【作者】 程博闻；

【导师】 崔永芳； 杜启云；

【作者基本信息】 天津工业大学 ， 纺织工程， 2003， 博士

【摘要】 工业上生产纤维素纤维的传统方法为粘胶法，该法虽然历史悠久、工艺成熟，但工艺路线复杂，能耗多，特别是生产中对环境造成严重的污染。因此改革传统的粘胶生产工艺，开发对环境无污染的制造纤维素纤维新技术受到了国内外专家的广泛重视。此外，对纤维素纤维的阻燃改性，特别是结合环境友好特点采用无卤、低毒、低烟雾、高效阻燃剂更是纤维素纤维研究领域中的热点之一。 通过纤维素氨基甲酸酯法（Cellulose Carbamate 简称CC）纺制纤维素纤维被誉为环境友好型纤维素纤维。本文采用环境友好的纤维素氨基甲酸酯法生产阻燃纤维素纤维，首先研究了碱法、液氨法、电子束辐射法、蒸汽闪爆和氨闪爆法及超声波法活化纤维素后其结构的变化，在此基础上探讨了纤维素氨基甲酸酯的合成方法及其条件，又自己合成了三种纤维素用磷系阻燃剂。最后，通过共混纺丝制得了阻燃纤维素纤维，并对阻燃纤维素的阻燃性能及膨胀阻燃作用机理进行了探讨和研究。 本论文研究的主要创新内容为： 1．通过物理或化学的方法对纤维素进行预处理以增加其活性表面积、改善其微孔结构，提高纤维素的可及度，促进试剂在其中的渗透、扩散和润胀，提高纤维素的反应性能是本论文研究的重要方面。关于活化的方法有很多种，本研究在国内首次用电子束辐射、蒸汽闪爆和氨闪爆法活化纤维素浆粕后用于制备纤维素氨基甲酸酯，并通过扫描电镜、X-射线衍射、红外光谱及其它手段对处理后纤维素的结构及性能进行了研究。其中氨闪爆法活化纤维素浆粕制备纤维素氨基甲酸酯在国外也未见报导。研究结果表明，在辐射后纤维素的聚合度降低，分子量分布变窄，反应性能提高，电子辐射对晶型和结晶度影响不大；蒸汽闪爆/氨闪爆处理纤维素浆粕增大了纤维素之间的空隙和纤维素中的孔隙，大大提高了试剂对纤维素的可及度，聚合度略有下降，纤维素的反应性能也明显提高，蒸汽闪爆后纤维素的晶型和结晶度基本没有变化，氨闪爆后纤维素的结晶度有所降低，结晶结构有部分由纤维素Ⅰ转变为纤维素Ⅲ，纤维素的反应性能也明显提高。 2．本论文通过三氯氧磷（POCl₃）或三氯硫磷（PSCl₃）与新戊二醇反应，再与乙二胺反应，合成了高效的纤维素用阻燃剂2，2′—氧代双（5，5—二甲基—11l，3，2—二噁磷烷—2，2′—二硫化物）（DDPS）、1，2—二（2—氧代—5，5—二甲基—1，3，2—二氧磷杂环己—2—氨基）乙烷（DDPN）以及1，2—二（2—硫代—5，5—二甲基—1，3，2 天津工业大学博士学位论文 摘要一二氧磷杂环己一2一氨基）乙烷山DPSN)。对合成工艺进行了改进和优化，使产率均在85 ％以上。采用元素分析、FTIR、核磁共振、质谱等分析方法对所合成的H种阻燃剂进行了结构鉴定。三种阻燃剂的TG—DTA与DSC结果显示，DDPS阻燃剂的起始分解温度为205‘’C，成炭速度快，800丫时的降解残留量高达32见DDPS阻燃剂具有优良的成炭性。DDPN阻燃剂的起始分解温度为 285’C，600’C时的降解残留量为 4％，成炭性不好。DDPSN阻燃剂急剧分解区为 120’C—270‘C，800‘C时的成炭性为10％，成炭性比DDPN好，但比DDPS差，这一方面可能与DDPSN合成的纯度不高有关。其中DDPSN阻燃剂的合成不仅填补了该领域的合成空白，而且对纤维素的阻燃性能优良，为无卤膨胀阻燃体系的研究开辟了新途经，因此，具有重要的理论意义和现实意义。3．采用动态热失重法对DDPS阻燃剂进行了非等温动力学研究，利用Kissinger法和积分法分别计算了DDPS阻燃剂的表观活化能和表观指前因子，并以升温速率为10℃／＊n 的DDPS阻燃剂热重曲线为基础，利用9种常见的机理函数进行曲线拟合，判断得出 DDPS阻燃剂的热分解机理函数为卜(l－刀‘’‘＝hi，表明 DDPS阻燃剂的热分解反应机理是随机成核和生长（n—3）。4．将自己合成的阻燃剂加入到纤维素氨基甲酸酯（CC）溶液中纺丝得到环境友好型阻燃纤维素纤维及阻燃纤维素薄膜，并研究了它们的热裂解、阻燃性能及阻燃机理，研究结果显示：阻燃纤维素膜的初始热失重温度提前，热失重速率最大时对应的温度减小，800 t时的炭量增加。阻燃剂中阻燃效率的大小依次为＊＊PSN＞＊＊PS＞＊＊PN。随着阻燃剂含量增加，阻燃纤维素的成炭速度（＊FR）和残炭率（CY）都增加。当阻燃剂含量大于 18％时，纤维素膜均能够达到阻燃要求。三种阻燃剂和纤维素氨基甲酸酯阻燃体系的研究在国内外也未见报道。 本人还在前人研究的基础上利用傅立叶红外（FTIR）谱图、广角X光衍射 （WAXD）、扫描电子显微镜（SEM）、光学显微镜、差示扫描量热仪（DSC）、克达尔定氮元素分析、铜氨溶液测定纤维素聚合度等多种手段对纤维素的碱法、液氨法、超声彼法活化纤维素后其结构的变化和合成纤维素衍生物过程中结构及性能的变化 旬进行了较为系统地研究。探讨了纤维素氨基甲酸酯的合成方法及工艺条件，并通过在纤维素氨基甲酸酯与粘胶的共混纺丝纺丝液中加入阻燃剂纺制得到了阻燃纤维素纤维，对纤维的各种性能进行了测试分析。更多还原

【Abstract】 The technology for manufacturing cellulose fiber traditionally by Viscose spinning is of long history and well-developed in industry, but it has many disadvantages such as complex process, large energy consume, and serious pollution to the environment during it production process. The innovation on the traditional technology to develop new ones for manufacturing cellulose fiber with non-pollute to the environment is, therefore, drawing great attentions of the experts. In addition, modifications in fire-retardant on cellulose fiber, especially by employing non-halogen containing, little toxic, little smoke and high effective fire retardants is also one of hot research pot in the art.Cellulose fiber made from cellulose carbamate(CC) is named eco-friendly cellulose fiber. In this paper, an eco-friendly fire-retardant cellulose fiber was prepared. Based on the investigation on the changes of the cellulose structure after its activation by alkali, ammonia, electronic beam radiation, steam explosion, ammonia explosion and ultrasonic respectively, the synthesis of the cellulose carbamate was discussed. In addition, three phosphorus based fire retardants were synthesis. Thus, the fire retardant cellulose fiber was prepared by blending spinning. And at last, the fire retardant properties of the fiber and the fire retardant mechanism were discussed.The innovated content in this paper are as follows:1 . The important aspect of this paper is that through physical or chemical pretreatment to cellulose, the active surface was increased, the micro-cavity structure was improved, the penetration, diffusion and swelling of the agent to it was promoted, and therefore the activity of the cellulose was enhanced. The active methods of electronic beam radiation, steam explosion, ammonia explosion are firstly employed in domestic to activate the cellulose and follow to prepare CC, among which ammonia explosion method has not been reported yet abroad. We comprehensively and systematically studied the changes of the structures and properties of cellulose in the process of cellulose activation and reaction by means of various techniques, including Fourier Transform Infrared Absorption Spectrum(FTIR),Wide-angle X-rayIVDiffraction(WAXD?Scanning Electron Microscopy(SEM?Optical Microscopy, Differential Scanning Calorimetry(DSC),Kjeldahl Nitrogen Element Analysis, Degree of Polymerization of Cellulose and Fiber Mechanical Property Measurement etc. The results show that the degree of the polymerization decreases, the distribution of molecular weight gets narrow, and its reactivity rises. Electronic radiation has hardly effects on the lattice and crystallinity, but the lattice form converted from cellulose I to cellulose II and the crystallinity of cellulose decreased after ammonia explosion.2. Three phosphorus based fire retardants, l,2-bis(2-oxy-5,5- dimethyl-l,3,2-dioxaphosphorinane-2,2’-disulfide)(DDPS),l,2-bis(2-oxy-5,5-dimethyl-l,3,2-di oxaphosphorinane phosphoryl amide) ethane (DDPN) and l,2-bis(2-oxy-5,5-dimethyl-l,3,2- dioxaphosphorinane -2,2- disulfide phosphoryl amide) ethane (DDPSN) , were synthesized. All the three fire retardants were identified by elemental analysis > TG-DTA, DSC, FTIR,’HNMR, MS. Among them, DDPS is the best with an initial decomposition temperature of 205癈 and good carbon-forming ability, and DDPN is the worst with an initial decomposition temperature of 285癈 and bad carbon-forming ability. In addition, the synthesis technology was optimized and the yields are all above 85%.3. Nonisothermal kinetics researches on DDPS were carried out using dynamic thermalgravity. The aspect activation energy and A was calculated using Kissinger and integral methods. Based on the thermalgravity line of DDPS at an elevating rateof 1 0癈/min, its thermal decomposition function was set up as [- ln(l - a)]1/3 =kt ,which shows that the mechanism of thermal decomposition of DDPS is random nuclear f更多还原