WO2018095358A1 - 一种含磷氮硅聚合物阻燃剂及其制备方法与应用 - Google Patents

一种含磷氮硅聚合物阻燃剂及其制备方法与应用 Download PDF

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WO2018095358A1
WO2018095358A1 PCT/CN2017/112580 CN2017112580W WO2018095358A1 WO 2018095358 A1 WO2018095358 A1 WO 2018095358A1 CN 2017112580 W CN2017112580 W CN 2017112580W WO 2018095358 A1 WO2018095358 A1 WO 2018095358A1
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phosphorus
nitrogen
flame retardant
epoxy resin
dopo
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French (fr)
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戴李宗
陈婷
刘诚
王世成
陈国荣
袁丛辉
许一婷
曾碧榕
罗伟昂
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Xiamen University
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
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    • B29C39/38—Heating or cooling
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    • 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
    • C08G59/20—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 epoxy compounds used
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    • 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
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    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
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    • 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
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
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    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0026—Flame proofing or flame retarding agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2905/00—Use of metals, their alloys or their compounds, as mould material
    • B29K2905/02—Aluminium
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    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
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    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention belongs to the technical field of organic flame retardants, and particularly relates to a phosphorus-nitrogen-containing silicon polymer flame retardant and a preparation method and application thereof.
  • Epoxy resin is a kind of polymer material with high strength, good bonding performance, good corrosion resistance and excellent dielectric properties. It is widely used in civil engineering, electronic appliances, aerospace and automotive machinery. It plays an indispensable position in all sectors of the national economy. However, epoxy resin is a relatively flammable material. This shortcoming also greatly limits the application of epoxy resin. The flame retardant of epoxy resin has also been the subject of unremitting research by researchers.
  • Multi-element flame retardant is a kind of flame retardant technology which has emerged in recent years.
  • CN201510132367.3 discloses a phosphorus-containing and nitrogen-expanded flame retardant as an epoxy resin reactive flame retardant curing agent, which not only has resistance. The burning effect can also cure the epoxy resin, and the cured product has good mechanical properties.
  • CN201510132367.3 discloses a DOPO-derived flame retardant, which utilizes phosphorus-nitrogen synergistic flame retardant effect of phosphorus-nitrogen flame retardant, and has better thermal stability and good char formation effect, and is used for polymer such as epoxy resin.
  • the flame retardant and flame retardant effect of the material expands the application range of DOPO flame retardant.
  • the flame retardant effect of the multi-element flame retardant is good, but most of the existing flame retardants are mainly small molecules, and there are often disadvantages of lowering the thermal stability or mechanical properties of the material.
  • Another object of the present invention is to provide a process for preparing the above-mentioned phosphorus-nitrogen-containing silicon polymer flame retardant.
  • step (2) sequentially adding the phosphorus-containing epoxy monomer EP-DOPO, aminopropyl cage polysilsesquioxane (POSS-NH 2 ), sodium methoxide and the first obtained in the step (1) to another reaction vessel.
  • the organic solvent is heated to 60-120 ° C, protected by nitrogen, reacted for 4-24 hours, and then precipitated with methanol to obtain a filter cake.
  • the filter cake is washed with methanol, and the obtained white solid is dried in a vacuum drying oven at 60 ° C for 24 hours.
  • the phosphorus-nitrogen-containing silicon polymer flame retardant The phosphorus-nitrogen-containing silicon polymer flame retardant; the molar ratio of the phosphorus-containing epoxy monomer EP-DOPO, aminopropyl cage polysilsesquioxane and sodium methoxide is 1:0.01-0.1:0.01-0.1.
  • the first organic solvent is dichloromethane, toluene or tetra Carbon chloride.
  • the second organic solvent is toluene, N,N-dimethylformamide or 1,4-dioxane.
  • the above-mentioned phosphorus-nitrogen-containing silicon polymer flame retardant is used in the preparation of a flame-retardant epoxy resin.
  • the epoxy resin prepolymer is weighed to 70 to 110 ° C, 0.1 to 50 wt% of the phosphorus-nitrogen-containing silicon polymer flame retardant is added, and stirred until uniformly uniform. Then, the curing agent 4,4-diaminodiphenylmethane (DDM) was added to the stoichiometric ratio until completely dissolved, and then poured into an aluminum mold, and a temperature rising program was set to cure to obtain a flame-retardant epoxy resin.
  • DDM 4,4-diaminodiphenylmethane
  • the epoxy resin prepolymer is an E51 bisphenol A type epoxy resin.
  • the mass ratio of the epoxy resin prepolymer to the curing agent 4,4-diaminodiphenylmethane is 8:2.02.
  • the heating procedure is: curing at 120 ° C for 4 h, curing at 140 ° C for 2 h, and curing at 180 ° C for 2 h.
  • the preparation method of the present invention prepares a phosphorus-nitrogen silicon integrated polymer flame retardant by using a phosphorus-containing epoxy monomer and a POSS-NH 2 as an initiator, and a phosphorus-nitrogen-silicon polymer flame retardant is prepared by a ring-opening reaction of propylene oxide.
  • the polymer type flame retardant tends to have better compatibility with the polymer matrix. Since the polymer molecular chain contains a large amount of -CO-bond, the polymer molecular chain has a certain softness. The property further improves the compatibility of the flame retardant with the polymer matrix; at the same time, the flame retardant epoxy resin after curing has good thermal stability and mechanical properties;
  • the aminopropyl cage polysilsesquioxane (POSS-NH 2 ) used in the present invention is an organic/inorganic intramolecular hybrid system at the molecular level, and its core is a cage-shaped inorganic skeleton composed of silicon oxide.
  • POSS-NH 2 has better stability at high temperature, and its nano-size effect makes it improve thermal stability and oxidation resistance. At the same time, it can improve the mechanical properties of the material.
  • the phosphorus-nitrogen-containing silicon polymer flame retardant of the present invention contains 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and aminopropyl cage polyhalogen
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • POSS-NH 2 aminopropyl cage polyhalogen
  • POSS-NH 2 has better solubility in epoxy resin
  • POSS-NH 2 has poor solubility in epoxy resin, which makes the flame retardant in epoxy resin.
  • Self-assembly will form a nanostructure with POSS as the core and DOPO as the shell, which has nano-enhancement effect on the matrix material.
  • Synergistic flame retardant effect between phosphorus, nitrogen and silicon in the phosphorus-nitrogen-containing silicon polymer flame retardant of the invention Improve the flame retardant properties of epoxy resin
  • the molecular weight of the phosphorus-nitrogen-containing silicon polymer flame retardant of the invention is controllable, and the phosphorus, nitrogen and silicon content ratio in the system can be controlled by adjusting the molecular weight of the polymer;
  • the synthesis reaction of the preparation method of the invention is simple, the raw material cost is low, and the yield of the product is high.
  • Example 1 is a nuclear magnetic resonance spectrum of a phosphorus-nitrogen-containing silicon polymer flame retardant in Example 1;
  • the epoxy resin prepolymer was an E51 bisphenol A type epoxy resin.
  • the oxygen index of the flame-retardant epoxy resin of this example was measured according to GB/T 2406-2009 to be 28.1%.
  • the flame retardancy epoxy resin of this example was found to have an oxygen index of 27.5% according to GB/T 2406-2009.
  • the oxygen index of the flame retardant epoxy resin of this example was measured according to GB/T 2406-2009 to be 28.8%.
  • step (1) (1) Add 2.88 g (38.89 mmol) of glycidol, 8 g (37.04 mmol) of DOPO, 3.94 g (38.89 mmol) of triethylamine and 50 mL of toluene to a single-mouth bottle in an ice bath, step (1) 2 h; The mixture was repeatedly quenched three times, and the organic phase was dried over anhydrous magnesium sulfate, suction filtered, and the solvent was evaporated to give the monomer EP-DOPO.
  • the oxygen index of the flame-retardant epoxy resin of this example was measured according to GB/T 2406-2009 to be 28.3%.
  • the oxygen index of the flame-retardant epoxy resin of this example was measured according to GB/T 2406-2009 to be 28.2%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)
  • Fireproofing Substances (AREA)

Abstract

一种含磷氮硅聚合物阻燃剂及其制备方法和应用，其化学式结构为：，其中，m＝10～100，n＝10～100。所述含磷氮硅聚合物阻燃剂中磷、氮、硅三者之间的协同阻燃效果提高了环氧树脂的阻燃性能。

Description

一种含磷氮硅聚合物阻燃剂及其制备方法与应用 技术领域
本发明属于有机阻燃剂技术领域，具体涉及一种含磷氮硅聚合物阻燃剂及其制备方法与应用。
背景技术
环氧树脂是一类具有强度高、粘结性能好、耐腐蚀性好及介电性能优异等优点的高分子材料，被广泛应用于土木建筑、电子电器、航天航空及汽车机械等领域中，在国民经济各部门中起着不可或缺的位置。然而，环氧树脂是一类相对易燃的材料，这个缺点也大大限制了环氧树脂的应用，环氧树脂的阻燃也一直是研究者们不懈探讨的课题。
多元素阻燃剂是近年来兴起的一类阻燃技术，CN201510132367.3公开了一种含磷、氮膨胀型阻燃剂，作为一种环氧树脂反应型阻燃剂固化剂，不仅具有阻燃效果，还可以固化环氧树脂，固化物力学性能好。CN201510132367.3公开了一种DOPO衍生阻燃剂，利用磷氮阻燃剂的磷氮协同阻燃作用，及其较好的热稳定性和良好的成炭作用，用于环氧树脂等高分子材料的阻燃，阻燃效果好，拓展了DOPO阻燃剂的应用范围。含有多元素阻燃剂的阻燃效果良好，但现有的阻燃剂大多以小分子为主，往往存在着降低材料热稳定性或机械性能的缺点。
发明内容
本发明目的在于提供一种含磷氮硅聚合物阻燃剂。
本发明的另一目的在于提供上述含磷氮硅聚合物阻燃剂的制备方法。
本发明的目的在于提供上述含磷氮硅聚合物阻燃剂的应用。
本发明的技术方案如下：
一种含磷氮硅聚合物阻燃剂，其化学式结构为：
Figure PCTCN2017112580-appb-000001
其中，m＝10～100，n＝10～100。
上述含磷氮硅聚合物阻燃剂的制备方法，其合成路线如下所示：
Figure PCTCN2017112580-appb-000002
具体包括如下步骤：
(1)在冰浴下依次向反应容器中加入缩水甘油、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、三乙胺和第一有机溶剂，室温反应4～16h，接着用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后，得含磷环氧单体EP-DOPO；上述缩水甘油、DOPO和三乙胺的摩尔比为1∶0.5～2.5∶0.5～2.5
(2)依次向另一反应容器中加入步骤(1)中所得的含磷环氧单体EP-DOPO、氨丙基笼型聚倍半硅氧烷(POSS-NH2)、甲醇钠和第二有机溶剂，加热至60～120℃，通氮气保护，反应4～24h，接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂；上述含磷环氧单体EP-DOPO、氨丙基笼型聚倍半硅氧烷和甲醇钠的摩尔比为1∶0.01～0.1∶0.01～0.1。
在本发明的一个优选实施方案中，所述第一有机溶剂为二氯甲烷、甲苯或四 氯化碳。
在本发明的一个优选实施方案中，所述第二有机溶剂为甲苯、N，N-二甲基甲酰胺或1，4-二氧六环。
上述含磷氮硅聚合物阻燃剂在制备阻燃性环氧树脂中的应用。
在本发明的一个优选实施方案中，具体为：称取环氧树脂预聚体升温至70～110℃，加入0.1～50wt％的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，接着按化学计量比加入固化剂4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
进一步优选的，所述环氧树脂预聚体为E51双酚A型环氧树脂。
进一步优选的，所述环氧树脂预聚体与固化剂4，4-二氨基二苯甲烷的质量比为8∶2.02。
进一步优选的，所述升温程序为：120℃固化4h，140℃固化2h，180℃固化2h。
本发明的有益效果是：
1、本发明的制备方法通过制备含磷的环氧单体，以POSS-NH2为引发剂，利用环氧丙烷的开环反应制备出磷氮硅一体的聚合物阻燃剂，与小分子型阻燃剂相比，聚合物型的阻燃剂往往与聚合物基体具有更好的相容性，由于聚合物分子链中含有大量的-C-O-键，使聚合物分子链具有一定的柔软性，进一步提高了阻燃剂与高分子基体的相容性；同时固化后的阻燃性环氧树脂热稳定性与机械性能好；
2、本发明使用的氨丙基笼型聚倍半硅氧烷(POSS-NH2)是一个分子水平上的有机/无机分子内杂化体系,它的核心是硅氧组成的笼形无机骨架，相比于传统的线型硅氧烷改性体系，POSS-NH2在高温下具有更好的稳定性，并且，它的纳米尺寸效应使它在提高热稳定性、抗氧化性阻燃性能的同时能够提高材料的机械性能。
3、本发明的含磷氮硅聚合物阻燃剂中含有9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和氨丙基笼型聚倍半硅氧烷(POSS-NH2)这两部分结构，DOPO在环氧树脂中溶解性较好，而POSS-NH2在环氧树脂中溶解性较差，这使得阻燃剂在环氧树脂中会自组装形成以POSS为核、DOPO为壳的纳米结构，对基体材料具有纳米增强作用。
4、本发明的含磷氮硅聚合物阻燃剂中磷、氮、硅三者之间的协同阻燃效果 提高了环氧树脂的阻燃性能；
5、本发明的含磷氮硅聚合物阻燃剂的分子量可控，通过聚合物的分子量的调节可以控制体系中的磷、氮、硅含量比；
6、本发明的制备方法的合成反应较简单，原料成本低，产物的产率高。
附图说明
图1为实施例1中含磷氮硅聚合物阻燃剂的核磁共振氢谱图；
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
下述实施例中，环氧树脂预聚体为E51双酚A型环氧树脂。
实施例1
(1)在冰浴下依次向单口瓶中加入2.88g(38.89mmol)缩水甘油、7g(32.41mmol)DOPO、3.94g(38.89mmol)三乙胺和50mL二氯甲烷，室温反应8h；接着用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后得单体EP-DOPO。
(2)依次向双口瓶中加入5.72g(19.86mmol)步骤(1)中所得单体EP-DOPO、0.35g(0.40mmol)POSS-NH2、0.01g(0.20mmol)甲醇钠和30mL N，N-二甲基甲酰胺，加热至80℃，通氮气保护，反应进行12h；接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂(如图1所示)。
(3)称取20g环氧树脂预聚体升温至70℃，加入1.32g的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，接着加入5.05g4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
根据GB/T 2406-2009测得本实施例的阻燃性环氧树脂的氧指数为28.1％。
实施例2
(1)在冰浴下依次向单口瓶中加入2.88g(38.89mmol)缩水甘油、 7g(32.41mmol)DOPO、3.94g(38.89mmol)三乙胺和50mL二氯甲烷，反应8h；接着用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后得单体EP-DOPO。
(2)依次向双口瓶中加入5.72g(19.86mmol)步骤(1)中所得单体EP-DOPO、0.35g(0.40mmol)POSS-NH2、0.01g(0.20mmol)甲醇钠和30mL N，N-二甲基甲酰胺，加热至80℃，通氮气保护，反应进行12h；接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂。
(3)称取20g环氧树脂预聚体升温至70℃，加入0.61g的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，接着加入5.05g4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
根据GB/T 2406-2009测得本实施例的阻燃性环氧树脂的氧指数为27.5％。
实施例3
(1)在冰浴下依次向单口瓶中加入2.88g(38.89mmol)缩水甘油、7g(32.41mmol)DOPO、3.94g(38.89mmol)三乙胺和50mL二氯甲烷，反应8h；接着水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后得单体EP-DOPO。
(2)依次向双口瓶中加入5.72g(19.86mmol)步骤(1)中所得单体EP-DOPO、0.35g(0.40mmol)POSS-NH2、0.01g(0.20mmol)甲醇钠和30mL N，N-二甲基甲酰胺，加热至80℃，通氮气保护，反应进行12h；反接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂。
(3)称取20g环氧树脂预聚体升温至70℃，加入1.88g的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，接着加入5.05g4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
根据GB/T 2406-2009测得本实施例的阻燃性环氧树脂的氧指数为28.8％。
实施例4
(1)在冰浴下依次向单口瓶中加入2.88g(38.89mmol)缩水甘油、8g(37.04mm0l)DOPO、3.94g(38.89mmol)三乙胺和50mL甲苯，步骤(1)2h；接着用水反复淬洗三次，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后得单体EP-DOPO。
(2)依次向双口瓶中加入5.72g(19.86mmol)步骤(1)中所得单体EP-DOPO、0.35g(0.40mmol)POSS-NH2、0.01g(0.20mmol)甲醇钠和30mL甲苯，加热至80℃，通氮气保护，反应进行12h；接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂。
(3)称取20g环氧树脂预聚体升温至70℃，加入1.32g的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，接着加入5.05g4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
根据GB/T 2406-2009测得本实施例的阻燃性环氧树脂的氧指数为28.3％。
实施例5
(1)在冰浴下依次向单口瓶中加入2.88g(38.89mmol)缩水甘油、7g(32.41mmol)DOPO、3.94g(38.89mmol)三乙胺和50mL二氯甲烷，反应8h；接着用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后得单体EP-DOPO。
(2)依次向双口瓶中加入5.72g(19.86mmol)步骤(1)中所得单体EP-DOPO、0.70g(0.80mmol)POSS-NH2、0.02g(0.40mmol)甲醇钠和30mL N，N-二甲基甲酰胺，加热至80℃，通氮气保护，反应进行12h；接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂。
(3)称取20g环氧树脂预聚体升温至70℃，加入1.32g的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，接着加入5.05g4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
根据GB/T 2406-2009测得本实施例的阻燃性环氧树脂的氧指数为28.2％。
本领域普通技术人员可知，本发明的技术方案在下述范围内变化时，仍然能 够得到与上述实施例相同或相近的技术效果，仍然属于本发明的保护范围：
以上所述，仅为本发明的较佳实施例而已，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. 一种含磷氮硅聚合物阻燃剂，其特征在于：其化学式结构如下：
    Figure PCTCN2017112580-appb-100001
    其中，m＝10～100，n＝10～100。
  2. 如权利要求1所述的一种含磷氮硅聚合物阻燃剂的制备方法，其特征在于：其合成路线如下所示：
    Figure PCTCN2017112580-appb-100002
    具体包括如下步骤：
    (1)在冰浴下依次向反应容器中加入缩水甘油、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、三乙胺和第一有机溶剂，室温反应4～16h，接着用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂后，得含磷环氧单体EP-DOPO；上述缩水甘油、DOPO和三乙胺的摩尔比为1∶0.5～2.5∶0.5～2.5；
    (2)依次向另一反应容器中加入步骤(1)中所得的含磷环氧单体EP-DOPO、氨丙基笼型聚倍半硅氧烷(POSS-NH2)、甲醇钠和第二有机溶剂，加热至60～120℃，通氮气保护，反应4～24h，接着用甲醇沉淀得滤饼，滤饼用甲醇冲洗，所得白 色固体于真空干燥箱中60℃干燥24h，即得所述含磷氮硅聚合物阻燃剂；上述含磷环氧单体EP-DOPO、氨丙基笼型聚倍半硅氧烷和甲醇钠的摩尔比为1∶0.01～0.1∶0.01～0.1。
  3. 如权利要求2所述的制备方法，所述第一有机溶剂为二氯甲烷、甲苯或四氯化碳。
  4. 如权利要求2所述的制备方法，所述第二有机溶剂为甲苯、N，N-二甲基甲酰胺或1，4-二氧六环。
  5. 权利要求1所述的含磷氮硅聚合物阻燃剂在制备阻燃性环氧树脂中的应用。
  6. 如权利要求5所述的应用，其特征在于：具体为：称取环氧树脂预聚体升温至70～110℃，加入0.1～50wt％的含磷氮硅聚合物阻燃剂，搅拌至呈均一透明的状态，按化学计量比加入固化剂4，4-二氨基二苯甲烷(DDM)直至完全溶解，倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
  7. 如权利要求6所述的应用，其特征在于：所述环氧树脂预聚体为E51双酚A型环氧树脂。
  8. 如权利要求6所述的应用，其特征在于：所述环氧树脂预聚体与固化剂4，4-二氨基二苯甲烷的质量比为8∶2.02。
  9. 如权利要求6所述的应用，其特征在于：所述升温程序为：120℃固化4h，140℃固化2h，180℃固化2h。
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