固相氯化法用隔离剂的评价

通过研究隔离剂对氯化反应过程中烧结和粘结的影响，评价了多种隔离剂对气－ 固相氯化反应的作用，为隔离剂的选择提供了依据。研究结果表明，能够有效地减轻烧结现象的最佳隔离剂用量为４ ％ ，利用两种白炭黑的协同作用复配而得的隔离剂体系可以有效地减轻粘结现象。     

温度控制方式对气—固相氯化反应的影响

采用搅拌式固相法制备氯化等规聚丙烯（CIPP）,讨论了不同的温度控制方式对等规聚丙烯氯化反应的影响。结果表明,在恒定的温度条件下,100～103℃是较好的反应温度,温度过低产物的氯分布不均匀,温度过高容易发生脱氯化氢现象。在热处理方式下,由于气-固相反应特有的烧结和粘结影响严重,不利于氯化反应的进行。逐步长温的控温方式是制备CIPP的最佳温度控制方式。     

氯化高聚物生产现状与发展趋势

氯化高聚物作为高分子材料中的一个独立分支，目前在世界上已是到迅速发展。其生产方法主要有水相法、溶剂法和固相法。由于它具有阻燃性、耐化学腐蚀性、低毒性和经济性，可广泛应用于和个领域，国内需求潜力大，市场前景看好，以下简要分述我国几种主要氯化高聚物的产需情况。     

固相法氯化聚乙烯脱HCl热稳定性研究

本文采用固相氯化法制备了各种氯含量的氯化聚乙烯（ＣＰＥ）并用氯化氢吸收法系统考察了氯化条件、氯含量对固相法ＣＰＥ热稳定性的影响。结果表明氯化温度对ＣＰＥ的热稳定性有较大影响，高温氯化可以提高ＣＰＥ的热稳定性。在一定范围内随氯含量增加，ＣＰＥ热稳定性也相应增大。对ＣＰＥ脱除ＨＣｌ前后红外光谱及凝胶含量变化的研究表明ＣＰＥ热分解过程伴有交联结构形成。     

氯化聚乙烯工艺技术的比较

介绍了氯化聚乙烯的几种生产工艺，比较了釜式气固相氯化工艺、溶液法工艺、盐酸相悬浮工艺、水相悬浮法工艺，认为国外开发的水相悬浮法工艺优点显著。     

氯化聚乙烯的合成工艺及其应用

介绍了聚乙烯为原料,经氯化合成氯化烯的三种工艺（溶液法、悬浮法和固相法）。重点介绍了根据柔性设计理念而设计的沸腾床氯化工艺。介绍了氯化聚乙烯的应用和市场情况。     

固相研磨法制备纳米二氧化锆及其机理初探

通过在研钵内研磨，使固相的氧氯化锆分别与固相的氢氧化钠或六次甲基四胺或氢氧化钠和碳酸锂的混合研磨物发生反应，生成纳米二氧化锆粉体的前驱体氢氧化锆，然后中温(400℃)烧结制得纳米二氧化锆粉体，粒径约为10nm。并研究了不同沉淀剂、不同干燥方式对产物的影响。该法既节省能源又不污染环境，是一条绿色合成方法，具有工业化生产潜力。     

废农用聚乙烯薄膜固相氯化制备氯化聚乙烯的研究

本文研究了以废农用聚乙烯薄膜(WPE)为原料,固相氯化法制备氯化聚乙烯(CWPE)的工艺。研究了氯化温度、氯含量、引发剂、分散剂等因素对CWPE性能的影响。并通过红外光谱的研究阐述了CWPE结构与性能的关系。对CWPE的开发应用泎了简要的介绍。以固相法对废聚乙烯薄膜进行氯化制备氯化聚乙烯的研究,国内外至今尚未见报道。     

国外聚乙烯固相氯化工艺研究概述

本文概述了国外聚乙烯固相氯化方式的研究工作,扼要介绍了固相氯化工艺条件研究的进展情况。 国外聚乙烯固相氯化方式主要有四种:流化床、转动床、固定床和搅拌床,其中搅拌床固相氯化方式是PE固相氯化工艺研究和发展的方向。国外认为采用搅拌式固相氯化方式,以HDPE为原料,用含适量H_2O的Cl_2作氯化剂,TiO_2或SiO_2为防粘剂,以羧酸酐为增白剂,采取热处理或分段氯化工艺条件,完全有可能得到性能良好的CPE,使聚乙烯固相氯化工艺达到工业化生产的要求。     

固相法氯化等规聚丙烯的制备

探讨了等规聚丙烯原料性质对氯化反应的影响，同时研究了氯化反应的基本特征。结果表明，原料等规聚丙烯的熔融指数高、粒度小，有利于进行氯化反应。氯化反应速率随着氯化程度的加深逐渐下降，反应温度和反应程度都会影响氯化氢的脱除。采用搅拌式固相法，控制适当的反应条件可以制得氯化度高于６０％的ＣＩＰＰ产品。     

固相法合成涂料用高氯含量氯化聚乙烯

研究了固相合成高氯含量氯化聚乙烯过程中氯取代基，氯化温度、引发方式等对氯化速度的影响，及ＨＣＰＥ的降解。结果表明，大分子链上的氯取代代基对分子链进一步氯化起阻碍作用；氯化前期使用较高的温度或引发剂将使后面的氯化速度减慢；增大前期引发剂用量时，将会再次降低后期的氯化速度；通过机械剪切作用可使具有较高相对分子质量的ＨＣＰＥ大幅度降解。     

高氯化聚乙烯在防腐涂料中的应用研究

研究了固相法涂料用高氯化聚乙烯树脂的制备及其在防腐涂料中的应用。结果表明,适当降低原料高密度聚乙烯（ＨＤＰＥ）的分子量,产物高氯化聚乙烯（ＨＣＰＥ）树脂可直接用于涂料配制;调节ＨＤＰＥ的分子量及ＨＣＰＥ的氯含量,涂料粘度可在较大范围内变化。ＨＣＰＥ涂料的性能远优于过氯乙烯涂料而与氯化橡胶涂料相当,是替代氯化橡胶涂料的理想物质。     

Graft modification of highly chlorinated polyethylene (HCPE) with methyl methacrylate by the mechanochemistry reaction. I. Synthesis and characterization

Highly chlorinated polyethylene‐graft‐methyl methacrylate (HCPE‐g‐MMA; HCPE with chlorine contents > 60%), obtained by a mechanochemistry reaction, is discussed in detail. A two‐roll mill was used in the process. The reaction conditions affecting the structure of HCPE‐g‐MMA copolymers were measured in terms of calculation of graft efficiency (GE), graft degree (GD), and copolymerization rate/homopolymerization rate (R_c/R_h) by ¹H‐NMR spectroscopy. Based on these results, it is concluded that the chlorine contents of HCPE, the additional amount of MMA, and the mechanochemistry reaction time all have impacts on the structure of the polymer. The results also confirm that grafting is very much favored by the mechanochemistry reaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 811–816, 2003     

Graft‐modified HCPE with methyl methacrylate by the mechanochemistry reaction. II. Physical‐mechanical properties and processability

In this article, the physical‐mechanical properties and processability of graft‐modified highly chlorinated polyethylene (HCPE; chlorine contents: ≥ 60%) with methyl methacrylate (MMA) by mechanochemistry reaction were studied. The results showed that the HCPE‐g‐MMA system is superior to unmodified HCPE in physical‐mechanical properties, particularly in processability. In addition, the HCPE‐g‐MMA system, with about 62% chlorine content, was the same as PVC in its physical‐mechanical properties. The HCPE‐g‐MMA system, with about 65.5% chlorine content, is the same as chlorinated poly(vinyl chloride) (CPVC) in its physical‐mechanical properties, except that the Vicat softening temperature and processability of HCPE‐g‐MMA system are superior to PVC and CPVC. Compared with PVC and CPVC, the HCPE‐g‐MMA system proves better due to its lack of a toxic monomer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 282–287, 2004     

COMPETING/PARALLEL REACTION OF CHLORINE AND CHLORINE DIOXIDE DURING KRAFT PULP BLEACHING

The nature of chlorine dioxide substitution for chlorine in the chlorination reaction sequence of pulp bleaching in not well understood. Multiple results may be obtained by simply altering the order of chlorine-chlorine dioxide addition and the amount of chlorine dioxide substitution. Kinetic curves for chlorine, chlorine dioxide, and various levels of chlorine dioxide substitution were generated. The effects of these various processes on delignification (kappa number reduction) and Adsorbable Organic Halogen (AOX) generation were investigated. More than half of the AOX was found to be generated within the first one minute of any reaction sequence. Similar portions of the delignification were also found to occur within the first one minute of chlorination. The work examines the assumption that chlorine and chlorine dioxide react with different portions of the lignin. Thus chlorine and chlorine dioxide compete for only a part of the lignin molecule. The order of chemical addition dictates which chemical most rapidly attacks the competitive region. The hypothesis that chlorine dioxide substitution is simply a competing/parallel reaction sequence was studied.     

UV enhanced gas-solid synthesis of chlorinated poly vinyl chloride characterized by a UV-Vis online analysis method☆

Dynamic characteristics of UV enhanced gas–solid PVC chlorination process were revealed by a UV–Vis spectral online analysis method. Experimental results showed an instantaneous increase of the chlorination rate as soon as UV lightwas affiliated, which demonstrated the intensified effect of UV radiation on PVC chlorination directly. Different affiliationmethods of UV light were then studied, proving that continuous UV radiation could enhance the chlorination process significantly while intermittent UV radiation was able to initiate the chlorination reaction once it was conducted. Besides, experiments were carried out to study the influences of parameters on the chlorination process such as UV wavelength, chlorination temperature, partial pressure of chlorine gas and PVC raw materials. Among all the parameters, chlorination temperature and partial pressure of chlorine gas were testified as two key factors to determine the chlorination performance. Thermal analysis of CPVC products showed that their corresponding properties such as the glass transition temperature (T_g) and the homogeneity of chlorine distribution in polymer phase were improved with the increase of chlorine content.     

无溶剂光氯化悬浮法制备低氯化度的氯化等规聚丙烯

用无溶剂光氯化悬浮法进行等规聚丙烯 (IPP)氯化反应 ,考察了反应时间、引发剂、通氯量、悬浮剂和金属盐等因素对氯化速度的影响 ,以偶氮二异丁腈为引发剂 ,m(IPP)∶m(H2 O) =1∶1 5,通氯量为 40mL min ,反应时间 1 0h ,可得到氯质量分数在 2 5%左右的氯化聚丙烯。金属离子可明显缩短其诱导期 ,但反应后期 ,金属离子的存在对氯化反应起抑制作用。     

聚丙烯水相悬浮热氯化

研究了等规聚丙烯(IPP)水相悬浮热氯化,考察了氯化时间和温度、IPP粒径、搅拌转速、通氯速率等条件对氯化反应的影响。发现氯含量随氯化温度的升高而增大,随IPP粒径的减小而呈线性增大;在IPP充分分散条件下搅拌和通氯速率对氯化几无影响。扫描电镜(SEM)照片显示,氯化反应首先发生在粒子表面,氯化产物将粒子表面孔隙填充,增加了氯向粒子内部扩散的阻力,致使粒子内部的氯化反应缓慢。     

五氯苯甲腈的合成

以苯甲腈和氯气为原料，用气固催化氯化法研制了五氯苯甲腈。考察了催化剂、反应温度、原料配比等因素对产品纯度的影响，其收率达９０％以上，产品纯度９９％。     

In situ chlorination of poly(vinyl chloride) in aqueous hydrochloric acid

Based on environmental, safety, corrosion and technological considerations a new method has been developed for chlorination of PVC in aqueous hydrochloric acid solvent by controlled electrolytic in situ generation of chlorine using graphite and chlorine-selective Ti-RuO₂ electrodes. The byproduct, HCl gas, is dissolved at the moment of its formation and acts as starting material of further chlorination. This way, the application of corrosive chlorine gas is avoided. The chlorination conditions have been optimized. The highest chlorine content was found at 5.5 h reaction time using a graphite electrode. The obtained chlorinated PVC did not contain any CCl₂ units.