CN104448830A - Phosphorus-silicon composite flame retardant as well as preparation method and application thereof - Google Patents

Phosphorus-silicon composite flame retardant as well as preparation method and application thereof Download PDF

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CN104448830A
CN104448830A CN 201410680503 CN201410680503A CN104448830A CN 104448830 A CN104448830 A CN 104448830A CN 201410680503 CN201410680503 CN 201410680503 CN 201410680503 A CN201410680503 A CN 201410680503A CN 104448830 A CN104448830 A CN 104448830A
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flame
retardant
phosphorus
silicon
composite
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CN 201410680503
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CN104448830B (en )
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袁章林
王锦成
韦小凤
李涛涛
庹文海
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上海工程技术大学
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Abstract

The invention discloses a phosphorus-silicon composite flame retardant as well as a preparation method and application thereof. The phosphorus-silicon composite flame retardant is a cage-like tetraphenyl trisilicate phosphorus silsesquioxane shown in the description, and the flame retardant is prepared according to the following steps: firstly hydrolyzing POSS to chipping POSS under the action of an organic alkali, and then carrying out reaction of the chipping POSS with metaphosphoric acid. Experiments show that the phosphorus-silicon composite flame retardant provided by the invention gives full play to the advantages of a silicon flame retardant and a phosphorus flame retardant, compensates defects of the silicon flame retardant and the phosphorus flame retardant, has significant synergistic flame retardance and complementarity, and excellent thermal insulation, smoke suppression and oxygen supply cutoff functions, also has the functions of protecting the environment, safety and preventing molten drop, can be directly used for preparing silicone rubber, can not only improve the flame retardance of the silicone rubber, but also perfect the thermal insulation, smoke suppression and mechanical properties of the silicone rubber, and the phosphorus-silicon composite flame retardant has the advantages of being low in preparation and application costs, easy to realize large-scale industrialized production, and the like.

Description

一种磷硅复合阻燃剂及其制备方法和应用 One phosphorus flame retardants and silicon composite preparation method and application

技术领域 FIELD

[0001] 本发明是涉及一种磷硅复合阻燃剂及其制备方法和应用,属于阻燃材料技术领域。 [0001] The present invention relates to a flame retardant and a phosphorus-silicon composite preparation method and application, it belongs to the technical field of fire-retardant material.

背景技术 Background technique

[0002] 目前,高分子材料阻燃剂领域中,应用较多的是卤系阻燃剂,虽然这类阻燃剂的阻燃效果很好,但由于卤素燃烧时释放卤化氢气体和不可降解性,现已被限制使用。 [0002] Currently, in the field of polymer materials flame retardant, more applications are halogen flame retardant, although such a good flame retardant effect, but since the release of hydrogen halide gas upon combustion and halogen nondegradable sex, has been restricted.

[0003] 硅系阻燃剂作为阻燃剂家族中的后起之秀,始于20世纪80年代初期。 [0003] silicon-based flame retardant as a flame rising star in the family, began in the early 1980s. 它不但具有高效、低毒、抑烟和促进成炭等优异的阻燃性能,而且相对于传统阻燃剂,硅系阻燃剂在加工性能和力学性能等方面也得到了显著提升,深受众多研究者的青睐。 It not only has high efficiency, low toxicity and excellent flame retardant properties, and smoke suppression promoting char etc., and with respect to the conventional flame retardant, silicone-based flame retardant in terms of processability and mechanical properties has also been significantly improved, by favored by many researchers. 目前,硅系阻燃剂主要有以下四类: Currently, silicon-based flame retardant mainly in the following four categories:

[0004] 1)有机硅系阻燃剂:它是一种高效、生态友好、防熔滴并抑烟的新一代非卤成炭型阻燃剂,不仅能改善基材的加工、机械及耐热等性能,而且循环利用效果也十分优异,主要包括聚硅氧烷,聚有机硅倍半硅氧烷等品种。 [0004] 1) a silicone-based flame retardant: It is a highly effective, eco-friendly, and the droplet preventing smoke generation suppressing non-halogen flame retardant char, not only to improve the processing of the substrate, and resistance to mechanical thermal and other properties, and the effect is very excellent in recycling, including polysiloxanes, silicones silsesquioxane varieties. 但单一的有机硅阻燃剂仅对部分高聚物主要是聚碳酸酯卓有成效,适用面不广; However, only a single part of silicone flame retardant polycarbonate polymer is mainly effective, not widely applicable;

[0005] 2)无机硅系阻燃剂:一定条件下,无机硅化合物无论作为聚合物的添加剂,还是与聚合物组成共混体体系,均具有较好的阻燃作用。 [0005] 2) inorganic silicon-based flame retardant: Under certain conditions, regardless of inorganic silicon compounds as an additive polymer, and polymer blends or systems, have a good flame retardant. 其阻燃的高聚物大多无毒少烟、燃烧值低、火焰传播速度慢,但一般需要与其它添加剂配合使用。 Most non-toxic polymer which less smoke retardant, low calorific value, flame propagation is slow, it is generally required to work with other additives.

[0006] 3)硅本质阻燃高聚物技术:因含硅基团的聚合物一般具有极高的本征阻燃性能、 热稳定性、氧化稳定性、憎水性以及良好的柔顺性,所得含硅本质阻燃高聚物除拥有阻燃、 耐高热、抗氧化、不易燃烧等特点外,还具有较高的耐湿性和分子链的柔软性。 [0006] 3) the nature of the flame retardant silicone polymer technology: because silicon group-containing polymer typically has a very high intrinsic flame retardant properties, thermal stability, oxidative stability, hydrophobicity, and good flexibility, resulting in addition to silicon-containing polymers have essentially flame retardant, heat-resistant, antioxidative, nonflammable, etc., but also has high flexibility and humidity resistance molecular chain. 此外,含硅本质阻燃高聚物受热分解产物主要是二氧化碳、水蒸气和二氧化硅,对环境友好,因而受到广泛的关注。 Furthermore, the nature of the silicon-containing flame retardant polymer thermal decomposition products are mainly carbon dioxide, water vapor and silica, environmentally friendly, due to the widespread attention. 但含硅本质阻燃高聚物的应用制造工艺复杂、价格昂贵。 But the nature of the silicon-containing flame retardant polymers application manufacturing process is complicated and expensive.

[0007] 4)硅阻燃剂的协效阻燃技术:含硅阻燃剂与其它传统阻燃剂一起使用,表现出显著的协同阻燃作用和互补性,在燃烧过程中,两者能相互促进,形成含硅炭化保护层,具有卓越的隔热抑烟、断绝氧的供应,并防止烙滴等功能;能改善材料的加工性能,对物理机械性能影响小。 [0007] 4) a silicon flame retardant synergist flame retardant technology: silicon-containing flame retardant used together with other conventional flame retardants exhibit significant synergistic flame retardant and complementarity, during combustion, can both each other is promoted to form carbonized silicon-containing protective layer having excellent heat supply and smoke suppression, cut off oxygen, and preventing baked dropwise function; to improve the processing properties of the material, a small influence on the mechanical properties.

[0008] 笼状八苯基倍半硅氧烷(简称为P0SS)是一种具有纳米结构、相容性好、阻燃性强的有机-无机杂化材料,它同时具备有机娃系与无机娃系阻燃剂的优点,表现出与基材较好的相容性,可在塑料、橡胶等材料中获得应用。 [0008] The cage octaphenyl silsesquioxane (abbreviated as P0SS) having a nano structure, good compatibility, flame retardancy strong organic - inorganic hybrid material, it also includes an organic-based and inorganic doll baby advantages flame retardants, exhibits good compatibility with the substrate, can find application in plastic material, rubber or the like.

[0009] 磷系阻燃剂不仅具有高效、多功能的特点,且安全环保,是目前卤系阻燃剂中最主要的替代品种,但其热稳定性较低,在熔融状态或较低温度下加工时,会在塑料、橡胶中产生泡沫,从而导致应用面不广。 [0009] The phosphorus-based flame retardant is not only efficient, multi-functional characteristics, safety and environmental protection, a halogen-based flame retardant is the most important alternative species, but lower thermal stability, lower temperatures in the molten state or when the process will produce foam plastic, rubber, resulting in not widely applied.

发明内容 SUMMARY

[0010] 针对现有技术所存在的上述缺陷和问题,本发明的目的是提供一种磷硅复合阻燃剂及其制备方法和应用,将传统的磷系阻燃剂引入笼状七苯基三硅醇倍半硅氧烷中,发挥二者各自的优势,实现磷系阻燃剂与笼状七苯基三硅醇倍半硅氧烷的协效阻燃目的。 [0010] For the above disadvantages and problems of the prior art exists, object of the present invention is to provide a flame retardant and a phosphorus-silicon composite preparation method and application, the phosphorus-based flame retardant incorporated traditional cage-like seven-phenyl three silsesquioxane silanols, the respective advantages of both play, to achieve synergistic flame retardant phosphorus-based flame retardant object cage seven three-phenyl silsesquioxane silanol.

[0011] 为实现上述发明目的,本发明采用的技术方案如下: [0011] In order to achieve the above object, the present invention employs the following technical solutions:

[0012] 一种磷硅复合阻燃剂,是具有如下结构的笼状七苯基三硅磷倍半硅氧烷: [0012] A silicon composite phosphorus flame retardant, having a cage-like seven-phenyl three silicon-phosphorus silsesquioxanes structure:

[0013] [0013]

Figure CN104448830AD00051

[0014] 一种制备本发明所述的磷硅复合阻燃剂的方法,包括如下步骤: [0014] The present invention is a process for the preparation of flame retardant phosphorus-silicon composite, comprising the steps of:

[0015]a)使笼状八苯基倍半硅氧烷(简称为P0SS)在有机碱作用下进行水解反应,制得缺角P0SS:笼状七苯基三硅醇倍半硅氧烷; [0015] a) that the cage octaphenyl silsesquioxane (abbreviated as P0SS) hydrolysis reaction under the action of an organic base to prepare a chipping P0SS: cage seven three silanol phenyl silsesquioxane;

[0016]b)将上述缺角P0SS:笼状七苯基三硅醇倍半硅氧烷与偏磷酸反应,得到所述的磷娃复合阻燃剂。 [0016] b) The above chipping P0SS: seven phenyltriethoxysilane cage silsesquioxane silanol is reacted with meta-phosphoric acid, to give the baby phosphorus compound flame retardant.

[0017] 作为优选方案,所述的笼状八苯基倍半硅氧烷(简称为P0SS)的制备,包括如下步骤: [0017] As a preferred embodiment, the preparation of the cage-like silsesquioxane octaphenyl (abbreviated as P0SS), comprising the steps of:

[0018] 1)使苯基三氯硅烷与苯和水体系在室温下搅拌8〜16小时后静置6〜12小时; [0018] 1) reacting benzene with phenyl trichlorosilane and the aqueous system was allowed to stand at room temperature After stirring for hours 6~12 8~16 hours;

[0019] 2)分液,除去底部的酸层,用蒸馏水或碱性溶剂冲洗有机相至pH= 7 ; [0019] 2) liquid separation, the bottom acid layer was removed, the organic phase washed with distilled water to solvent or alkaline pH = 7;

[0020] 3)向步骤2)处理后的有机相中加入苄基三甲基氢氧化铵的甲醇溶液,搅拌回流反应24〜36小时; [0020] 3) of step 2) after the treatment the organic phase was added benzyltrimethylammonium hydroxide in methanol, the reaction was stirred at reflux for 24~36 hours;

[0021] 4)过滤、干燥,得到所述的笼状八苯基倍半硅氧烷(简称为P0SS)。 [0021] 4) filtered, and dried to give the cage eight times the phenyl silsesquioxane (abbreviated as P0SS).

[0022] 作为进一步优选方案,按质量比计,苯基三氯硅烷:苯:水:苄基三甲基氢氧化铵甲醇溶液=( 5〇〜8〇) : (25〇〜400) : (2〇〜40) : (8〜I3);其中,苄基三甲基氢氧化铵甲醇溶液的体积百分比浓度为30〜50%。 [0022] As a further preferred embodiment, by mass ratio, phenyltrichlorosilane: benzene: water: benzyl trimethyl ammonium hydroxide in methanol = (5〇~8〇): (25〇~400): ( 2〇~40): (8~I3); wherein, benzyl trimethyl ammonium hydroxide by volume percent concentration of 30 ~ 50% methanol solution.

[0023] 作为优选方案,步骤a)所述的有机碱为四甲基氢氧化铵。 [0023] As a preferred embodiment, the organic base of step a) above is tetramethylammonium hydroxide.

[0024] 作为进一步优选方案,步骤a)所述的水解反应是使笼状八苯基倍半硅氧烷(简称为P0SS)在四氢呋喃、四甲基氢氧化铵水溶液中回流反应4〜6小时。 [0024] As a further preferred embodiment, step a) of the hydrolysis reaction is that the cage octaphenyl silsesquioxane (abbreviated as P0SS) was refluxed in tetrahydrofuran, tetramethylammonium hydroxide aqueous solution of 4 ~ 6 hours the reaction .

[0025] 作为更进一步优选方案,按质量比计,笼状八苯基倍半硅氧烷:四氢呋喃:四甲基氢氧化铵水溶液=(10〜20) : (100〜250) : (4〜8);其中,四甲基氢氧化铵水溶液的体积百分比浓度为25〜40%。 [0025] As a further preferred embodiment, by mass ratio, cage octaphenyl silsesquioxane: tetrahydrofuran: an aqueous solution of tetramethylammonium hydroxide = (10-20): (100~250): (4 ~ 8); wherein the volume percent tetramethylammonium hydroxide aqueous ammonium concentration of 25~40%.

[0026] 作为优选方案,步骤b)中,缺角P0SS:笼状七苯基三硅醇倍半硅氧烷与偏磷酸在四氧咲喃中于50〜80°C反应4〜6小时。 [0026] As a preferred embodiment, step b), chipping P0SS: seven phenyltriethoxysilane cage silsesquioxane silanols metaphosphate reaction at 50~80 ° C 4 ~ 6 hours in four oxygen Kou furans.

[0027] 作为进一步优选方案,按质量比计,笼状七苯基三硅醇倍半硅氧烷:偏磷酸:四氢呋喃=(1〇〜20) : (15 〜25) : (100 〜250)。 [0027] As a further preferred embodiment, by mass ratio, the cage seven three-phenyl silsesquioxane silanols: metaphosphoric acid: tetrahydrofuran = (1〇~20): (15 ~ 25): (100 ~ 250) .

[0028] -种应用本发明所述的磷硅复合阻燃剂制备的硅橡胶复合材料,按质量份数计, 至少包括:74. 5〜94. 5质量份硅橡胶生胶,0. 5〜1. 5质量份固化剂及5〜25质量份本发明所述的磷硅复合阻燃剂。 [0028] - silicone rubber composites phosphosilicate compound species of the present invention is applied to the flame retardant prepared parts by mass basis, at least comprising: 74 parts by mass of 5 5~94 silicone rubber adhesive, 05... ~ 1. 5 parts by mass of a curing agent and 5~25 parts by mass of flame retardant phosphorus-silicon composite according to the present invention.

[0029] 作为优选方案,所述的硅橡胶复合材料的制备包括如下步骤:将本发明所述的磷硅复合阻燃剂加入硅橡胶生胶中,搅拌混合均匀后加入固化剂,继续搅拌混合均匀后倒入模具中,进行真空排气后于80〜120°C固化反应60〜90分钟,最后冷却至室温。 [0029] As a preferred embodiment, the preparation of silicone rubber composite material comprising the steps of: phosphosilicate compound of the present invention, a flame retardant silicone rubber adhesive was added, stirred uniformly mixed curing agent was added, stirring continued mixing uniformly poured into a mold, vacuum exhaust 80~120 ° C after the curing reaction 60~90 minutes, and finally cooled to room temperature.

[0030] 作为进一步优选方案,进行真空排气的真空度为150〜160Pa。 [0030] As a further preferred embodiment, the degree of vacuum evacuation is 150~160Pa.

[0031] 与现有技术相比,本发明具有如下有益效果: [0031] Compared with the prior art, the present invention has the following advantages:

[0032] 本发明通过在硅系阻燃剂笼状八苯基倍半硅氧烷中引入传统的磷系阻燃剂,充分发挥了硅系阻燃剂和磷系阻燃剂二者的优势,弥补了各自缺陷,得到的复合磷硅阻燃剂具有显著的协同阻燃作用和互补性,以及卓越的隔热抑烟、断绝供氧的特性,还具有环保安全、防止熔滴等功能。 [0032] The present invention introduces a conventional phosphorus-based flame retardant by a silicon-based cage in octaphenyl silsesquioxane, takes full advantage of both the silicon-based flame retardants and phosphorus-based flame retardant make up their own shortcomings, the resulting composite phosphosilicate synergistic flame retardant has a significant flame retardant and complementarity, as well as excellent heat and smoke suppression, oxygen is cut off properties, but also environmentally safe, and other functions to prevent the droplet. 另外,本发明提供的磷硅复合阻燃剂为粉末状固体,可直接应用于硅橡胶的加工过程中,无需再进行繁琐的溶液或熔融插层处理,具有制备和应用成本低、易于规模化工业实施等优点,能改善材料的加工性能,对物理机械性能影响小。 Further, the phosphorus flame retardant of the present invention provides silicon composite powder is a solid, can be directly applied to the processing of silicone rubber, the solution no longer cumbersome or melt intercalation process, preparation and application of low cost, easy to scale industrial advantage of embodiments, etc., can improve the processing properties of the material, a small influence on the mechanical properties.

附图说明 BRIEF DESCRIPTION

[0033] 图1为笼状八苯基倍半硅氧烷(P0SS)的结构式; [0033] FIG. 1 is a cage-like silsesquioxane octaphenyl (P0SS) of the formula;

[0034] 图2为缺角P0SS:笼状七苯基三硅醇倍半硅氧烷的结构式; [0034] FIG 2 is a cutaway P0SS: a cage structure of formula seven three silanol phenyl silsesquioxane;

[0035] 图3为本发明提供的磷硅复合阻燃剂:笼状七苯基三硅磷倍半硅氧烷的结构式。 [0035] FIG. 3 phosphosilicate compound flame retardant of the present invention to provide: a cage-like structure of silicon formula seven phenyl silsesquioxane phosphorus.

具体实施方式 detailed description

[0036] 下面结合实施例和对比例对本发明做进一步详细、完整地说明。 [0036] The following Examples and Comparative Examples in further detail, a complete description of the present invention.

[0037] 实施例1 [0037] Example 1

[0038] 在圆底烧瓶中依次加入50g苯基三氯硅烷、250ml苯,边搅拌边缓慢加入20mL水, 体系在室温下搅拌12小时后静置10小时;利用分液漏斗除去底部的酸层,用蒸馏水或碱性溶剂冲洗使有机相至中性;向有机相中加入8mL苄基三甲基氢氧化铵的甲醇溶液,搅拌回流反应24小时;过滤、干燥,即得如图1所示结构的笼状八苯基倍半硅氧烷(P0SS)。 [0038] phenyltrichlorosilane were added 50g, 250ml of benzene in a round-bottomed flask, while stirring, was allowed to stand was slowly added 20mL of water, stirred at room temperature for 12 to 10 hours; acid using a separatory funnel and the bottom layer was removed , washed with distilled water or a basic solvent until neutral and the organic phase; the organic phase was added 8mL benzyltrimethylammonium hydroxide in methanol was stirred at reflux for 24 hours; filtered, and dried to obtain 1 cage structure octaphenyl silsesquioxane (P0SS).

[0039] 取10g笼状八苯基倍半硅氧烷置于圆底烧瓶中,依次向其中加入100mL四氢呋喃、 4mL25vol%四甲基氢氧化铵的水溶液,回流反应4小时;加入稀盐酸中和反应液至中性;浓缩除去其中的可挥发溶剂,得白色固体;将所得白色固体溶于苯中,并用无水硫酸镁处理, 过滤,浓缩干所得溶液,即得如图2所示结构的缺角P0SS:笼状七苯基三硅醇倍半硅氧烷。 [0039] Take 10g cage octaphenyl silsesquioxane placed in a round bottom flask, followed by 100mL of tetrahydrofuran, 4mL25vol% aqueous solution of tetramethylammonium hydroxide, and the reaction was refluxed for 4 hours was added thereto; and dilute hydrochloric acid was added the reaction solution to neutral; wherein the volatile solvent was removed and concentrated to give a white solid; the resulting white solid was dissolved in benzene, and dried over anhydrous magnesium sulfate, filtered and the resulting solution was concentrated to dryness, i.e. the structure shown in FIG. 2 is obtained chipping P0SS: seven phenyltriethoxysilane cage silsesquioxane silanol.

[0040] 取l〇g缺角P0SS,于50°C加入15g偏磷酸与100mL四氢呋喃溶液,然后升温至60°C,保温反应5小时后停止反应,过滤、浓缩,即得如图3所示结构的本发明所述的磷硅复合阻燃剂:笼状七苯基三硅磷倍半硅氧烷。 [0040] Take l〇g chipping P0SS, at 50 ° C was added 100mL of tetrahydrofuran and 15g metaphosphoric acid solution, and then warmed to 60 ° C, stopped the reaction after incubation for 5 hours, filtered, and concentrated to afford 3 phosphorus flame retardant silicon composite structure according to the present invention: a cage-like seven-phenyl silsesquioxane three silicon-phosphorus.

[0041] 实施例2 [0041] Example 2

[0042] 在圆底烧瓶中依次加入75g苯基三氯硅烷、350ml苯,边搅拌边缓慢加入30mL水, 体系在室温下搅拌16小时后静置6小时;利用分液漏斗除去底部的酸层,用蒸馏水或碱性溶剂冲洗使有机相至中性;向有机相中加入lOmL苄基三甲基氢氧化铵的甲醇溶液,搅拌回流反应36小时;过滤、干燥,即得如图1所示结构的笼状八苯基倍半硅氧烷(P0SS)。 [0042] 75g phenyltrichlorosilane were added successively, 350 ml of benzene in a round-bottomed flask, while stirring, was allowed to stand was slowly added 30mL of water, stirred at room temperature for 16 hours 6 hours; acid using a separatory funnel and the bottom layer was removed , washed with distilled water or a basic solvent until neutral and the organic phase; the organic phase was added lOmL benzyltrimethylammonium hydroxide in methanol was stirred at reflux for 36 hours; filtered, and dried to obtain 1 cage structure octaphenyl silsesquioxane (P0SS).

[0043] 取15g笼状八苯基倍半硅氧烷置于圆底烧瓶中,依次向其中加入200mL四氢呋喃、 6mL25vol%四甲基氢氧化铵的水溶液,回流反应5小时;加入稀盐酸中和反应液至中性;浓缩除去其中的可挥发溶剂,得白色固体;将所得白色固体溶于苯中,并用无水硫酸镁处理, 过滤,浓缩干所得溶液,即得如图2所示结构的缺角P0SS:笼状七苯基三硅醇倍半硅氧烷。 [0043] Take 15g cage octaphenyl silsesquioxane into a round bottom flask, 200mL of tetrahydrofuran were added, 6mL25vol% aqueous solution of tetramethylammonium hydroxide, and thereto was refluxed for 5 hours; and dilute hydrochloric acid was added the reaction solution to neutral; wherein the volatile solvent was removed and concentrated to give a white solid; the resulting white solid was dissolved in benzene, and dried over anhydrous magnesium sulfate, filtered and the resulting solution was concentrated to dryness, i.e. the structure shown in FIG. 2 is obtained chipping P0SS: seven phenyltriethoxysilane cage silsesquioxane silanol.

[0044] 取10g缺角P0SS,于40°C加入18g偏磷酸与200mL四氢呋喃溶液,然后升温至50°C,保温反应6小时后停止反应,过滤、浓缩,即得如图3所示结构的本发明所述的磷硅复合阻燃剂:笼状七苯基三硅磷倍半硅氧烷。 [0044] Take 10g chipping P0SS, at 40 ° C was added 200mL of tetrahydrofuran and 18g metaphosphoric acid solution, and then warmed to 50 ° C, reaction was stopped after 6 hours incubation the reaction was filtered, concentrated, i.e., the structure as shown in FIG. 3 obtained phosphorus flame retardant silicon composite according to the present invention: a cage-like seven-phenyl silsesquioxane three silicon-phosphorus.

[0045] 实施例3 [0045] Example 3

[0046] 在圆底烧瓶中依次加入80g苯基三氯硅烷、400ml苯,边搅拌边缓慢加入40mL水, 体系在室温下搅拌8小时后静置12小时;利用分液漏斗除去底部的酸层,用蒸馏水或碱性溶剂冲洗使有机相至中性;向有机相中加入13mL苄基三甲基氢氧化铵的甲醇溶液,搅拌回流反应36小时;过滤、干燥,即得如图1所示结构的笼状八苯基倍半硅氧烷(P0SS)。 [0046] phenyltrichlorosilane were added 80g, 400ml of benzene in a round-bottomed flask, while stirring, was allowed to stand was slowly added 40mL of water, stirred at room temperature for 8 hours and 12 hours; acid using a separatory funnel and the bottom layer was removed , washed with distilled water or a basic solvent until neutral and the organic phase; the organic phase was added 13mL benzyltrimethylammonium hydroxide in methanol was stirred at reflux for 36 hours; filtered, and dried to obtain 1 cage structure octaphenyl silsesquioxane (P0SS).

[0047] 取20g笼状八苯基倍半硅氧烷置于圆底烧瓶中,依次向其中加入250mL四氢呋喃、 8mL25vol%四甲基氢氧化铵的水溶液,回流反应6小时;加入稀盐酸中和反应液至中性;浓缩除去其中的可挥发溶剂,得白色固体;将所得白色固体溶于苯中,并用无水硫酸镁处理, 过滤,浓缩干所得溶液,即得如图2所示结构的缺角P0SS:笼状七苯基三硅醇倍半硅氧烷。 [0047] Take 20g cage octaphenyl silsesquioxane into a round bottom flask, 250mL of tetrahydrofuran was added thereto sequentially, 8mL25vol% aqueous solution of tetramethylammonium hydroxide, and the reaction was refluxed for 6 hours; and dilute hydrochloric acid was added the reaction solution to neutral; wherein the volatile solvent was removed and concentrated to give a white solid; the resulting white solid was dissolved in benzene, and dried over anhydrous magnesium sulfate, filtered and the resulting solution was concentrated to dryness, i.e. the structure shown in FIG. 2 is obtained chipping P0SS: seven phenyltriethoxysilane cage silsesquioxane silanol.

[0048] 取20g缺角P0SS,于60°C加入25g偏磷酸与250mL四氢呋喃溶液,然后升温至80°C,保温反应4小时后停止反应,过滤、浓缩,即得如图3所示结构的本发明所述的磷硅复合阻燃剂:笼状七苯基三硅磷倍半硅氧烷。 [0048] Take 20g chipping P0SS, at 60 ° C was added 250mL of tetrahydrofuran and 25g metaphosphoric acid solution, and then warmed to 80 ° C, reaction was stopped after 4 hours incubation the reaction was filtered, concentrated, i.e., the structure as shown in FIG. 3 obtained phosphorus flame retardant silicon composite according to the present invention: a cage-like seven-phenyl silsesquioxane three silicon-phosphorus.

[0049] 实施例1-3所制备的P0SS、缺角P0SS及本发明所述的磷硅复合阻燃剂的表征数据及热失重中心温度的检测数据详见表1所示。 [0049] P0SS prepared in Example 1-3, characterizing data phosphosilicate compound flame retardant according to the present invention and P0SS chipping and thermal weight loss of core temperature detection data shown in Table 1. 其中,热失重中心温度是采用《聚合物/层状硅酸盐纳米复合材料理论与实践》(漆宗能,尚文宇编著,化学工业出版社,2002)规定的热失重法检测。 Wherein the thermal reduction is the use of core temperature "Polymer / layered silicate nanocomposite Theory and Practice" (cases paint can, Shangwen Yu eds., Chemical Industry Press, 2002) and pyrolysis predetermined detected.

[0050] 表1 [0050] TABLE 1

[0051] [0051]

Figure CN104448830AD00071

[0052] 由表1所示的热失重中心温度数据可见:本发明提供的磷硅复合阻燃剂具有显著的协同阻燃作用。 [0052] The thermal reduction temperature of the center seen from the data shown in Table 1: phosphorus-silicon composite having a flame retardant of the present invention provides significant synergistic flame retardant.

[0053] 应用例1 [0053] Application Example 1

[0054] 向95克硅橡胶甲组分中,加入5g本发明所述的磷硅复合阻燃剂,于2000转/分钟搅拌使混合均匀(约5分钟);加入0. 8克固化剂,再于2000转/分钟搅拌使混合均匀(约0. 5分钟);将其倒入特氟龙模具中,在150Pa真空度下进行真空排气后于80°C固化反应90分钟,得到本发明的硅橡胶复合材料。 [0054] 95 g of silicone rubber to Group A, the flame retardant phosphorus-silicon composite according to the present invention, 5g, at 2000 revolutions / min with stirring to make a uniform mixture (about 5 minutes); was added 0.8 g curing agent, and then at 2000 rpm / min uniformly mixed with stirring (about 0.5 minutes); poured into a Teflon mold, after evacuation at 80 ° C the curing reaction under a vacuum of 150Pa for 90 minutes to give the present invention the silicone rubber composites.

[0055] 对比例1 [0055] Comparative Example 1

[0056] 本对比例与应用例1的不同之处仅在于:此对比例中未添加本发明所述的磷硅复合阻燃剂,其余内容均与应用例1所述相同,即: [0056] The difference in this Comparative Application Example 1 only: this ratio is not added to the present invention, the silicon composite phosphorus flame retardants, and the rest are the same as Application Example 1, namely:

[0057] 向95克硅橡胶甲组分中,加入0. 8克固化剂,于2000转/分钟搅拌使混合均匀; 将其倒入特氟龙模具中,在150Pa真空度下进行真空排气后于80°C固化反应90分钟,得到对比的硅橡胶复合材料。 [0057] To 95 g of silicone rubber in Group A, a curing agent was added 0.8 grams, at 2000 revolutions / min with stirring homogeneously mixed; poured into a Teflon mold, and evacuated under a vacuum of 150Pa 80 ° C after curing for 90 minutes, yielding a silicone rubber composite material for comparison.

[0058] 应用例2 [0058] Application Example 2

[0059] 向96. 5克硅橡胶甲组分中,加入10g本发明所述的磷硅复合阻燃剂,于1500转/ 分钟搅拌使混合均匀(约10分钟);加入1. 〇克固化剂,再于1500转/分钟搅拌使混合均匀(约1分钟);将其倒入特氟龙模具中,在156Pa真空度下进行真空排气后于KKTC固化反应75分钟,得到本发明的硅橡胶复合材料。 [0059] To 96.5 g Silastic Group A, the phosphorus flame retardant silicon composite according to the present invention is 10g at 1500 rev / min stirring homogenous (about 10 minutes); was added 1 g of cured billion agent, and then at 1500 rev / min stirring homogenous (approximately 1 minute); poured into a Teflon mold, after evacuation KKTC curing reaction under a vacuum of 156Pa for 75 minutes to obtain a silicone according to the present invention rubber composite.

[0060] 对比例2 [0060] Comparative Example 2

[0061] 本对比例与应用例2的不同之处仅在于:此对比例中未添加本发明所述的磷硅复合阻燃剂,其余内容均与应用例2所述相同,即: [0061] The difference in this Comparative Application Example 2 only in that: in this comparative example of the present invention is not added phosphorus silicate composite flame retardant, and the rest are the same as Application Example 2, namely:

[0062] 向96. 5克硅橡胶甲组分中,加入1. 0克固化剂,于1500转/分钟搅拌使混合均匀;将其倒入特氟龙模具中,在156Pa真空度下进行真空排气后于KKTC固化反应75分钟, 得到对比的硅橡胶复合材料。 [0062] To 96.5 g Silastic Group A was added 1.0 g hardener, to 1500 rev / min stirring mixed; poured into a Teflon mold, under vacuum at degree of vacuum of 156Pa KKTC exhaust gas after the curing reaction for 75 minutes to obtain a silicone rubber composite comparison.

[0063] 应用例3 [0063] Application Example 3

[0064] 向98克硅橡胶甲组分中,加入15g本发明所述的磷硅复合阻燃剂,于1000转/分钟搅拌使混合均匀(约15分钟);加入1. 4克固化剂,再于1000转/分钟搅拌使混合均匀(约1. 5分钟);将其倒入特氟龙模具中,在160Pa真空度下进行真空排气后于120°C固化反应60分钟,得到本发明的硅橡胶复合材料。 [0064] 98 g of silicone rubber to Group A, the flame retardant phosphorus-silicon composite according to the present invention is 15g at 1000 rev / min stirring homogenous (about 15 minutes); was added 1.4 g curing agent, then at 1000 rev / min stirring homogeneously mixing (approximately 1.5 minutes); poured into a Teflon mold, after evacuation at 120 ° C the curing reaction under a vacuum of 160Pa for 60 minutes to give the present invention the silicone rubber composites.

[0065] 对比例3 [0065] Comparative Example 3

[0066] 本对比例与应用例3的不同之处仅在于:此对比例中未添加本发明所述的磷硅复合阻燃剂,其余内容均与应用例3所述相同,即: [0066] The difference in this Comparative Application Example 3 only: this ratio is not added to the phosphorus-silicon composite according to the present invention, a flame retardant, and the rest are the same as Application Example 3, namely:

[0067] 向98克硅橡胶甲组分中,加入1. 4克固化剂,于1000转/分钟搅拌使混合均匀; 将其倒入特氟龙模具中,在160Pa真空度下进行真空排气后于120°C固化反应60分钟,得到对比的硅橡胶复合材料。 [0067] To 98 g of silicone rubber Group A was added 1.4 g curing agent, at 1000 rev / min stirring mixed; poured into a Teflon mold, and evacuated under a vacuum of 160Pa after 120 ° C cure for 60 minutes, yielding a silicone rubber composite material for comparison.

[0068] 采用《聚合物/层状硅酸盐纳米复合材料理论与实践》(漆宗能,尚文宇编著, 化学工业出版社,2002)规定的热失重法测试阻燃剂粉体的热失重中心温度;采用GB/T 1701-2001、GB10707-2008国家标准测试硅橡胶材料的力学性能和阻燃性能。 [0068] The "Polymer / layered silicate nanocomposite Theory and Practice" (cases paint can, Shangwen Yu eds., Chemical Industry Press, 2002) and pyrolysis heat retardant powder predetermined test weight loss core temperature; 1701-2001 employed, mechanical properties and flame retardancy GB / T GB10707-2008 national standard test silicone rubber material.

[0069] 关于应用例1-3及对比例1-3所得硅橡胶材料的拉伸强度、断裂伸长率、热失重中心温度和氧指数的测试数据详见表2所示。 [0069] For Comparative Application Examples 1-3 and 1-3 obtained silicone rubber material tensile strength, elongation at break of the test data, and TGA oxygen index core temperature shown in Table 2.

[0070]表2. [0070] Table 2.

[0071] [0071]

Figure CN104448830AD00091

[0072] 由表2测试结果可见:添加有本发明所述的复合磷硅阻燃剂的硅橡胶材料,不仅阻燃性得到了提高,其隔热抑烟及力学性能均得到改善。 [0072] From Table 2 Test Results: silicone rubber material added with a silicon compound of the present invention, a phosphorus flame retardant, not only has improved flame resistance, heat and smoke suppression and its mechanical properties were improved.

[0073] 最后有必要在此说明的是,以上实施例仅用以说明本发明的技术方案而非限制本发明,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围内。 [0073] Finally, described herein is necessary that the above embodiments are intended to illustrate the present invention and not to limit the present invention, although the present invention has been described in detail, with reference to the preferred embodiments by those of ordinary skill in the art should understood aspect of the invention may be modified or equivalently substituted without departing from the spirit and scope of the technical solutions of the present invention, which should fall within the claimed scope of the claimed invention.

Claims (10)

  1. 1. 一种磷硅复合阻燃剂,其特征在于,是具有如下结构的笼状七苯基三硅磷倍半硅氧烧: A flame retardant phosphorus silicate compound, wherein a cage having the structure of silicon seven phenyl silsesquioxane burning phosphorus:
    Figure CN104448830AC00021
  2. 2. -种制备权利要求1所述的磷硅复合阻燃剂的方法,其特征在于,包括如下步骤: a) 使笼状八苯基倍半硅氧烷(简称为POSS)在有机碱作用下进行水解反应,制得缺角POSS:笼状七苯基三硅醇倍半硅氧烷; b) 将上述缺角POSS:笼状七苯基三硅醇倍半硅氧烷与偏磷酸反应,得到所述的磷硅复合阻燃剂。 2. - Method phosphosilicate complex flame retardant according to claim 1 prepared kind claims, characterized in that, comprising the steps of: a) a cage-like silsesquioxane octaphenyl (abbreviated as POSS) acts organic bases the hydrolysis reaction, the product chipping POSS: cage seven three silanol phenyl silsesquioxane; b) the above chipping POSS: seven phenyltriethoxysilane cage silsesquioxane silanol reaction metaphosphate to obtain the phosphosilicate compound flame retardant.
  3. 3. 如权利要求2所述的方法,其特征在于,所述的笼状八苯基倍半硅氧烷的制备包括如下步骤: 1) 使苯基三氯硅烷与苯和水体系在室温下搅拌8〜16小时后静置6〜12小时; 2) 分液,除去底部的酸层,用蒸馏水或碱性溶剂冲洗有机相至pH= 7 ; 3) 向步骤2)处理后的有机相中加入苄基三甲基氢氧化铵的甲醇溶液,搅拌回流反应24〜36小时; 4) 过滤、干燥,得到所述的笼状八苯基倍半硅氧烷。 3. The method according to claim 2, wherein said cage prepared octaphenyl silsesquioxane comprises the steps of: a) reacting benzene with phenyl trichlorosilane and the water system at room temperature the organic phase 3) 2) after the processing of step; after stirring for 8~16 hours standing 6~12 hours; 2) liquid separation, the bottom acid layer was removed, rinsed with distilled water or a basic organic solvent phase to pH = 7 was added benzyltrimethylammonium hydroxide in methanol, the reaction was stirred at reflux for 24~36 hours; 4) filtered, and dried to give the cage octaphenyl silsesquioxane.
  4. 4. 如权利要求2所述的方法,其特征在于:步骤a)所述的有机碱为四甲基氢氧化铵; 所述的水解反应是使笼状八苯基倍半硅氧烷在四氢呋喃、四甲基氢氧化铵水溶液中回流反应4〜6小时。 4. The method according to claim 2, characterized in that: the organic base of step a) above is tetramethylammonium hydroxide; the hydrolysis reaction is that the cage octaphenyl silsesquioxane in tetrahydrofuran , tetramethylammonium hydroxide aqueous solution refluxed for 4 ~ 6 hours.
  5. 5. 如权利要求4所述的方法,其特征在于:按质量比计,笼状八苯基倍半硅氧烷:四氢呋喃:四甲基氢氧化铵水溶液=(1〇〜20) : (100〜250) : (4〜8);其中,四甲基氢氧化铵水溶液的体积百分比浓度为25〜40%。 5. The method according to claim 4, wherein: the mass ratio, a cage-like silsesquioxane octaphenyl: tetrahydrofuran: an aqueous solution of tetramethylammonium hydroxide = (1〇~20): (100 ~ 250): (4 to 8); wherein the volume percent concentration of tetramethylammonium hydroxide aqueous solution was 25~40%.
  6. 6. 如权利要求2所述的方法,其特征在于:步骤b)中,缺角POSS:笼状七苯基三硅醇倍半娃氧烧与偏磷酸在四氢呋喃中于50〜80°C反应4〜6小时。 6. The method according to claim 2, wherein: in step b), the POSS chipping: seven phenyltriethoxysilane cage silsesquioxane silanol burn with oxygen Wa metaphosphate at 50~80 ° C in tetrahydrofuran 4 ~ 6 hours.
  7. 7. 如权利要求6所述的方法,其特征在于:按质量比计,笼状七苯基三硅醇倍半硅氧烷:偏磷酸:四氢呋喃=(1〇〜20) : (15〜25) : (100〜250)。 7. The method according to claim 6, wherein: the mass ratio, the cage seven three-phenyl silsesquioxane silanols: metaphosphoric acid: tetrahydrofuran = (1〇~20): (15~25 ): (100~250).
  8. 8. -种应用权利要求1所述的磷硅复合阻燃剂制备的硅橡胶复合材料,其特征在于: 按质量份数计,至少包括:74. 5〜94. 5质量份娃橡胶生胶,0. 5〜1. 5质量份固化剂及5〜 25质量份权利要求1所述的磷硅复合阻燃剂。 8. - P silicon composite silicone rubber flame retardant composite prepared according to claim 1 kind of application, wherein: parts by mass basis, at least comprising: 5 74 parts by mass of 5~94 baby rubber adhesive. , 0. 5~1. 5 parts by mass of a curing agent and -5 to 25 parts by mass of a phosphorus-silicon composite of claim 1, wherein said flame retardant.
  9. 9. 如权利要求8所述的硅橡胶复合材料,其特征在于,所述的硅橡胶复合材料的制备包括如下步骤:将权利要求1所述的磷硅复合阻燃剂加入硅橡胶生胶中,搅拌混合均匀后加入固化剂,继续搅拌混合均匀后倒入模具中,进行真空排气后于80〜120°C固化反应60〜90分钟,最后冷却至室温。 9. The silicone rubber composite according to claim 8, wherein preparing the silicone rubber composite material comprising the steps of: phosphorus flame-silicon composite according to claim 1 added in the silicone rubber adhesive after stirring and mixing uniformly the curing agent is added, stirring is continued after mixing uniformly poured into a mold, vacuum exhaust 80~120 ° C after the curing reaction 60~90 minutes, and finally cooled to room temperature.
  10. 10. 如权利要求9所述的硅橡胶复合材料,其特征在于:进行真空排气的真空度为150 〜160Pa。 10. The silicone rubber composite according to claim 9, wherein: the exhaust gas vacuum degree of vacuum of 150 ~160Pa.
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