CN103012848A - Halogen-free intumescent flame retardant and preparation method thereof - Google Patents

Halogen-free intumescent flame retardant and preparation method thereof Download PDF

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CN103012848A
CN103012848A CN 201210488809 CN201210488809A CN103012848A CN 103012848 A CN103012848 A CN 103012848A CN 201210488809 CN201210488809 CN 201210488809 CN 201210488809 A CN201210488809 A CN 201210488809A CN 103012848 A CN103012848 A CN 103012848A
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flame retardant
halogen
intumescent
meth
free
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CN 201210488809
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Chinese (zh)
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徐元清
赵俊伟
房晓敏
丁涛
郝喜才
任艳蓉
郭红丽
卞龙骧
张延兵
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河南大学
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Abstract

The invention discloses a halogen-free intumescent flame retardant and a preparation method thereof. The structural formula of the flame retardant is shown in the specification, wherein R is H or methyl. The flame retardant contains diphenyl phosphate and a coking structure, namely contains 'acid source' and 'carbon source' of the intumescent flame retardant simultaneously, and further has the plasticizing capability. The preparation process of the halogen-free intumescent flame retardant disclosed by the invention is simple, safe, easy to operate and free of pollution to environment; and the yield is more than 70%. The product is white to light gray powder; and the halogen-free intumescent flame retardant has the advantages of high flame retardant efficiency, low toxicity, no pollution and the like.

Description

一种无卤膨胀型阻燃剂及其制备方法 Halogen-free flame retardant and intumescent preparation

技术领域 FIELD

[0001] 本发明涉及一种无卤膨胀型阻燃剂,同时还涉及该阻燃剂的制备方法,属于阻燃剂技术领域。 [0001] The present invention relates to a non-halogen intumescent flame retardant, and also relates to a method for preparing the flame retardant, flame retardants belonging to the technical field.

背景技术 Background technique

[0002] 阻燃剂又称难燃剂,耐火剂或防火剂,是一种能够使高分子材料不易着火燃烧或能够减慢燃烧速度的助剂。 [0002] flame retardant, also known as flame retardants, flameproofing agents or flameproofing agents, a polymer material capable of easy ignition combustion or burning aids can slow speed.

[0003] 有机阻燃剂中用量最大的是卤系阻燃剂,具有添加量少、阻燃效率高、价格相对低廉等优势,但该类阻燃剂在燃烧时产生大量有毒和腐蚀性的气体,引发了人们对其环保问题的担忧。 [0003] The amount of organic flame retardant is a halogen flame retardant biggest, has added less, high flame retardant efficiency, relatively inexpensive, and other advantages, but such a large amount of toxic and corrosive flame retardant during combustion gas, sparked concerns about its environmental problems. 近年来,世界各国正不断限制含卤阻燃剂的使用。 In recent years, the world is constantly restrict the use of halogen-containing flame retardants.

[0004] 磷系阻燃剂是无卤阻燃剂中的佼佼者,其中膨胀型阻燃剂则更是阻燃剂研究和应用的热点。 [0004] The phosphorus-based flame retardant is a halogen flame retardant leader, wherein the IFR is even more flame retardant hot research and application. 膨胀型阻燃剂以磷、氮为主要活性组分,不含卤素,也不采用氧化锑为协效剂。 Intumescent flame retardant phosphorus and nitrogen as the main active component, halogen-free, nor is the use of antimony oxide synergist. 膨胀型阻燃剂是由“三源”构成的:含有磷的“酸源”,含有结炭结构的“炭源”和含N的“气源”等。 Intumescent flame retardant is a "three sources" consisting of: phosphorus-containing "acid source", containing coke structure "carbon source" and the N-containing "gas source" and the like. 用膨胀型阻燃剂阻燃的高聚物受热时,表面能生成一层均匀的炭质泡沫层,此层隔热、隔氧、抑烟,并能防止产生熔滴,故具有良好的阻燃性,且符合当今阻燃剂少烟、低毒的发展趋势。 When heated with intumescent flame retardant polymer, the surface can generate a uniform layer of carbonaceous foam layer, this insulation layer, oxygen barrier, smoke suppression, and to prevent droplet, it has good resistance flammable, flame retardants and smoke less with the current development trend of low toxicity.

[0005] 传统的膨胀型阻燃剂由聚磷酸铵、季戊四醇和三聚氰胺组成,其最大缺点是添加量大、易溶于水,在应用时阻燃效果会不断降低。 [0005] by the conventional intumescent flame retardant ammonium polyphosphate, melamine and pentaerythritol, whose biggest drawback is added in an amount, soluble in water, flame-retardant effect will continue to decrease upon the application. 将“三源”集于同一个分子中的单分子一直是阻燃剂研究的热点。 The "three sources" set in the same molecule a single molecule has been the focus of study of flame retardants. 但目前所报道的大多阻燃效率不高,添加量较大,通常在质量百分数超过30%以上时才能达到较好的阻燃效果,因此对材料的力学性能影响较大。 But the reported mostly flame retardant efficiency is not high, it is greater, usually in order to achieve better flame-retardant effect in the mass percentage of more than 30%, so a greater impact on the mechanical properties of the material.

发明内容 SUMMARY

[0006] 本发明的目的是提供一种阻燃效率高,添加量少的无卤膨胀型阻燃剂。 [0006] The object of the present invention is to provide a high flame retardant efficiency, adding a small amount of non-halogen intumescent flame retardant.

[0007] 为了实现以上目的,本发明的技术方案是提供一种无卤膨胀型阻燃剂,其结构通式为: [0007] To achieve the above object, the technical solution of the present invention is to provide a non-halogen intumescent flame retardant, which is the structural formula:

[0008] [0008]

Figure CN103012848AD00041

[0009] 其中,R为H或甲基。 [0009] wherein, R is H or methyl. 优选R为H。 Preferably R is H.

[0010] 本发明所采用的两种原料分别为氯代磷酸二(甲基)苯酯(以下简称磷酰氯)和1-氧代-4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2. 2. 2]辛烷(以下简称ΡΕΡΑ)。 [0010] The two materials used in the present invention are chloro di (meth) phenyl ester (hereinafter referred to as phosphorus oxychloride) and 1-oxo-4-hydroxymethyl-1-phospha-2,6, three 7- oxabicyclo [2.2.2] octane (hereinafter referred ΡΕΡΑ). 其中磷酰氯的合成参照文献(叠氮磷酸二苯酯的合成工艺改进.化学试剂,1992,14(6) :345);ΡΕΡΑ的合成参照文献(Fire retardancy of thermoplastic materials by intumescence.1ndEng Chem Prod Res Dev,1984,23 (2) : 233 - 238)。 Synthesis of reference literature which phosphorus oxychloride (Synthesis of diphenylphosphoryl azide improved chemical reagents, 1992,14 (6):. 345); ΡΕΡΑ synthesized according to the literature (Fire retardancy of thermoplastic materials by intumescence.1ndEng Chem Prod Res dev, 1984,23 (2): 233 - 238). 两种原料的结构式如下: Two starting materials of the formula as follows:

[0011] [0011]

Figure CN103012848AD00051

[0012] 本发明的目的还在于提供一种无卤膨胀型阻燃剂的制备方法。 [0012] The object of the present invention is to provide a method for preparing a non-halogen intumescent flame retardant.

[0013] 本发明的技术方案还在于提供一种无卤膨胀型阻燃剂的制备方法,步骤如下:将氯代磷酸二(甲基)苯酯、1-氧代-4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2. 2. 2]辛烷、 溶剂和催化剂依次加入反应瓶中,0-30°C下滴加缚酸剂lh,30-80°C反应l_30h ;之后纯化分离得到无卤膨胀型阻燃剂。 [0013] aspect of the present invention is to provide a method for preparing a non-halogen intumescent flame retardant, as follows: the chloro di (meth) phenyl ester, 4-hydroxymethyl-1-oxo - 1- phospha-2,6,7-trimethyl-oxabicyclo [2.2.2] octane, solvent and catalyst were added the reaction flask, dropwise lh acid binding agent at 0-30 ° C, 30-80 ° C reaction l_30h; isolated after purification to obtain a halogen intumescent flame retardant.

[0014] 所述的氯代磷酸二(甲基)苯酯和1-氧代-4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2. 2. 2]辛烷摩尔比为1:0. 5-1. 5,优选1:0. 8-1. 2。 [0014] The chlorinated phosphoric acid di (meth) acrylate, and phenyl 1-oxo-4-hydroxymethyl-1-phospha-2,6,7-trimethyl-oxabicyclo [2.2.2] octane molar ratio of 1: 05-15, preferably 1: 08-12.

[0015] 所述的缚酸剂为N,N-二甲基苯胺、吡啶或三乙胺,缚酸剂与磷酰氯的物质的量比为O. 5-3 :1,优选O. 8-1. 2 :1。 Acid-binding agent [0015] is the N, N- dimethylaniline, pyridine or triethylamine, molar ratio of the acid-binding agent is phosphorus oxychloride O. 5-3: 1, preferably O. 8- 1.2: 1.

[0016] 所述的溶剂为氯仿、二氯甲烷、乙腈、四氢呋喃或乙酸乙酯,用量为每摩尔磷酰氯加入溶剂500-3000mL,优选1000_2000mL。 [0016] The solvent, chloroform, dichloromethane, acetonitrile, tetrahydrofuran or ethyl acetate, an amount of solvent per mole of phosphorus oxychloride was added 500-3000mL, preferably 1000_2000mL.

[0017] 所述的催化剂为无水三氯化铝、无水氯化锌、无水氯化镁、无水氯化亚铁或4-(N,N-二甲氨基)吡啶,催化剂的用量为每摩尔磷酰氯加入O. l_20g的催化剂,优选 [0017] The catalyst is anhydrous aluminum chloride, anhydrous zinc chloride, anhydrous magnesium chloride, anhydrous ferric chloride or 4- (N, N- dimethylamino) pyridine, amount of catalyst per the catalyst was added phosphorus oxychloride O. l_20g molar, preferably

2-10g。 2-10g.

[0018] 所述的分离纯化为反应完成后,反应液进行减压过滤,滤液蒸馏回收溶剂,固体粗产品经充分水洗后,在真空条件下于40°C干燥至恒重。 Purification of the [0018] After completion of the reaction, the reaction liquid was filtered under reduced pressure, and the filtrate was distilled to recover the solvent, the crude solid product was sufficiently washed with water, and dried under vacuum at 40 ° C to a constant weight.

[0019] 本发明的无卤膨胀型阻燃剂不含有卤素,属于环境友好型阻燃剂,其分子结构中同时含有磷酸酯和结炭结构,即同时含有膨胀型阻燃剂的“酸源”和“碳源”,在未添加“气源”的情况下也可获得理想的阻燃效果。 [0019] The halogen-free intumescent flame retardant of the present invention do not contain halogens, are environment-friendly flame retardant, its molecular structure containing both phosphate and coke structure, i.e. containing both "acid source Intumescent Flame Retardant "and" carbon source ", is not added in the" case of air, "the desired flame retarding effect can be obtained. 此外,磷酸苯酯还具有增塑功能。 In addition, further phenyl phosphate having a plasticizing function.

[0020] 本发明制备方法过程简单、安全、易操作,同时对环境无污染,产率可达70%以上。 [0020] The preparation process of the present invention the method is simple, safe, easy to operate, while the environmental pollution, the yield up to 70%. 反应中生成的氯化氢气体经缚酸剂吸收后对设备无腐蚀;得到的产品为白色到浅灰色粉末状固体。 The hydrogen chloride gas formed in the reaction after acid-binding agent absorbs no corrosion of the device; the obtained product is a white to pale gray powder. 产品阻燃效率高;不含有卤素,具有低毒、无污染等特点。 Products of high flame retardant efficiency; no halogen, having low toxicity, pollution-free characteristics.

附图说明 BRIEF DESCRIPTION

[0021] 图1为实施例1、2和3中无卤膨胀型阻燃剂的红外谱图; [0021] FIG. 1 is a halogen-free Examples 1, 2 and 3, the infrared spectrum of Intumescent Flame embodiment;

[0022] 图2为实施例1、2和3中无卤膨胀型阻燃剂的核磁谱图; [0022] FIG. 2 of Example 1, 2 and 3 in a non-halogen intumescent flame retardant NMR spectrum;

[0023] 图3为实施例1、2和3中无卤膨胀型阻燃剂的质谱图; [0023] FIG. 3 of Example 1, 2 and 3 in a non-halogen intumescent flame retardant spectrum;

[0024] 图4为实施例1、2和3中无卤膨胀型阻燃剂的热分析图谱。 [0024] FIG. 4 is a thermal analysis of Examples 1, 2 and 3 in the spectrum of the non-halogen intumescent flame retardant.

具体实施方式 detailed description

[0025] 实施例1 [0025] Example 1

[0026] 本实施例中无卤膨胀型阻燃剂的结构式为: [0026] The structural formula of the present embodiment is a non-halogen intumescent flame retardant:

[0027] [0027]

Figure CN103012848AD00061

[0028] 本实施例无卤膨胀型阻燃剂的制备方法,步骤如下:将O. 15mol氯代磷酸二苯酯、O. 075molPEPA、75mL 二氯甲烷,1. 5g无水氯化镁依次加入三口烧瓶中,30°C滴加O. 15mol三乙胺lh。 [0028] Preparation Example halogen-free intumescent flame retardant of the present embodiment, the following steps: The O. 15mol diphenyl chlorophosphate, O 075molPEPA, 75mL methylene chloride, 1 5g of anhydrous magnesium chloride, three-necked flask were added medium, 30 ° C was added dropwise triethylamine O. 15mol lh. 滴加完成后,升温至55°C,并在氮气氛下搅拌反应20h。 After the addition was complete, warmed to 55 ° C, and the reaction was stirred under a nitrogen atmosphere for 20h. 减压过滤,滤液蒸馏回收溶剂,固体粗产品用5 X 300mL水洗涤,在40°C下烘干,得到产品48. 3g,收率77. 9%。 Was filtered under reduced pressure, the filtrate was distilled off to recover the solvent, the crude solid product was washed 5 X 300mL of water, dried at 40 ° C, to give the product 48. 3g, yield 77.9%. 产品红夕卜、核磁、质谱和热重图谱分别见图1、图2、图3和图4。 Product Bu Xi red, NMR, mass spectroscopy, and TGA profiles are shown in Figure 1, 2, 3 and 4.

[0029] 1H 核磁结果分析:(DMS0-d6) δ :4. 23-4. 25 (d, J=4. OHz, 2H, CH2),4. 62-4. 64 (d, J=4. OHz, 6H, 3CH2),7. 26-7. 32 (m, 6H, Ar-H) 7. 44-7. 48 (m, 4H, Ar-H)。 [0029] 1H NMR analysis results: (DMS0-d6) δ:.... 4 23-4 25 (. D, J = 4 OHz, 2H, CH2), 4 62-4 64 (d, J = 4. OHz, 6H, 3CH2), 7. 26-7. 32 (m, 6H, Ar-H) 7. 44-7. 48 (m, 4H, Ar-H).

[0030]红外结果分析:(KBr, cnT1) : 3061 (Ar-H),2904 (-CH2-),1482,1585 (苯环C=C),1306 (P=O),1183,964(PO-Ph)。 [0030] Infrared analysis results: (KBr, cnT1): 3061 (Ar-H), 2904 (-CH2 -), 1482,1585 (benzene ring C = C), 1306 (P = O), 1183,964 (PO -Ph).

[0031]质谱结果分析(ESI) =C17H18O8P2 计算值(M+)413. 1,实测值413.1。 [0031] Mass analysis results (ESI) = C17H18O8P2 calcd (M +) 413. 1, Found 413.1.

[0032] 热重数据见表I。 [0032] TGA data in Table I.

[0033] 表10MDP的热重数据 [0033] Thermogravimetric data table 10MDP

[0034] [0034]

Figure CN103012848AD00062

[0035] 注:a600°C时的残炭量。 [0035] Note: The amount of residual carbon at a600 ° C.

[0036] 实施例2 [0036] Example 2

[0037] 本实施例中无卤膨胀型阻燃剂的结构式同实施例1。 [0037] The structural formula of the present embodiment, non-halogen intumescent flame retardant in Example 1.

[0038] 本实施例无卤膨胀型阻燃剂的制备方法,步骤如下:将O. 15mol氯代磷酸二苯酯、O. 15molPEPA、150mL四氢呋喃,2. 25g 4_(N,N_ 二甲氨基)吡啶依次加入三口烧瓶中,(TC滴加O. 3mol三乙胺lh。滴加完成后,升温至80°C,并在氮气氛下搅拌反应lh。减压过滤,滤液蒸馏回收溶剂,固体粗产品用5X300mL水洗涤,在40°C下烘干,得到产品51. 5g,收率83. 1%。产品红外、核磁、质谱和热重图谱及结果分析同实施例1。 [0038] Preparation Example halogen-free intumescent flame retardant of the present embodiment, the following steps: The O. 15mol diphenyl chlorophosphate, O 15molPEPA, 150mL of tetrahydrofuran, 2 25g 4_ (N, N_ dimethylamino) three-neck flask were added pyridine, (the TC of triethylamine was added dropwise O. 3mol lh. after the addition was complete, warmed to 80 ° C, and the reaction stirred for lh under a nitrogen atmosphere was filtered under reduced pressure, the filtrate was distilled off to recover the solvent, the crude solid product IR, NMR, and mass spectra and the results of thermogravimetric analysis in Example 1 product was washed with 5X300mL water, dried at 40 ° C, to give the product 51. 5g, 83. 1% yield.

[0039] 实施例3 [0039] Example 3

[0040] 本实施例中无卤膨胀型阻燃剂的结构式同实施例1。 [0040] The structural formula of the present embodiment, non-halogen intumescent flame retardant in Example 1.

[0041] 本实施例无卤膨胀型阻燃剂的制备方法,步骤如下:将O. 15mol氯代磷酸二苯酯、O. 225molPEPA、450mL乙腈,O. 015g无水氯化锌依次加入三口烧瓶中,15°C滴加O. 075mol吡啶lh。 Example Preparation of non-halogen intumescent flame retardant [0041] the present embodiment, the following steps: The O. 15mol diphenyl chlorophosphate, O 225molPEPA, 450mL acetonitrile, O 015g of anhydrous zinc chloride were added three-necked flask. medium, 15 ° C was added dropwise pyridine O. 075mol lh. 滴加完成后,升温至30°C,并在氮气氛下搅拌反应30h。 After the addition was complete, warmed to 30 ° C, and the reaction was stirred under a nitrogen atmosphere for 30h. 减压过滤,滤液蒸馏回收溶齐U,固体粗产品用5父3001^水洗涤,在401:下烘干,得到产品48. lg,收率77. 6%。 Was filtered under reduced pressure, and the filtrate solvent recovered by distillation together U, the crude solid product was washed with 5 water parent ^ 3001, 401: the drying, to give the product 48. lg, 77. 6% yield. 产品红夕卜、核磁、质谱和热重图谱及结果分析同实施例1。 Product Bu Xi red, NMR, mass spectrum and thermogravimetric analysis results of Example 1 and the same embodiment.

[0042] 实施例4 [0042] Example 4

[0043] 本实施例中无卤膨胀型阻燃剂的结构式为: [0043] The structural formula of the non-halogen intumescent flame retardant embodiments of the present embodiment is:

[0044] [0044]

Figure CN103012848AD00071

[0045] 将O. 15mol氯代磷酸二甲基苯酯、O. 18molPEPA、300mL氯仿,3g无水三氯化铝依次加入三口烧瓶中,25°C滴加O. 45molN,N-二甲基苯胺lh。 [0045] The chlorophosphate O. 15mol dimethylphenyl, O. 18molPEPA, 300mL chloroform, 3g of anhydrous aluminum chloride were added three-neck flask, 25 ° C was added dropwise O. 45molN, N- dimethyl aniline lh. 滴加完成后,升温至65°C,并在氮气氛下搅拌反应15h。 After the addition was complete, warmed to 65 ° C, and the reaction was stirred under a nitrogen atmosphere for 15h. 减压过滤,滤液蒸馏回收溶剂,固体粗产品用5X300mL水洗涤,在40°C下烘干,得到产品52. lg,收率78. 9%。 Was filtered under reduced pressure, the filtrate was distilled off to recover the solvent, the crude solid product was washed with 5X300mL water, dried at 40 ° C, to give the product 52. lg, yield 78.9%. [0046] 应用实施例 [0046] Application Example

[0047] 将环氧树脂200g、邻苯二甲酸二丁酯30g加入到500mL烧杯中,于80°C水浴中使环氧树脂软化,然后加入不同比例的实施例1中阻燃剂,充分搅拌后加入三乙烯四胺26g,注入127mmX 12. 7mmX3. 2mm的聚四氟模具中;室温固化5小时后,再升温至85°C固化2h,得到阻燃样条。 [0047] The epoxy resin 200g, 30g of dibutyl phthalate was added to the 500mL beaker, softening an epoxy resin at 80 ° C-water bath, followed by addition of different ratios of the flame retardant in Example 1, thoroughly stirred after addition of 26g triethylenetetramine, polytetrafluoroethylene injection mold in 127mmX 12. 7mmX3 2mm; after 5 hours for curing at room temperature, warmed to 85 ° C and then cured 2h, to give flame spline. 样条的极限氧指数按照GB/T2406. 2-2009测试,垂直燃烧等级按照GB/T2408-2008测试,结果见下表2。 Spline limiting oxygen index in accordance with GB / T2406. 2-2009 test, in accordance with the vertical combustion level GB / T2408-2008 test, the results in Table 2 below.

[0048] 表2阻燃剂阻燃性能试验结果 [0048] Table 2 flame retardant performance test results

[0049] [0049]

Figure CN103012848AD00072

Claims (10)

  1. 1. 一种无卤膨胀型阻燃剂,其特征在于,结构式如下所示: A non-halogen intumescent flame retardant, wherein the formula as follows:
    Figure CN103012848AC00021
    其中,R为H或甲基。 Wherein, R is H or methyl.
  2. 2.根据权利要求1所述的一种无卤膨胀型阻燃剂,其特征在于,所述的R为H。 2. Halogen-free intumescent flame retardant according to claim 1, wherein said R is H.
  3. 3. —种如权利要求1所述的无卤膨胀型阻燃剂的制备方法,其特征在于,步骤如下:将氯代磷酸二(甲基)苯酯、1-氧代-4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2. 2. 2]辛烷、溶剂和催化剂依次加入反应瓶中,0_30°C下缓慢滴加缚酸剂lh,30-80°C反应l_30h ;之后纯化分离得到无卤膨胀型阻燃剂;氯代磷酸二(甲基)苯酯和1-氧代-4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2. 2. 2]辛烷摩尔比为1:0. 5-1.5 ;所述的氯代磷酸二(甲基)苯酯结构式如下所示, 3. - Preparation of the species, such as a non-halogen intumescent flame retardant as claimed in claim wherein, the steps of: chloro di (meth) phenyl ester, 1-oxo-4-hydroxymethyl 2,6,7-trimethyl-1-phospha-oxabicyclo [2.2.2] octane, solvent and catalyst were added the reaction flask was slowly added dropwise lh acid binding agent at 0_30 ° C, 30- 80 ° C the reaction l_30h; isolated after purification of a halogen-free intumescent flame retardant; chloro di (meth) acrylate, and phenyl 1-oxo-4-hydroxymethyl-1-phospha--2,6,7 - three-oxabicyclo [2.2.2] octane molar ratio of 1: 0 5-1.5; the chloro di (meth) phenyl ester of the formula shown below.
    Figure CN103012848AC00022
    式中,R为H或甲基; 所述的1-氧代-4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2. 2. 2]辛烷结构式如下所示, Wherein, R is H or methyl; the 1-oxo-4-hydroxymethyl-1-phospha-2,6,7-trimethyl-oxabicyclo [2.2.2] octane structural formula As shown,
    Figure CN103012848AC00023
  4. 4.根据权利要求3所述的一种无卤膨胀型阻燃剂的制备方法,其特征在于,所述的氯代磷酸二(甲基)苯酯和1-氧代-4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2. 2. 2]辛烷摩尔比为1:0. 8-1. 2。 4. The method of claim 3 prepared Halogen-free flame retardant intumescent claim, wherein said chlorinated di (meth) phenyl ester and 4-hydroxymethyl-1-oxo 1-phospha-2,6,7-trimethyl heteroaryl oxabicyclo [2.2.2] octane molar ratio of 1: 08-12.
  5. 5.根据权利要求3所述的一种无卤膨胀型阻燃剂的制备方法,其特征在于,所述的溶齐IJ为氯仿、二氯甲烷、乙腈、四氢呋喃或乙酸乙酯,溶剂用量为每摩尔氯代磷酸二(甲基)苯酯加入溶剂500-3000mL。 The method for producing a non-halogen intumescent flame retardant according to claim 3, characterized in that said flush solution IJ, chloroform, dichloromethane, acetonitrile, tetrahydrofuran or ethyl acetate, an amount of solvent dicalcium phosphate per mole of chloro (methyl) phenyl acetate solvent was added 500-3000mL.
  6. 6.根据权利要求5所述的一种无卤膨胀型阻燃剂的制备方法,其特征在于,所述溶剂的用量为每摩尔氯代磷酸二(甲基)苯酯加入溶剂1000-2000mL。 The production method of claim 5 Halogen-free flame retardant intumescent claim, wherein the amount of said solvent per mole of chloro-di (meth) phenyl ester solvent was added 1000-2000mL.
  7. 7.根据权利要求3所述的无卤膨胀型阻燃剂的制备方法,其特征在于,所述的催化剂为无水三氯化铝、无水氯化锌、无水氯化镁、无水氯化亚铁或4- (N,N- 二甲氨基)吡啶,催化剂用量为每摩尔氯代磷酸二(甲基)苯酯加入0. l-20g的催化剂。 The method for preparing non-halogen intumescent flame retardant according to claim 3, wherein said catalyst is anhydrous aluminum chloride, anhydrous zinc chloride, anhydrous magnesium chloride, anhydrous chloride ferrous or 4- (N, N- dimethylamino) pyridine, the amount of catalyst per mole of chloro-di (meth) phenyl ester was added 0. l-20g catalyst.
  8. 8.根据权利要求7所述的一种无卤膨胀型阻燃剂的制备方法,其特征在于,催化剂的用量为每摩尔氯代磷酸二(甲基)苯酯加入2-10g的催化剂。 8. The preparation method of 7 Halogen-free flame retardant intumescent claim, wherein the amount of catalyst per mole of chloro-di (meth) phenyl ester was added 2-10g catalyst.
  9. 9.根据权利要求3所述的一种无卤膨胀型阻燃剂的制备方法,其特征在于,所述的缚酸剂为N,N- 二甲基苯胺、吡啶或三乙胺,缚酸剂与氯代磷酸二(甲基)苯酯的物质的量比为.0. 5_3 : I o 9. The method of claim 3 prepared Halogen-free flame retardant intumescent claim, wherein said acid binding agent is N, N- dimethylaniline, pyridine or triethylamine, the acid binding agent chlorophosphate di (meth) acrylate in the molar ratio of benzene to .0 5_3:. I o
  10. 10.根据权利要求3所述的一种无卤膨胀型阻燃剂的制备方法,其特征在于,所述的分离纯化为反应完成后,反应液进行减压过滤,滤液蒸懼回收溶剂,固体粗产品经充分水洗后,在真空条件下于40°C干燥至恒重。 10. The method of claim 3 prepared Halogen-free flame retardant intumescent claim, wherein the separation and purification after the completion of the reaction, the reaction liquid was filtered under reduced pressure, and the filtrate was evaporated to recover the solvent fear, solid the crude product was sufficiently washed with water, under vacuum at 40 ° C and dried to a constant weight.
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CN102532601A (en) * 2011-01-20 2012-07-04 河南大学 Novel halogen-free fire retardant ethanediamine diphenyl diphosphate and preparation method thereof

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US3883478A (en) * 1973-12-07 1975-05-13 Fmc Corp Flame-Retardant Polyester Fiber Compositions
CN102532601A (en) * 2011-01-20 2012-07-04 河南大学 Novel halogen-free fire retardant ethanediamine diphenyl diphosphate and preparation method thereof

Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN103992352A (en) * 2014-06-11 2014-08-20 苏州科技学院相城研究院 PEPA (polymeric pentaerythrityl phosphate) compound as caged tricyclic flame-retardant charring agent and preparation method of PEPA compound
CN103992352B (en) * 2014-06-11 2017-01-18 苏州科技学院相城研究院 Three cage ring flame char-forming agent methyl silicate ester compounds and methods of pepa

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