阻燃聚酯的制备、性能与应用研究

【作者】 牛明军；

【导师】 李新法； 陈金周；

【作者基本信息】 郑州大学 ， 材料学， 2000， 硕士

【摘要】 聚酯因具有可燃性已严重影响了其在许多方面的应用和发展，我们以聚对苯二甲酸乙二醇酯（PET）为基材，选择高效多元复合阻燃体系，采用双螺杆挤出机挤出造粒新工艺，研制出了新型阻燃聚酯材料；通过锥型量热仪（CONE）和热失重（TG）相结合的研究手段系统研究了PET和阻燃聚酯的热行为、热降解动力学以及烟释放、热释放与成炭的关系；利用XLY-2型流交仪研究了PET和阻燃聚酯的流变行为；利用微机控制电子万能试验机等研究了PET和阻燃聚酯的物理力学性能；在优化工艺和配方的基础上制备了高档阻燃PET人造发丝料，并应用于高档人造发丝的工业化生产。 1．尽管TG和CONE对PET及阻燃聚酯的热降解、交联和成炭的研究实验条件上有很大的差别，但所得的实验结果有很大的一致性。SB/FR阻燃体系能够促进阻燃聚酯提前分解成炭，提高残炭量，并随着阻燃剂配比的不同，残炭量出现了极大值，隔热、隔氧阻止热裂解的进一步发展。 2．通过PET及阻燃聚酯的热降解动力学分析，求得了不同失重率的反应活化能E和频率因子lgA，本工作未见报道；根据时—温等效原理得到了一系列恒失重率的温度—时间曲线，为确定材料在某一温度下的使用寿命或达到某一使用寿命所允许的最高使用温度提供了科学依据。 3．首次在50kWm^-2条件下利用CONE研究了阻燃聚酯的阻燃性能。结果表明：.SB/FR能协同作用延长阻燃聚酯的点燃时间，并随着阻燃剂配比的不同，点燃时间出现了极大值；同一配比的情况下，随着阻燃剂用量的增加，点燃时间延长。说明了点燃时间延长是聚合物气相阻燃的特征。 4．SB/FR阻燃剂的加入降低了体系的热释放速率、总热释放量、平均有效燃烧热，使最大热释放速率对应的时间提前。热释放的速度及总量均与质量损失速率及量相联系，实质是凝聚相成炭提前与残炭量增加所致，显示了阻燃剂的凝聚相阻燃特征。 5．SB/FR使阻燃聚酯的烟释放速率、烟释放量、CO、CO₂释放量有所降低，烟性能、毒性下降。随着阻燃剂配比的不同，烟释放量有一极小值。同一配比时，随着用量的减少，比消光面积减小，发烟量减小。 6．研究剪切速率、剪切应力和温度与阻燃聚酯熔体表观粘度的关系表明， 阻燃聚酯熔体的表观粘度随着温度的升高而降低；粘流活化能（凸E）随着剪 切速率的增大而减小：在实验温度下，阻燃聚酯熔体的表现粘度随剪切速率和 剪切应力的增大而降低，非牛顿指数（n）小于1，阻燃聚酯熔体为假塑性流 体。 7．该阻燃聚酯应用于高档阻燃PET人造发丝料，具有优良的纺丝工艺性 能，生产的高档阻燃人造发丝阻燃效果优异、手感好、柔软度适中、垂度好。厂 完全适用于阻燃人造发套的需要。 8．采用双螺杆挤出机挤出造粒，工艺先进，混合和加工性能良好，已经 推广应用，产生了良好的经济和社会效益。 9．研制开发的高档阻燃PET人造发丝料，产品配方设计科学合理、思路 新颖，制备工艺先进，有所创新。经河南省科学技术情报研究所文献检索，填 补了国内该项空白。更多还原

【Abstract】 The application and development of polyester in many fields twaysl have been seriously affected because of its flammability. With polyethylene terephthalate(PET) as main raw material , choosing highly-effective blend system for flame retardance and adopting two-screw extruder as a new technology, we succeed in a new-typed polyester material for flame retardance. In this thesis, thermal behaviors, heat- degradation kinetics, and the relationship between smoke, heat release and char residue of PET and flame-retarding polyester by the combination of CONE with TG as a research method. A XLY-2 type capillary rheometer was used to study their rheological behaviorc and in addition, mechanical properties were studied by electronic verstatile experimental machine controlled by computer. On basis of majorized technology and proportion, artificial hair silk material was prepared which has been applied in artificial hair silk industry. Besides some valuable conclusions drawn are as folow: 1. In spite of the divergence of TG on CONE in experimented conditions, both results are in great agreement. SB/FR system can prompt the advance decomposition of flame-retarded earlier and char residue is raised and its maximum occurs as the ratio of flame-retarded varies , the prohition of thermal decomposition rise further by thermal insulation and oxygen insulation. 2. The kinetic analysis of PET and flame-retarding polyester leads to reaction actification energy(E) and frequency factor(lgA) in different weight loss ratio and this work above has never been reported. According to Time-Temperature Principle, the temperature-time curves for a series of constant weight loss rates are obtained, which offers scientifical proofs to establish the span for use at a certain temperature or the maximum temperature for use. 3. For the first time, CONE analysis under 5OkW.m2 show that the synergistic effect of SB/FR can lengthen time to ignition (TTI) , the maximum of which occurs with the variation of the composition of flame-retardant. At the composition, TTI is prolonged with the increase of the content of flame-retardant, which illustrates that the delay of TTI characterizes the gas-phase flame retardance for polymer. 4. Addition of the flame-retardant (SB/FR) reduce HIRR(HIEAT Release Rate ),TLIR(Total Heat Release and EHC (Effective Heat of Combustion) and in addition ,the time which is correspondent with the maximum HIRR is advance the correlation between both rate and content of heat release and both rate and content of mass loss, in fact ,result from the earlier formation of condensed phase into char and a rise in char residue, which shows the characteristics of condensed phase for flame-retardant. 5. SB/FR reduce SPR(smoke Production Rate), SP(Smoke Production), production of co and cc2 and toxicity of the polyester . As the composition of flame-retardant varies, TSP has a minimum and at the some composition SEA (specific Extinction Area) and TSP drop with the reduction of its content. 6. The influence of shear rate, shear stress and temperature on apparent melt viscocity of flame-retarding PET was studied and results show that apparent melt viscocity drops with the increasing of temperature, and so does activation energy for viscous flow (E) with the increasing of shear rate. At experimental temperature, the apparent melt viscosity decreases with the increasing of shear rate and shear stress and value of non-Newton index(n) is less than 1 , which indicates that melt of flame-retarding polyester更多还原