水相法合成氯化等规聚丙烯的研究

采用水相法合成氯化等规聚丙烯(CIPP)．研究了反应速度及溶解性能的影响因素。介绍了水相法CIPP的性能及其在油墨上的应用。     

等规聚丙烯的深度氯化及其在涂料中的应用

采用溶液催化氯化工艺对等规聚丙烯（IPP）进行深度氯化，制得氯含量达52％～62％的氯化等规聚丙烯（CIPP）。该氯化等规聚丙烯可代替过氯乙烯、氯化橡胶用于各种防腐涂料，所得防腐蚀涂料具有良好的性能。     

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。     

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。     

低等规聚丙烯的研制Ⅰ.低等规聚丙烯的微观结构和性能

采用低等规聚丙烯催化剂制得ＬＩＰＰ,并测定其微观和性能结果表明。ＬＩＰＰ是短距有序长距无序的等规和少量间规立体嵌段均聚物,其性能与高等规聚丙烯和副产无规聚丙烯有较大的差别。     

分散剂体系对氯乙烯—醋酸乙烯—丙烯酸酯三元共聚树脂性能的影响

本文研究了氯乙烯—醋酸乙烯—丙烯酸酯三元悬浮共聚合反应中分散剂体系对树脂颗粒形态及溶解性能的影响。结果表明,使用复合分散剂制得的树脂颗粒形态不规整,表观密度较低,类似于疏松型氯醋树脂,溶解性能也较满意;而单用分散剂A制得的树脂颗粒形态为球形,表观密度较高,类似于紧密型氯醋树脂,溶解性能较差。     

氯化改性等规聚丙烯树脂合成的研究

采用溶液氯化方法,对固相接枝制得的等规聚丙烯接枝马来酸酐共聚物（IPP－g-MA）进行氯化反应,制得氯含量为30％－55％的氯化改性等规聚丙烯（MCPP）。用FT－IR、X光衍射、DSC和^13C NMR表征了产物的结构。MCPP树脂配制的聚丙烯塑料涂料和金属防腐蚀涂料均有很好的性能。     

丙烯超临界聚合中原生晶特征

通过广角X射线衍射(WAXD)对由丙烯超临界聚合和传统本体淤浆法制得的等规聚丙烯原生结晶特征进行了研究,并讨论了聚合工艺、预聚温度、粒径、分子量等对原生晶特征的影响。结果表明,超临界聚合法制备的等规聚丙烯(SC-iPP)呈现出α和γ的混合晶型,而采用传统淤浆法制备的等规聚丙烯(C-iPP)只含有单一α晶型,这是因为超临界的高温高压状态,使得体系传热传质阻力较小,更有利于原生晶型的发展。此外,预聚温度、粒径、分子量等因素也对丙烯超临界聚合所制得的SC-iPP结晶特征有显著影响。     

POE增韧改性本体聚丙烯的实验研究

以小本体粉料聚丙烯(PPH-075)和共聚聚丙烯(PPR-1003)为基体树脂,通过与聚烯烃弹性体(POE8150)、滑石粉、白炭黑以及其他助剂进行共混,制备汽车保险杠专用料。考察了原料牌号、基体树脂配比、POE用量、填料用量等对共混体系性能的影响。结果表明:PPH075,PPR1003,POE和填料的质量份数分别为70,5,20和15时,制得的改性聚丙烯的综合性能较好,可满足汽车保险杠对材料的性能要求。     

改性聚丙烯在涂料中的应用

用等规聚丙烯与马来酸酐的固相接枝法，制得具有不同酸值的改性聚丙烯树脂，对其涂膜性能进行了研究。并将其与环氧／聚酯粉末涂料共混，研究了共混物的涂膜性能。结果表明，固相接枝聚丙烯树脂单独或者作为环氧／聚酯粉末涂料的一个组分用于粉末涂料，具有很好的涂膜性能。     

固相法氯化等规聚丙烯的溶液性能

研究了固相法CIPP的稀溶液和浓溶液性能 ,结果表明 ,随着氯含量的增加CIPP稀溶液的特性粘数和浓溶液的粘度都呈下降趋势。溶液粘度随氯化反应温度的升高上升较快 ,在力化学降解下CIPP的溶液粘度下降较快。CIPP固含量超过 2 0 % ,粘度上升较快     

Unified production of chlorinated isotactic polypropylene and chlorinated paraffin via a solvent free chlorination process

An environmentally friendly method for producing chlorinated isotactic polypropylene (CIPP) with chlorine percentage of 28–35, by weight is proposed, in which a reactive solvent, paraffin, is used to replace the commonly used inert solvent of carbon tetrachloride (CTC), an ozone depleting substance being phased out under the Montreal Protocol. This method utilizes the principle that paraffin can dissolve isotactic polypropylene (IPP) at about 150°C and the resulting solution can be chlorinated concurrently, forming two useful products, viz. chlorinated paraffin (CP) and CIPP, which are mutually soluble even at lower temperature, e.g., 70°C. The present method is superior to the conventional CTC solvent method because it can reduce the solvent emission dramatically, enhance the volume efficiency of reactor, and achieve a unified production of CIPP and CP under atmospheric pressure. The structure and properties of CIPP produced by two different methods are determined by differential scanning calorimetry, attenuated total reflectance‐Fourier transform infrared spectroscopy, proton magnetic resonance (¹H‐NMR), and ¹³C‐NMR. The results indicate that IPP chain can be homogeneously chlorinated in paraffin as in CTC solvent via a radical mechanism. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

丙烯酸多脂环(烯)酯与其均聚物的表面张力研究

采用滴体积法及Wilhelmy动态接触角测定法测定了丙烯酸双环戌烯基酯 (DCPA)、丙烯酸三环戌烯基酯 (TCPA)、丙烯酸异冰片酯 (IBA)、甲基丙烯酸正丁酯 (BMA)与其均聚物 ,以及氯化聚丙烯 (C1PP)与聚苯乙烯 (PSt)的表面张力及其色散分量与极性分量 ;分别测定了水与CH2 I2 对聚合物PDCPA、PTCPA、PIBA、PBMA、C1PP与PSt表面的动态接触角。以及DCPA、IBA与BMA分别对PSt表面的动态接触角。水、CH2 I2 与PSt为参比物 ,它们的表面张力及其色散分量与极性分量为已知的。从这些数据中得到一些规律性现象 ,并进行了解释。     

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。     

Study of structure and thermal properties of polypropylene and chlorinated polypropylene by infrared spectroscopy and differential scanning calorimetry

The infrared spectra of chlorinated polypropylene (CPP) are interpreted and tentative assignments of C—Cl stretching vibration of CPP are proposed. Recently, infrared spectrophotometry has been applied as a useful tool for the investigation of polymer transitions. The solid-state transition in isotactic polypropylene (IPP) was studied by infrared method in the range of ?50° to 30°C; and from the temperature dependence of the peak absorbance, transition at -10°C was detected. This temperature of -10°C agrees well with the T_g2 detected by other methods. From these results, it is presumed that T_g2 is attributed to a motion (thermal expansion) of IPP segments in either crystalline and amorphous region. The thermal transition of chlorinated isotactic polypropylene (CIPP) was also examined with differential scanning calorimetry and infrared method, and two thermal transitions were observed. A higher transition (T_H) has a minimum at a degree of chlorination of about 39 wt-%; and a lower transition (T_L) changes linearly with increasing degree of chlorination. Infrared results indicate that T_H may be associated with a motion (thermal expansion) in chlorinated segments, and T_L may be associated with a motion in unchlorinated segments. These results of infrared studies also suggest that CIPP may have a block structure.     

Prospects in the application of a frontally curable epoxy resin for cured-in-place-pipe rehabilitation

Photocurable acrylates and vinyl esters are among the most commonly used resins in cured-in-place-pipe (CIPP) rehabilitation technology, as they impart excellent thermomechanical properties in composite pipes. In the quest for achieving a higher energy efficiency of the photo-curing process in CIPP, the frontal polymerization technique is a viable alternative that requires a lower irradiation dosage coupled with exceptionally high curing speeds and depths. Herein, for the first time, we report the application of frontal polymerization in the rehabilitation of underground pipes using a newly developed frontally curable epoxy-based resin (Trelleborg Self-Curing*). The neat resin is characterized for degree of cure, glass transition temperature, and mechanical properties via FTIR, DMA, and tensile tests, respectively. In a comprehensive way, the properties are benchmarked against commercially available acrylate (Trelleborg Light Cure*) and vinyl ester (Trelleborg Rapid Cure*) resins to evaluate their applicability for CIPP. The results show a higher glass transition temperature and final monomer conversion for the frontally cured resin, which cures significantly faster than the reference resins under the same irradiation conditions. In proof-of-concept trials, the newly developed resin successfully cures polymeric liners in a PVC host pipe with 100% water tightness and without losing its structural integrity. Results from ring stiffness tests for cured composite pipes additionally show that liners cured with Trelleborg Self-Curing* resin pass the minimum required Young's modulus for non-pressure drainage pipes as per ASTM F1216. Thus, frontally curable epoxy-based resins are a promising and competitive alternative to acrylates and vinyl esters in CIPP.     

第三单体对丙烯酰胺／苯乙烯无皂乳液共聚反应的影响

考察了作为第三单体的甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）、丙烯酸（AA）或二甲基二烯丙基氯化铵（DMDAAc）对丙烯酰胺（AAm）／苯乙烯（St）共聚反应速率和乳液性质的影响。研究结果表明在AAm／St二元共聚体系中添加所选用的第三单体都加快共聚反应速率，第三单体的水溶性越大，其增加反应速率的幅度也越大；随着第三单体水溶性的提高，乳液的稳定性增大；增大BA的质量分数可以使乳液的稳定性和表面电荷密度增大。     

Predictors of solvent effectiveness for dissolution of coal preasphaltenes

The dissolvabilities of coal preasphaltenes in several solvents with various solvent parameters were correlated. Generally dissolvability increased with increasing net hydrogen-bonding index, increasing donor number (DN) and increasing value of donor number minus acceptor number (AN) of the solvent. However, these trends show significant scatter and are not satisfactory as predictors of individual solvent behaviour. Plots of preasphaltene dissolvability against Hildebrand solubility parameter produce curves with broad maxima and several off-line points. Best results are obtained with DN/AN ratios, which yield smooth curves with narrow maxima and little scatter. These ratios are also shown to be useful predictors of the effectiveness of solvents for the extraction and swelling of coal.     

纤维素溶解体系的研究进展

综述了纤维素无机溶剂及有机溶剂的研究进展,分析比较了各溶剂体系的优缺点。其中有机溶剂中离子液体和N-甲基氧化吗啉的溶解能力最强,无机溶剂中碱/尿素或硫脲/水体系的溶解能力最强。但纤维素在各个溶解体系中都有一定程度的降解。