【作者】 吴勇；

【导师】 朱靖；

【作者基本信息】 河南工业大学 ， 有机化学， 2011， 硕士

【摘要】 聚磷腈是一类以氮磷单双键交替排列为主链的线型或环状的聚合物。作为一种新型的材料，它们在社会各行业都有着广泛的研究和应用，特别是阻燃材料领域，随着人们对无氯、低毒、低烟、耐久、低成本以及环保经济阻燃材料的要求，磷腈类化合物作为膨胀型阻燃剂因具有良好的阻燃性能而受到世界各国的广泛关注。环氧树脂作为高分子材料以其良好的特性已成为三大通用型热固性树脂之一，在社会诸多领域有着广泛的应用，但其易燃性却对人的生命和安全生产造成较大的隐患。为此，本论文主要是研究磷腈类化合物对环氧树脂的阻燃。首先以氯化铵和五氯化磷为原料合成六氯环三磷腈（HCCP），并采用正交设计对其合成工艺进行优化，得出了较佳合成条件和影响反应的较大因素，对合成六氯环三磷腈的机理进行了初步探讨。以HCCP为原料，合成了六对硝基苯氧基环三磷腈（PN-p-NO₂）、六对醛基苯氧基环三磷腈（PN-p-CHO）、六邻醛基苯氧基环三磷腈（PN-o-CHO），经还原反应分别得到六对氨基苯氧基环三磷腈（PN-p-NH₂）、六对羟甲基苯氧基环三磷腈（PN-p-OH）和六邻羟甲基苯氧基环三磷腈（PN-o-OH）；经过氧化反应得到六对羧基苯氧基环三磷腈（PN-p-COOH）。分别使用元素分析、熔点测定、FT-IR、NMR、DSC等测试手段对这些环磷腈化合物进行了结构表征和性能测试。以乙醇胺和二乙醇胺与丙烯酸甲酯经迈克尔加成反应分别得到N-羟乙基-3-胺基-N,N-二丙酸甲酯（M₁）和N, N-二羟乙基-3-氨基丙酸甲酯（M₂）两种（AB₂型）单体，以前者M₁和HCCP反应得到的酯端基超支化聚（氨-酯）；后者M₂和PN-p-OH反应得到羟端基的超支化聚（氨-酯）。以PN-p-OH、四氢呋喃和环氧氯丙烷在三氟化硼乙醚催化下反应得到了超支化聚四氢呋喃缩水甘油醚。并利用FTIR、NMR、GPC等手段对产物结构进行了表征，测定了羟端基超支化聚（氨-酯）的羟值，对超支化聚四氢呋喃缩水甘油醚的环氧值也进行了测定。分别以4、4’-二氨基二苯甲烷（DDM）、4、4’-二氨基二苯砜（DDS）和PN-p-NH₂及其混合物为固化剂对双酚A型环氧树脂（DGEBA）进行固化；以PN-p-OH和PN-o-OH与DGEBA反应得到环氧树脂预聚体，以DDS、DDM和邻苯二甲酸酐（PA）进行固化；分别以酯端基超支化聚（氨-酯）、羟端基超支化聚（氨-酯）和超支化聚四氢呋喃缩水甘油醚添加到DGEBA中，以DDM固化；均得到含环三磷腈的阻燃型环氧树脂。并通过热重分析（TGA）对其热稳定性和阻燃性进行测试。更多还原

【Abstract】 Polyphosphazene are polymers having chemical structures containing alternating basedphosphorus and nitrogen atoms forming a ring structure and linear compounds havingchain-like backbones of phosphorus and nitrogen atoms with alternating double and singlebonds. As a new materials, phosphazenes have a wide range of research and application in allsocial sectors, especially in flame retardant material area. With the demand the fire-retardantmaterials is toward to halogen-free, low posin, low smoke, durable, low cost as well asenvironment friendship, as intumescent flame retardant phosphazene compounds attractedworld wide attention because of excellent flame retardancy. As one of three general purposethermosetting resins, Epoxy resin polyer with good properties have a wide application inmany fields, but its flammability has caused large hazard for human life and safety. So thispaper is to study the epoxy resin retardant with phosphazenes.First, hexachlorocyclotriphosphazene（HCCP） was prepared by the reaction of ammoniumchloride with phosphorus pentachloride. The optimal reaction conditions and larger factorseffecting reaction were obtained by orthogonal design, and the synthetic mechanism wasdiscussed preliminarily.Hexakis（4-aldehydephenoxy）-cyclotriphosphazene（PN-p-CHO）, hexakis （2-aldehyde-phenoxy）-cyclotriphosphazene（PN-o-CHO） and hexakis（4-nitrophenoxy）-cyclotriphospha-zene（PN-NO₂） were synthesized with HCCP as a raw material. Hexakis（4-h-ydroxypheno-xy）-cyclotriphosphazene（PN-p-OH）, hexakis（2-hydroxyphenoxy）-cyclotriphosphazene（PN-o-OH）, hexakis（4-aminophenoxy）-cyclotriphosphazene （PN-NH₂）, hexakis （4-carboxyl-phenoxy）cyclotriphosphazene （PN-p-COOH） were obtained respectively after reduction andoxidation reactions. Their structures and properties were characterized by elemental analysis,melting point, FTIR,1H NMR and31P NMR.As two monomer, dimethyl3,3’-（2-hydroxyethylazanediyl）dipropanoate （M₁） and methyl3-（bis（2-hydroxyethyl）amino）propanoate （M₂） were synthesized via Michael additionreaction of ethanolamine and diethanolamine with methyl acrylate respectively.The hyperbranched poly（amine-ester） with ester terminal groups and hydroxyl groups weresynthesized via reaction of two monomers with HCCP and PN-o-OH respectively. Thehyperbranched polytetrahydrofuran glycidyl ether was synthesized based on the reaction ofPN-p-OH with THF and epichlorohydrin using boron trifluoride etherate as catalyst. The molecular composition of the hyperbranched polymer were characterized by FTIR, NMR andGPC. The hydroxyl value of the hydroxyl end groups of hyperbranched poly（amine-ester）and epoxy value of the hyperbranched polytetrahydrofuran glycidyl ether were determined.The commercial epoxy resin Diglycidyl ether of bisphenol-A （DGEBA） was cured with4,4’-diaminodiphenylsulfone（DDS），4,4’-diaminodiphenylmethane （DDM），PN-p-NH₂andtheir mixture respectively; The epoxy resin prepolymers were obtained in turn after thereaction of DGEBA with PN-p-OH and PN-o-OH, and then cured with DDS, DDM and PArespectively; the hydroxyl end groups and ester end groups of hyperbranchedpoly（amine-ester） and hyperbranched polytetrahydrofuran glycidyl ether were added toDGEBA respectively, after reaction the products were cured with DDM. In this way, Thecured different flame retardant epoxy resins with the cyclotriphosphazene were obtained.Their thermodynamic stability and flame-retardant properties were evaluated by usingthermogravimetric analysis （TGA）.更多还原