【作者】 蒋健美；

【导师】 梁云；

【作者基本信息】 华南理工大学 ， 制浆造纸工程， 2010， 硕士

【摘要】 随着社会经济的发展,科学技术的不断进步,社会对纸的需求量不断增长,对纸的品种及性能的需求更为强烈。纸的使用范围越来越广,根据使用的不同目的,赋予纸以相应的要求也日益强烈。为了满足航空航天及耐高温领域的应用需求,耐高温特种纸基复合材料的研发势在必行。为保证耐高温特种纸基复合材料的性能,需对纸页进行树脂增强处理,传统的环氧树脂又难以满足耐高温的要求,这就需要合成对特种纸粘结性好的耐高温树脂。聚苯并噁嗪作为一种新型的酚醛树脂,不仅具有优异的热性能、阻燃性和电绝缘性,而且克服了传统酚醛树脂在固化成形过程中释放小分子的缺点,制品孔隙率低,接近零收缩,因此引起人们广泛的研究兴趣。为了改善特种纸的机械性能,耐高温性韧性及阻燃等综合性能,本文首先通过分子设计确定了苯并噁嗪的结构,进一步通过共聚和共混的方法对其进行改性。本文通过在苯并噁嗪中引入可聚合基团等合成了一系列高耐热性的具有一定分子量的苯并噁嗪中间体,与传统的小分子型苯并噁嗪中间体相比,由于其本身具有一定的分子量,因而进一步固化以后,具有比小分子型苯并噁嗪固化后更加优异的韧性,将其作为纸基复合材料的增强树脂,固化成型后形成的三维网络结构中,交联点之间分子链的长度和柔韧性,将实现对短切纤维的充分缠结和包裹,将有利于获得强韧性的纸基复合材料。进一步采用环氧树脂或橡胶树脂进行共聚或共混,以及通过在苯并噁嗪中引入有机和/或无机阻燃成分等制备高性能的特种纸。1.本论文分别以双酚AF,双酚A,甲醛,MDA,己二胺为原料合成了三种双酚二胺型的苯并噁嗪中间体BOZ-AFMDA,BOZ-AMDA,BOZ-HDM,并且通过加热固化反应合成了聚苯并噁嗪。PBOZ-AFMDA具有较好的综合性能,5%失重时温度为480℃,700℃氮气氛中的残碳率为87.28%,交联固化对应着低温和高温两个阶段,分别对应于150℃和170℃。BOZ-AMDA体系热性能次之,固化后所得树脂5%的失重温度为350℃,700℃氮气氛中的残碳率高达44%,其低温和高温交联温度分别对应于150℃,209℃。BOZ-AHDM固化后所得树脂热性能较差5%的失重温度为150℃,700℃氮气氛中的残碳率为30%。2.采用合成的系列苯并噁嗪树脂浸渍增强纸页(原纸定量60g/m2),结果表明,对纸页的力学性能增强作用由强到弱依次为AFMDA,AMDA,AHDM,苯并噁嗪对纸页的物理强度的提高有十分优异的效果,尤其是AFMDA体系,AFMDA体系浸渍特种纸基材料,其抗张强度可达7.42kN/m,撕裂强度可达2707mN。不同环氧值环氧树脂对纸页增强效果差异显著,以E44增强效果最佳,E44增强纸页的抗张强度,撕裂度,伸长率可达到6.52 kN/m,2964 mN,2.19%。当环氧树脂含量为30%时性能最佳,其700℃氮气氛中的残碳率为28.3%。3.采用液态橡胶改善树脂及纸基材料的韧性,结果表明,树脂基体的韧性大幅度提高,纸页的韧性也随之改善,但对树脂及纸页的耐热性有一定影响。ATBN体系较之CTBN有较好的增韧效果。4.采用阻燃剂及阻燃环氧树脂与苯并噁嗪树脂共混或共聚树脂浸渍纸基原纸,结果表明,含卤苯并噁嗪树脂AFMDA体系阻燃性能较好,室温极限氧指数为27.1%。溴化环氧树脂不仅使纸页有良好的阻燃性(EC1750体系的极限氧指数可达到27.8%),同时也使纸页力学性能得到保持。阻燃剂与环氧树脂共同改性纸页有优异的综合性能,极限氧指数达到28.4,在氮气氛中5%失重温度为300℃,700℃时的残碳率为72.9%。更多还原

【Abstract】 With the social and economic development, Scientific technologies advances insociety ,demand for paper and paper variety and performance become more intense. Widththe use of paper, according to different usage purposes, to give papers to the appropriaterequirements also increased. To meet the field of aerospace and high temperature applications,high temperature specialty research and development is imperative.To ensure thermal stability performance of special paper, Enhanced resin is required .The traditional high-temperature epoxy resin is hard to meet the needs, which requiressynthesis good high temperature resin for specialty paper bonding. Benzoxazine as a new typeof phenolic resin, not only has excellent thermal properties, flame resistance and electricalinsulation, and overcome the shortcomings of release of small molecules in formingcuring process of traditional phenolic resin, products has low porosity, near-zero shrinkage,thus causing the widespread interest in the study.In order to improve the mechanical properties of specialty paper, heat resistance andtoughness, flame retardant and other comprehensive performance, In this paper, methods ofmolecular design, and the third component copolymer resin blend were used. In this paper, theintroduction of the benzoxazine polymerizable groups such as A series of high heat resistancebenzoxazine intermediate with a molecular weight has been synthesised , and compared withtraditional small molecule-based benzoxazine intermediates ,benzoxazine with a molecularweight of its own, thus further solidifying , with more excellent toughness than smallmolecule-based benzoxazine , as paper-based composites reinforced resin, curing molding toform three-dimensional network structure, and successive point between the molecular chainlength and flexibility, to realize the full tangles of short fiber and packages,which will helpenhance paper strength and toughness of composites. Further with the epoxy resin copolymer,rubber modified blends the mechanical properties and toughness of specialty paper, andthrough the introduction of benzoxazine organic and / or inorganic flame retardant ingredientsPreparation of specialty paper.1. In this thesis, with bisphenol AF, bisphenol A, formaldehyde, MDA, diamine as rawmaterial ,three diamine bisphenol-type benzoxazine BOZ-AFMDA, BOZ-AMDA,BOZ-HDM has been synthesized, and by heating polymerization reaction of the benzoxazine.PBOZ-AFMDA has good overall performance, with 5% weight loss temperature of 480℃,700℃in nitrogen atmosphere, the residual carbon was 87.28%, the initial temperature ofintermediate thermal ring-opening polymerization is 177℃, exothermic peak temperature to 234℃. BOZ-AMDA system thermal performance in hot pursuit , a 5% weight losstemperature of post-curing resin was 350℃, 700℃in nitrogen atmosphere, the residualcarbon rate of 44%. The thermal ring-opening polymerization of the initial temperature of 209℃, exothermic peak temperature of 251℃. BOZ-AHDM cured resin derived poor thermalperformance of a 5% weight loss temperature was 150℃, 700℃in nitrogen atmosphere,the residual carbon was 30%.2. Series of synthetic Benzoxazine resin were adopted to impregnated enhanced sheet,the results show that the mechanical properties of paper sheet enhanced , the order ofenhancement from strong to weak :AFMDA, AMDA, AHDM, benzoxazine has a veryexcellent results to improve the physical strength of paper sheet, especially AFMDA system,AFMDA system based materials impregnated special paper, the tensile strength of up to7.42kN / m, tear strength up to 2707mN. Values of epoxy resin on the sheet enhancementsignificantly different to enhance the best is E44, E44 enhance the tensile strength of the sheet,tear, elongation up to 6.52 kN / m, 2964 mN, 2.19% . When the epoxy resin content is 30%,the best performance, the 700℃in nitrogen atmosphere, the residual carbon rate was28.3%.3. Improve toughness of the resin and paper-based materials with liquid rubber and thetoughness of the resin matrix significantly improved ,the toughness of the sheet also willimprove, but the heat-resistant of sheet and resin to vary on some extent. toughening effect.ofATBN system is better than CTBN .4. flame retardants and flame-retardant epoxy resins adopted with benzoxazine blend orcopolymer resin impregnated paper-based base paper, the results show that the benzoxazineresins containing halogen flame retardant AFMDA system is better at room temperature,limiting oxygen index of 27.1 %. Brominated epoxy resin not only own good flame resistanceof sheet (EC1750 system, limiting oxygen index up to 27.8%), while also maintaining themechanical properties of paper sheets. Common modification of epoxy resin flame retardantsheet has excellent overall performance, limiting oxygen index of 28.4, in nitrogenatmosphere 5% weight loss temperature of 300℃, 700℃when the residual carbon was72.9%.更多还原