toxicity compared to diethylamine and diethylenetriamine, and is a kind of Commonly used water-based epoxy fatty amine curing agent, the coating prepared by using it has fast curing, moderate temperature and good transparency; therefore, it is often used as a film-forming material for intumescent fireproof coatings.
  • triethylenetetramine triethylenetetramine
  • the coating prepared by using it has fast curing, moderate temperature and good transparency; therefore, it is often used as a film-forming material for intumescent fireproof coatings.
  • aliphatic amine curing agents have disadvantages such as volatility and strong toxicity. In recent years, with the improvement of people's awareness of environmental protection, their use is often limited. At the same time, the epoxy resin cured by aliphatic amine curing agent has poor mechanical properties due to the lack of rigid groups between the chains, which limits its application range, and due to the low glass transition temperature, its thermodynamic properties are extremely poor, often in The fire will promote the burning of the flame, which is not good for the protection of steel.
  • triethylenetetramine is used as the curing agent of the epoxy-based fireproof coating, and it is not flame-retardantly modified, and mainly plays the role of an adhesive.
  • the main purpose of the present invention is to provide a hyperbranched phosphorus-containing silicon aliphatic amine flame-retardant curing agent and the fire-resistant coating prepared by using it in view of the deficiencies in the prior art.
  • the fire-resistant coating obtained by the flame-retardant curing agent has long fire resistance , good water resistance, excellent adhesion, short drying time, good crack resistance and other advantages, the obtained fire retardant coating can have good flame retardancy and mechanical properties, etc.; and the preparation process involved is simple, the cost is low, and it is suitable for popularization and application.
  • a hyperbranched type phosphorus-containing silicon fatty amine flame retardant curing agent its preparation method comprises the steps:
  • step 2) Add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), azobisisobutyronitrile (AIBN) and an organic solvent to the filtrate obtained in step 1), Under stirring conditions, carry out heat preservation reaction, evaporate the solvent; then dissolve the obtained solid product in an alcohol solvent, filter, collect the filtrate, and evaporate the solvent; then dissolve in water, filter, collect the filtrate, evaporate to dryness, and dry to obtain The hyperbranched phosphorus-containing silicon fatty amine flame retardant curing agent.
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • AIBN azobisisobutyronitrile
  • the organic solvent can be selected from DMF and the like; the alcohol solvent can be selected from absolute ethanol and the like.
  • the triethylenetetramine is added to the organic solvent at a temperature of -10 to 0°C; the time for adding trichlorovinylsilane is 1 to 1.5 hours.
  • reaction time at room temperature in step 1) is 3 to 5 hours.
  • the mass ratio of triethylenetetramine to DMF is 1:5 ⁇ 5:1.
  • the molar ratio of triethylenetetramine to trichlorovinylsilane is 3:2 ⁇ 2:1.
  • the molar ratio of the triethylenetetramine to the introduced sodium carbonate is 1:2-2:1.
  • the molar ratio of triethylenetetramine to DOPO is 3:2 ⁇ 2:1.
  • the molar ratio of triethylenetetramine to AIBN is 30:2 ⁇ 20:1.
  • the mass ratio of the triethylenetetramine to the alcohol solvent introduced in the dissolving step in step 1) or 2) is 1:5-5:1.
  • the mass ratio of the triethylenetetramine to the water introduced in the dissolving step in step 2) is 1:5 ⁇ 5:1.
  • the heat preservation reaction temperature in step 2) is 80-120° C., and the time is 12-24 hours.
  • the drying temperature in step 2) is 80-110° C.
  • the drying time is 18-24 hours.
  • the present invention also provides a fire retardant coating based on the above-mentioned hyperbranched phosphorus-containing silicon fatty amine flame-retardant curing agent, each component and its mass percentage include: hyperbranched triethyltetraamine-based phosphorus-containing silicon fatty amine Flame retardant curing agent 5-30%, epoxy resin 35-60%, polyphosphate amine 15-20%, pentaerythritol 10-20%, melamine 10-15%, titanium dioxide 1-5%, hydroxyethyl cellulose 0.5- 1%, dispersant 0.5-1%, defoamer 0.5-1%, n-octanol 0.5-1%.
  • the epoxy resin is E44, E51, E53 type bisphenol A type epoxy resin, bisphenol F type epoxy resin or the like.
  • the dispersant is wetting and dispersing agent 5040 and the like.
  • the defoamer is silicone defoamer 470 and the like.
  • the linear small molecule triethylenetetramine becomes a hyperbranched macromolecule, reducing its volatility and further reducing its toxicity; at the same time Introduce phosphaphenanthrene groups between the chains to increase the glass transition temperature of the cured epoxy resin; use the cured fireproof coating, due to the special structure of silicon-phosphaphenanthrene at the molecular scale, it can simultaneously play the gas phase of DOPO
  • the quenching effect and the network condensed phase effect formed by siloxane can greatly improve the flame retardant performance of the obtained fireproof coating; at the same time, the obtained hyperbranched linear macromolecular curing agent can increase the interchain force and make use of its cured
  • the mechanical properties of epoxy resin have been greatly improved, and the mechanical properties of fire-resistant coatings have been effectively improved at the same time.
  • the hyperbranched phosphorus-containing silicon-containing fatty amine flame retardant curing agent of the present invention can simultaneously exert the gas phase quenching effect of DOPO and the network condensed phase effect formed by siloxane, and synergistically improve the fire prevention effect of the curing agent itself and the fireproof coating ; At the same time, it can increase the force between the chains and simultaneously improve the mechanical properties of the obtained fireproof coating;
  • the fire-resistant coating obtained in the present invention has the advantages of long fire-resistant time, good water resistance, excellent adhesion, short drying time, good crack resistance, etc., and can have good flame-retardant and mechanical properties, etc., and is suitable for popularization and application.
  • Fig. 1 is the structural representation of a kind of hyperbranched type phosphorus-containing silicon aliphatic amine flame retardant curing agent gained in embodiment 1;
  • Fig. 2 is the proton nuclear magnetic resonance spectrogram of embodiment 1 gained hyperbranched type phosphorus-containing silicon aliphatic amine flame retardant curing agent;
  • Fig. 3 is the nuclear magnetic resonance phosphorus spectrogram of embodiment 1 gained hyperbranched type phosphorus-containing silicon fatty amine flame retardant curing agent;
  • Fig. 4 is the E51 epoxy resin sample bar UL-94 test digital photo that embodiment 1 gained hyperbranched type phosphorus-containing silicon aliphatic amine flame retardant curing agent prepares;
  • Fig. 5 is the back temperature curve of the large plate combustion method of the intumescent fireproof coating obtained in Application Example 1 and Comparative Example.
  • the dispersant used is wetting and dispersing agent 5040; the defoamer is silicone defoamer 470.
  • a hyperbranched type phosphorus-containing silicon fatty amine flame retardant curing agent its chemical structure schematic diagram is shown in Figure 1 (in the figure); the specific preparation method comprises the following steps:
  • Fig. 2 and Fig. 3 are respectively the H NMR spectrum and the NMR phosphorus spectrum of the hyperbranched type phosphorus-containing silicon aliphatic amine flame retardant curing agent obtained in this embodiment.
  • the results show that DOPO and triethylene glycol have appeared in the H NMR spectrum. There is only one single peak of phosphorus in the NMR phosphorus spectrum.
  • Fig. 4 is the digital photograph of the E51 epoxy resin sample UL-94 test prepared by the hyperbranched phosphorus-containing silicon aliphatic amine flame retardant curing agent obtained in this example.
  • a fire-retardant coating based on a hyperbranched type phosphorus-containing silicon fatty amine flame-retardant curing agent each component and its mass percentage are: the hyperbranched type triethyltetramine-based phosphorus-containing silicon fatty amine flame-retardant obtained in Example 1 Curing agent 10%, E51 type epoxy resin 50%, polyphosphate amine 15%, pentaerythritol 10%, melamine 10%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, N-octanol 0.5%, its preparation method comprises the following steps:
  • a fire retardant coating based on a hyperbranched phosphorus-containing silicon fatty amine flame retardant curing agent its preparation method is roughly the same as that of Application Example 1, the difference is that each component and its mass percentage are: hyperbranched triethyl Tetraamine-based phosphorus-containing silicon fatty amine flame retardant curing agent 15%, E51 type epoxy resin 45%, polyphosphate amine 15%, pentaerythritol 10%, melamine 10%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersion Agent 0.5%, defoamer 0.5%, n-octanol 0.5%.
  • a fire retardant coating based on a hyperbranched phosphorus-containing silicon fatty amine flame retardant curing agent its preparation method is roughly the same as that of Application Example 1, the difference is that each component and its mass percentage are: hyperbranched triethyl Tetraamine-based phosphorus-containing silicon fatty amine flame retardant curing agent 20%, E51 type epoxy resin 40%, polyphosphate amine 15%, pentaerythritol 10%, melamine 10%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersion Agent 0.5%, defoamer 0.5%, n-octanol 0.5%.
  • a water-based intumescent fireproof coating the preparation method of which is roughly the same as that of Application Example 1, the difference is that the components and their mass percentages are: 10% of triethylenetetramine, 50% of E51 epoxy resin, poly Ammonium phosphate 15%, pentaerythritol 10%, melamine 10%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%.
  • a water-based intumescent fireproof coating its preparation method is roughly the same as Application Example 1, the difference is that each component and its mass percentage are: 10% of triethylenetetramine, 5% of DOPO, E51 type epoxy resin 45%, polyphosphate amine 15%, pentaerythritol 10%, melamine 10%, titanium dioxide 3%, hydroxyethyl cellulose 0.5%, dispersant 0.5%, defoamer 0.5%, n-octanol 0.5%.
  • the fire retardant coating prepared by using the hyperbranched phosphorus-containing silicon fatty amine flame retardant curing agent of the present invention can effectively take into account the excellent flame retardant effect and mechanical properties, is environmentally friendly and pollution-free, and has good durability. Capacitive, good adhesion, suitable for popularization and application.
  • the preparation method involved in the invention is simple and effective, and has wide application fields.

Abstract

一种超支化型含磷硅脂肪胺阻燃固化剂，通过对三亚乙基四胺进行超支化并接枝有机磷杂菲等基团制备得到。利用所述阻燃固化剂制备的防火涂料具有耐火时间长，耐水性好，附着力优异，干燥时间短，抗裂性好等优点，可有效兼具良好的阻燃和力学性能等；且涉及的制备工艺简单，成本较低，适合推广应用。

Description

一种超支化型含磷硅脂肪胺阻燃固化剂及其制备方法和在防火涂料中的应用 技术领域
本发明属于防火涂料技术领域，具体涉及一种超支化型含磷硅脂肪胺阻燃固化剂及其制备方法和在防火涂料中的应用。
背景技术
膨胀型防火涂料通常由粘合剂、膨胀阻燃体系和填料助剂组成，当火灾发生时，粘合剂融化，膨胀阻燃体系中的酸源分解释放酸性物质，酸性物质促使粘合剂和碳源脱水碳化，使气源分解，释放不燃性气体并生成粘流态焦炭，两者结合形成蜂窝状炭层，从而隔绝空气和热量传递，以达到优秀的防火隔热效果。
环氧树脂是目前使用最为广泛的热固性材料，以脂肪胺类为固化剂的环氧树脂，因其具有较低的玻璃化转变温度和固化温度，且反应快和绝缘性，具有较好的粘附力，常常被用作粘接剂和涂料的粘合剂。其中，三亚乙基四胺(三乙烯四胺)作为水溶性脂肪胺类固化剂，相对于二乙胺和二亚乙基三胺，具有挥发性较小、毒性较低等优点，是一种常用的水性环氧脂肪胺类固化剂，利用其所制得的涂料，固化快，温度适中，透明度好；因此常被用作膨胀型防火涂料的成膜物。
但脂肪胺类固化剂具有挥发性，毒性强等缺点，近些年随着人们环保意识的提高，使用常常受限。同时利用脂肪胺类固化剂固化后的环氧树脂，由于链间缺乏刚性基团，其力学性能不佳，限制了其使用范围，且由于玻璃化转变温度低，其热力学性能极差，常常在火灾中会促进火焰的燃烧，这对于钢材的保护是不利的。专利CN109535889A中使用三亚乙基四胺为环氧基防火涂料的固化剂，未对其进行阻燃改性，主要发挥粘合剂作用。
因此，进一步改进脂肪胺类固化剂，探索并优化其防火涂料的制备工艺，具有重要的实际应用价值和研究意义。
发明内容
本发明的主要目的在于针对现有技术存在的不足，提供一种超支化型含磷硅脂肪胺阻燃固化剂及利用其制备的防火涂料，该阻燃固化剂所得的防火涂料具有耐火时间长，耐水性好，附着力优异，干燥时间短，抗裂性好等优点，所得防火涂料可兼具良好的阻燃和力学性能等；且涉及的制备工艺简单，成本较低，适合推广应用。
为实现上述目的，本发明采用的技术方案为：
一种超支化型含磷硅脂肪胺阻燃固化剂，其制备方法包括如下步骤：
1)将三亚乙基四胺溶于有机溶剂中，然后在搅拌条件下滴加三氯乙烯基硅烷，进行室温反应；然后滴加碳酸钠的饱和溶液(中和反应的副产物盐酸)；蒸干有机溶剂，再将其溶解 于醇溶剂中，过滤，收集滤液；
2)向步骤1)中所得滤液中加入9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)，偶氮二异丁腈(AIBN)和有机溶剂，在搅拌条件下，进行保温反应，蒸干溶剂；再将所得固体产物溶解于醇溶剂中，过滤，收集滤液，蒸干溶剂；再溶解于水，过滤，收集滤液，蒸干，干燥，即得所述超支化型含磷硅脂肪胺阻燃固化剂。
上述方案中，所述有机溶剂可选用DMF等；醇溶剂可选用无水乙醇等。
上述方案中，所述三亚乙基四胺在-10～0℃温度条件加入有机溶剂中；三氯乙烯基硅烷的滴加时间为1～1.5h。
上述方案中，步骤1)中所述室温反应时间为3～5h。
上述方案中，所述三亚乙基四胺与DMF质量比为1:5～5:1。
上述方案中，所述三亚乙基四胺与三氯乙烯基硅烷的摩尔比为3:2～2:1。
上述方案中，所述三亚乙基四胺与引入的碳酸钠的摩尔比为1:2～2:1。
上述方案中，所述三亚乙基四胺与DOPO的摩尔比为3:2～2:1。
上述方案中，所述三亚乙基四胺与AIBN的摩尔比为30:2～20:1。
上述方案中，所述三亚乙基四胺与步骤1)或2)中溶解步骤引入醇溶剂的质量比为1:5～5:1。
上述方案中，所述三亚乙基四胺与步骤2)中溶解步骤引入水的质量比为1:5～5:1。
上述方案中，步骤2)中所述保温反应温度为80～120℃，时间为12～24h。
上述方案中，步骤2)中所述干燥温度为80～110℃，时间为18～24h。
本发明还提供了一种基于上述超支化型含磷硅脂肪胺阻燃固化剂的防火涂料，各组分及其所占质量百分比包括：超支化型三乙基四胺基含磷硅脂肪胺阻燃固化剂5～30％，环氧树脂35～60％，聚磷酸胺15～20％，季戊四醇10～20％，三聚氰胺10～15％，二氧化钛1～5％，羟乙基纤维素0.5～1％，分散剂0.5～1％，消泡剂0.5～1％，正辛醇0.5～1％。
上述方案中，所述环氧树脂为E44、E51、E53型双酚A型环氧树脂、双酚F型环氧树脂等。
上述方案中，所述分散剂为润湿分散剂5040等。
上述方案中，所述消泡剂为有机硅消泡剂470等。
本发明的原理为：
本发明通过对三亚乙基四胺进行超支化并接枝有机磷杂菲基团，使线性小分子三亚乙基四胺变成超支化化大分子，降低其挥发性，进而降低其毒性；同时引入磷杂菲基团于链间，提高其固化环氧树脂的玻璃化转变温度；利用其固化后的防火涂料，由于分子尺度存在硅- 磷杂菲这一特殊结构，能够同时发挥DOPO的气相淬灭效应和硅氧烷形成的网状凝聚相效应，进而大大提升所得防火涂料的阻燃性能；同时，所得超支化行型大分子固化剂，能够增加链间作用力，使利用其固化的环氧树脂力学性能得到巨大提升，同步有效提升提高防火涂料的力学性能。
与现有技术相比，本发明的有益效果为：
1)本发明所述超支化型含磷硅脂肪胺阻燃固化剂可同时发挥DOPO的气相淬灭效应和硅氧烷形成的网状凝聚相效应，协同提高固化剂自身和防火涂料的防火效果；同时可增加链间作用力，同步提高所得防火涂料的力学性能；
2)本发明所得防火涂料具有耐火时间长，耐水性好，附着力优异，干燥时间短，抗裂性好等优点，可兼具良好的阻燃和力学性能等，适合推广应用。
附图说明
图1为实施例1所得一种超支化型含磷硅脂肪胺阻燃固化剂的结构示意图；
图2为实施例1所得超支化型含磷硅脂肪胺阻燃固化剂的核磁共振氢谱图；
图3为实施例1所得超支化型含磷硅脂肪胺阻燃固化剂的核磁共振磷谱图；
图4为实施例1所得超支化型含磷硅脂肪胺阻燃固化剂制备的E51环氧树脂样条UL-94测试数码照片；
图5为应用例1与对比例所得膨胀型防火涂料的大板燃烧法背温曲线图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
以下实施例中，采用的分散剂为润湿分散剂5040；消泡剂为有机硅消泡剂470。
实施例1
一种超支化型含磷硅脂肪胺阻燃固化剂，其化学结构示意图见图1(图中)；具体制备方法包括如下步骤：
1)在0℃，将25g三亚乙基四胺溶于125g DMF中，保持搅拌，并在1h内向其中滴加16.76g三氯乙烯基硅烷(三亚乙基四胺与三氯乙烯基硅烷的摩尔比为3.3:2)，滴加完后室温反应5h，反应完后向其中滴加碳酸钠的饱和溶液(三亚乙基四胺与引入的碳酸钠摩尔比为1:2)；蒸出溶剂DMF，再将其溶解于无水乙醇，过滤，取滤液；
2)向步骤1)中所得滤液中加入24.6g DOPO(9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物，三亚乙基四胺与DOPO的摩尔比为3:2)，1.4g AIBN(偶氮二异丁腈，三亚乙基四胺与AIBN 摩尔比为20:1)和125g DMF，保持搅拌，80～120℃反应12h，蒸出溶剂DMF，溶解于125g无水乙醇，过滤，取滤液，蒸出无水乙醇；再溶解于125g水，过滤，取滤液，蒸出水；80℃干燥18～24h，即得到一种超支化型含磷硅脂肪胺阻燃固化剂。
图2和图3分别为本实施例所得超支化型含磷硅脂肪胺阻燃固化剂的核磁共振氢谱图和核磁共振磷谱图，结果表明：核磁共振氢谱中出现了DOPO和三亚乙基四胺的所对应的峰，核磁共振磷谱中只有一个磷单峰。
图4为本实施例所得超支化型含磷硅脂肪胺阻燃固化剂制备的E51环氧树脂样条UL-94测试数码照片。
应用例1
一种基于超支化型含磷硅脂肪胺阻燃固化剂的防火涂料，各组分及其所占质量百分比为：实施例1所得超支化型三乙基四胺基含磷硅脂肪胺阻燃固化剂10％，E51型环氧树脂50％，聚磷酸胺15％，季戊四醇10％，三聚氰胺10％，二氧化钛3％，羟乙基纤维素0.5％，分散剂0.5％，消泡剂0.5％，正辛醇0.5％，其制备方法包括以下步骤：
1)按上述配比要求称取原料；
2)将称取的聚磷酸铵、季戊四醇、三聚氰胺、二氧化钛、研磨至无颗粒粉状，然后加水充分研磨混合均匀；再加入消泡剂和分散剂，继续充分研磨；
3)最后加入超支化型三乙基四胺基含磷硅脂肪胺阻燃固化剂和E51型环氧树脂以及正辛醇充分研磨混合均匀，即得所述防火涂料。
应用例2
一种基于超支化型含磷硅脂肪胺阻燃固化剂的防火涂料，其制备方法与应用例1大致相同，不同之处在于各组分及其所占质量百分比为：超支化型三乙基四胺基含磷硅脂肪胺阻燃固化剂15％，E51型环氧树脂45％，聚磷酸胺15％，季戊四醇10％，三聚氰胺10％，二氧化钛3％，羟乙基纤维素0.5％，分散剂0.5％，消泡剂0.5％，正辛醇0.5％。
应用例3
一种基于超支化型含磷硅脂肪胺阻燃固化剂的防火涂料，其制备方法与应用例1大致相同，不同之处在于各组分及其所占质量百分比为：超支化型三乙基四胺基含磷硅脂肪胺阻燃固化剂20％，E51型环氧树脂40％，聚磷酸胺15％，季戊四醇10％，三聚氰胺10％，二氧化钛3％，羟乙基纤维素0.5％，分散剂0.5％，消泡剂0.5％，正辛醇0.5％。
对比例1
一种水性膨胀型防火涂料，其制备方法与应用例1大致相同，不同之处在于各组分及其所占质量百分比为：三乙基四胺10％，E51型环氧树脂50％，聚磷酸胺15％，季戊四醇10％， 三聚氰胺10％，二氧化钛3％，羟乙基纤维素0.5％，分散剂0.5％，消泡剂0.5％，正辛醇0.5％。
将实施例1～3及对比例1所得膨胀型防火涂料分别进行耐火性能测试，结果见表1。
对比例2
一种水性膨胀型防火涂料，其制备方法与应用例1大致相同，不同之处在于各组分及其所占质量百分比为：三乙基四胺10％，DOPO 5％，E51型环氧树脂45％，聚磷酸胺15％，季戊四醇10％，三聚氰胺10％，二氧化钛3％，羟乙基纤维素0.5％，分散剂0.5％，消泡剂0.5％，正辛醇0.5％。
将应用例1～3和对比例1～2所得膨胀型防火涂料分别进行阻燃性能、力学性能和耐久性能等测试，结果见表1。
表1实施例1～3及对比例1所得膨胀型防火涂料的性能测试结果
Figure PCTCN2021122191-appb-000001
上述结果表明：利用本发明所述超支化型含磷硅脂肪胺阻燃固化剂制备的防火涂料可有效兼顾优异的阻燃效果和力学性能，环保无污染，耐久性好，与基材的相容性，附着性良好，适合推广应用。本发明涉及的制备方法简单有效，适用领域广泛。
显然，上述实施例仅仅是为清楚地说明所作的实例，而并非对实施方式的限制。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。 这里无需也无法对所有的实施方式予以穷举。而因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围之内。

Claims (10)

  1. 一种超支化型含磷硅脂肪胺阻燃固化剂的制备方法，其特征在于，包括如下步骤：
    1)将三亚乙基四胺溶于有机溶剂中，然后在搅拌条件下滴加三氯乙烯基硅烷，进行室温反应；然后滴加碳酸钠的饱和溶液；蒸干有机溶剂，再将其溶解于醇溶剂中，过滤，收集滤液；
    2)向步骤1)中所得滤液中加入9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物，偶氮二异丁腈和有机溶剂，在搅拌条件下，进行保温反应，蒸干溶剂；再将所得固体产物溶解于醇溶剂中，过滤，收集滤液，蒸干溶剂；再溶解于水，过滤，收集滤液，蒸干，干燥，即得所述超支化型含磷硅脂肪胺阻燃固化剂。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤1)中所述室温反应时间为3～5h。
  3. 根据权利要求1所述的制备方法，其特征在于，所述三亚乙基四胺与三氯乙烯基硅烷的摩尔比为3:2～2:1。
  4. 根据权利要求1所述的制备方法，其特征在于，所述三亚乙基四胺与引入的碳酸钠的摩尔比为1:2～2:1。
  5. 根据权利要求1所述的制备方法，其特征在于，所述三亚乙基四胺与DOPO的摩尔比为3:2～2:1。
  6. 根据权利要求1所述的制备方法，其特征在于，所述三亚乙基四胺与AIBN的摩尔比为30:2～20:1。
  7. 根据权利要求1所述的制备方法，其特征在于，所述三亚乙基四胺与步骤1)或2)中溶解步骤引入醇溶剂的质量比为1:5～5:1；所述三亚乙基四胺与步骤2)中溶解步骤引入水的质量比为1:5～5:1。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤2)中所述保温反应温度为80～120℃，时间为12～24h。
  9. 权利要求1～8任一项所述制备方法制得的超支化型含磷硅脂肪胺阻燃固化剂。
  10. 权利要求9所述超支化型含磷硅脂肪胺阻燃固化剂在防火涂料中的应用，其特征在于，各组分及其所占质量百分比包括：超支化型含磷硅脂肪胺阻燃固化剂5～30％，环氧树脂35～60％，聚磷酸胺15～20％，季戊四醇10～20％，三聚氰胺10～15％，二氧化钛1～5％，羟乙基纤维素0.5～1％，分散剂0.5～1％，消泡剂0.5～1％，正辛醇0.5～1％。
PCT/CN2021/122191 2021-09-29 2021-09-30 一种超支化型含磷硅脂肪胺阻燃固化剂及其制备方法和在防火涂料中的应用 WO2023050315A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111150310.8 2021-09-29
CN202111150310.8A CN113698610B (zh) 2021-09-29 2021-09-29 一种超支化型含磷硅脂肪胺阻燃固化剂及其制备方法和在防火涂料中的应用

Publications (1)

Publication Number Publication Date
WO2023050315A1 true WO2023050315A1 (zh) 2023-04-06

Family

ID=78662264

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/122191 WO2023050315A1 (zh) 2021-09-29 2021-09-30 一种超支化型含磷硅脂肪胺阻燃固化剂及其制备方法和在防火涂料中的应用

Country Status (2)

Country Link
CN (1) CN113698610B (zh)
WO (1) WO2023050315A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116675924A (zh) * 2023-06-25 2023-09-01 广东安拓普聚合物科技有限公司 耐寒阻燃型复合弹性体及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114874416B (zh) * 2022-04-28 2023-11-21 浙大宁波理工学院 一种磷硅改性脂肪胺类固化剂及其制备方法、应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4742088A (en) * 1986-09-12 1988-05-03 Kolon Industries, Inc. Phosphorus-containing nitrogen compounds as flame retardants and synthetic resins containing them
JP2002201364A (ja) * 2001-01-05 2002-07-19 Fujitsu Ltd 難燃性樹脂組成物およびこれを用いたビルドアップ基板
CN101792537A (zh) * 2010-03-17 2010-08-04 北京理工大学 一种含dopo基团的硅烷偶联剂及其制备方法
CN106554483A (zh) * 2016-11-23 2017-04-05 厦门大学 一种磷杂菲结构反应型阻燃剂及其应用
CN113652001A (zh) * 2021-07-23 2021-11-16 宁波诺丁汉大学 一种含磷的溶剂型阻燃剂及其制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102066451B (zh) * 2008-04-11 2014-08-06 巴斯夫欧洲公司 作为环氧树脂的固化剂的包含末端氨基的超支化聚合物和低聚物
KR20130037667A (ko) * 2010-03-02 2013-04-16 바스프 에스이 에폭시 수지를 위한 경화제로서의 선형 트리에틸렌테트라민의 용도
WO2015054698A1 (en) * 2013-10-11 2015-04-16 Connora Technologies, Inc. Sterically hindered aliphatic polyamine cross-linking agents, compositions containing and uses thereof
CN104558528A (zh) * 2013-12-30 2015-04-29 惠州学院 一种含磷多胺自乳化环氧树脂固化剂、其制备方法及用途
CN107057517B (zh) * 2016-12-22 2019-11-05 广东一通科技股份有限公司 一种倍半硅氧烷交联的硅氮磷协同阻燃水性环氧树脂及其制备方法
CN111315839B (zh) * 2017-08-15 2022-09-20 Ddp特种电子材料美国公司 室温可固化的双组分增韧的环氧粘合剂
CN107964089A (zh) * 2017-11-23 2018-04-27 长春工业大学 一种固化剂、基于dopo可低温固化的无卤阻燃环氧树脂及其制备方法
CN112961359A (zh) * 2021-02-24 2021-06-15 北华大学 NH2-POSS-bisDOPO阻燃剂及其制备方法与应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4742088A (en) * 1986-09-12 1988-05-03 Kolon Industries, Inc. Phosphorus-containing nitrogen compounds as flame retardants and synthetic resins containing them
JP2002201364A (ja) * 2001-01-05 2002-07-19 Fujitsu Ltd 難燃性樹脂組成物およびこれを用いたビルドアップ基板
CN101792537A (zh) * 2010-03-17 2010-08-04 北京理工大学 一种含dopo基团的硅烷偶联剂及其制备方法
CN106554483A (zh) * 2016-11-23 2017-04-05 厦门大学 一种磷杂菲结构反应型阻燃剂及其应用
CN113652001A (zh) * 2021-07-23 2021-11-16 宁波诺丁汉大学 一种含磷的溶剂型阻燃剂及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116675924A (zh) * 2023-06-25 2023-09-01 广东安拓普聚合物科技有限公司 耐寒阻燃型复合弹性体及其制备方法
CN116675924B (zh) * 2023-06-25 2024-03-19 广东安拓普聚合物科技股份有限公司 耐寒阻燃型复合弹性体及其制备方法

Also Published As

Publication number Publication date
CN113698610A (zh) 2021-11-26
CN113698610B (zh) 2022-05-10

Similar Documents

Publication Publication Date Title
WO2023050315A1 (zh) 一种超支化型含磷硅脂肪胺阻燃固化剂及其制备方法和在防火涂料中的应用
CN112961528B (zh) 一种环保型防火涂料及其制备方法
CN102585347B (zh) 一种无卤膨胀型阻燃聚丙烯混合物及其制备方法
WO2015062257A1 (zh) 磷-氮系膨胀型阻燃剂、其合成方法及其应用
CN108440907A (zh) 一种高介电性能复合材料的制备方法
CN103865101A (zh) 一种高效磷氮系阻燃剂及制备方法
CN107722293B (zh) 一种含氮超支化阻燃剂及其制备方法和应用
CN111961075B (zh) 一种硅-氮阻燃前驱体及其制备方法，一种硅-氮杂化阻燃溶胶及其制备方法
CN112210191B (zh) 一种磷/氮/硅协效阻燃改性环氧树脂的方法
CN108948946B (zh) 一种复合防火涂料及其制备方法
CN103059675A (zh) 保温隔热的室内超薄型钢结构防火涂料及其制备方法
CN109721710A (zh) 一种新型化合物dopo-ma及其合成方法
CN114350230B (zh) 一种阻燃高硬度环氧树脂地坪漆的制备方法
CN102344510A (zh) 一种三源一体膨胀型阻燃剂的制备方法
CN106349503B (zh) 季戊四醇衍生物的膨胀型阻燃剂及其制备方法
WO2024021366A1 (zh) 一种防火涂层材料
CN107501526B (zh) 一种dopo型环氧树脂固化剂及其制备方法
CN113372747B (zh) 一种本征阻燃透明有机硅防火涂料及制备方法
CN107955569B (zh) 一种飞机阻燃剂及其阻燃胶粘剂
CN113174057B (zh) 一种氮磷协效Al基MOFs阻燃剂及其制备方法与应用
WO2023060571A1 (zh) 一种生物基大分子修饰纳米磷酸锆阻燃剂及利用其制备的防火涂料
CN113061394A (zh) 一种阻燃天然生漆膜及其制备方法
CN113025248A (zh) 一种热固环氧胶及其制备方法
CN105670257A (zh) 一种阻燃绝缘复合材料及其制备方法
CN105585931B (zh) 一种含有聚磷酸铵酯环保透明防火涂料的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21958887

Country of ref document: EP

Kind code of ref document: A1