茂金属催化聚合的聚1-丁烯的结构表征

以 η5 五甲基茂基三苄氧基钛 (Cp Ti(OBz) 3 和改性甲基铝氧烷 (mMAO)为催化剂 ,合成立体嵌段聚 1 丁烯 ,分子量高 ,分子量分布窄 ( Mw/ Mn=1 1～ 1 2 ) .聚合产物经沸乙醚、沸庚烷连续抽提分离 ,聚合物在两种溶剂中都能部分溶解 .各级份经13C NMR ,WAXD ,DSC和GPC等手段分析 ,结果表明乙醚可溶级份是无规聚 1 丁烯 ,庚烷可溶级份是立体嵌段聚 1 丁烯 ,庚烷不溶级份是等规聚 1 丁烯 .聚合温度较低 (0℃和30℃ )时 ,聚合物有结晶性 ,结晶度达 30 %以上 ,DSC分析有两个吸热峰 ;聚合温度较高 (4 0℃ )时 ,聚合物无结晶尖锐X射线衍射峰 ,也无熔融吸热峰 .     

硬质PVC复合改性界面研究进展

综述了增强增韧硬质PVC方面所做的研究工作及最新的研究进展,探究了增强、增韧PVC的方法以及机理,机理包括:多重银纹,剪切屈服,剪切屈服-银纹化,逾渗,空穴。目前的改性方法包括:改性无机粒子增强增韧PVC,如微米粒子、纳米粒子、"核-壳"结构粒子、其它无机粒子;聚合物和无机粒子/聚合物以及接枝改性增强增韧PVC。     

可控/“活性”自由基聚合制备聚乙烯及聚卤代烯烃

可控/“活性”自由基聚合(CLRP)可以用于制备分子量分布窄、分子链缺陷少的聚合物,如聚乙烯(PE)、聚氯乙烯(PVC)、聚偏氯乙烯(PVDC)和聚偏氟乙烯(PVDF),且易控制上述单体与其他单体共聚得到嵌段聚合物。本文调研了近年来可控/“活性”自由基聚合(如碘转移聚合(ITP)、氮氧稳定自由基聚合(NMP)、可逆加成断裂链转移(RAFT)聚合和金属催化的活性自由基聚合(OMRP)等)制备聚乙烯和聚卤代烯烃等方面的工作,并指出了未来的发展方向。     

取代芳基钛酸酯类化合物催化苯乙烯间规聚合

以取代芳基钛酸酯化合物为催化剂催化苯乙烯聚合,考察了催化剂、聚合温度,摩尔比nAl/nTi以及聚合时间等因素对聚合行为及产物性质的影响。并用13C-NMR、FT-IR、DSC等手段表征了聚合产物。结果表明:在nAl/nTi=1 000,聚合温度为60℃条件下,2,2′-硫代双(4-甲基-6-叔丁基酚氧基)二氯化钛催化苯乙烯聚合显示出很高的催化活性,其活性为6.87×105g sPS/(mol Ti.h),所得聚合物为间规聚苯乙烯,间规度96.9%,分子量为1.98×105。     

聚l-谷氨酸苄酯的制备及成膜

用三光气法合成了L-谷氨酸苄酯均聚物,讨论了N-羧基环内酸酐开环聚合的机理。用红外光谱、差示扫描量热测试技术分别对聚合产物进行了表征和分析。结果表明,N-羧基-L-谷氨酸-苄酯-环内酸酐开环聚合得到了聚L-谷氨酸苄酯。研究了不同温度和时间对聚合物分子量的影响。40℃是完成聚合反应的适宜温度。随着反应时间的增加,聚合产物分子量线性增加。用四氢呋喃作溶剂制备了PBLG薄膜,薄膜的密度为1.098 g/cm3。讨论了不同浸泡时间对聚合物吸水率的影响,结果显示,PBLG的吸水率随着时间的增加而增大,其变化范围为2.64%~5.58%,并且在48 h内逐渐趋于平稳;在相同状态下,断裂界面处的吸水率远高于其它部位。     

二乙醇胺改性聚乳酸的直接熔融聚合法合成及其表征

以乳酸(LA)、二乙醇胺(DEA)为原料,采用熔融聚合法直接合成了二乙醇胺改性聚乳酸,并用特性粘数、FT-IR、1H NMR、GPC、DSC、XRD等手段进行表征,探讨了催化剂种类和用量、熔融聚合反应时间、反应温度以及不同投料比、不同构型乳酸对聚合物合成的影响.在单体投料摩尔比n(DEA):n(L-LA)=1:200、160℃、70Pa、催化剂SnO用量0.7(wt)%、熔融聚合8h条件下,聚合物重均相对分子质量(Mw)可达8100.随着投料比中DEA的增加,产物特性粘数逐步降低,Mw逐渐减小,玻璃化温度(Tg)有降低的趋势.以L-LA聚合得到的聚合物的Mw、分散度(Mw/Mn)和结晶度均比由D,L-LA得到的产物的更高.因此,笔者认为,由于D,L-A与L-LA存在反应速率差异,因而二者有不同的反应历程.新合成方法有利于降低二乙醇胺改性聚乳酸作为药物缓释载体等生物医学材料的合成成本.     

有机非金属盐阴离子聚合研究进展

有机非金属盐阴离子聚合是活性/可控阴离子聚合的一个重要分支。有机非金属盐阴离子聚合方法最大的特点是可以在很宽的温度范围内(-20~70℃)引发(甲基)丙烯酸酯类单体聚合,分子量分布窄,显示出可控/活性的特征。该聚合方法为分子设计和合成(甲基)丙烯酸烷基酯的均聚物、嵌段聚合物、接枝聚合物和功能性聚合物提供了有效的途径。本文综述了有机非金属盐阴离子引发剂在合成(甲基)丙烯酸酯类单体中的研究进展,包括聚合的反应机理、特点、研究现状及其前景展望。     

超浓乳液聚合制备PU/PS的SIPN粉状树脂研究

将聚氨酯予聚体 (PU ) 苯乙烯 (St)的复合体系 ,用超浓乳液聚合方法制备了半互穿聚合物网络(SIPN)复合聚合物 ,得到了用聚氨酯予聚体改性的聚苯乙烯 (PU/PS)SIPN粉状树脂 .研究了分散相的比例(α)和聚合温度对聚合稳定性及聚合转化率 -时间的关系 ;测定了聚合物胶乳粒子的大小、形态 ,玻璃化温度 ,动态力学性能等 .结果表明 ,超浓乳液聚合较之本体聚合具有较高的聚合速率 ,容易控制所制备的胶乳粒径 ,能够制得PU/PS复合聚合物的SIPN粉状树脂 .该粉状树脂便于加工 ,具有良好的强韧性 ,有利于扩大应用     

(Ph_3·P)_2·PdCI_2催化的丙炔氯均聚合

用(Ph_3·P)_2·PdCl_2催化丙炔氯均聚,得到褐色或黑色产物。研究了聚合条件对聚合反应的影响。聚合产物的红外光谱分析表明它是丙炔氯的均聚物。元素分析结果显示聚合物除大部分链段为-C=C- CH_2Cl外,还有部分其它链段存在。聚合物的电导率为10~(1)S·m~(-1)。TG分析表明丙炔氯聚合物较丙炔醇易受热分解。GPC测得聚合物的数均相对分子质量为1350。     

疏水改性聚丙烯酰胺溶液的分子模拟

设计了几种不同的非离子型改性聚丙烯酰胺(HM-PAM)和阴离子型改性聚丙烯酰胺(HM-HPAM). 通过分子动力学模拟(MD)方法研究了在聚合物链上加入不同疏水改性单体对提高聚丙烯酰胺耐盐性的影响, 考察了盐浓度对疏水改性聚丙烯酰胺的回旋半径(R_g)、 特性黏数([η])、 径向分布函数(RDF)和均方位移(MSD)的影响以及聚合物的微观结构与特性黏数之间的关系. 研究结果表明, 引入疏水改性单体后, 改性聚丙烯酰胺具有较好的耐盐性. 通过研究非键作用与氢键相互作用可知, 体系中溶质和溶剂间的相互作用及氢键作用越弱, 溶液的特性黏数越大. O-H原子对的RDF结果表明, 聚合物链的伸展与聚合物链及官能团间的相互作用有关. 当RDF峰较弱时, 聚合物链与水的作用越弱, 越有利于聚合物链保持舒展状态, 溶液的特性黏数也就越大. 另外, 从聚合物链的MSD曲线发现, 聚合链的移动性与特性黏数呈负相关.     

Raman spectra of extended-chain syndiotactic poly(vinyl chloride)

Raman spectra have been obtained for a typical poly(vinyl chloride) (PVC) of low crystallinity and for a highly crystalline sample of syndiotactic PVC obtained by irradiation of a urea-canal complex. Raman measurements have been made on the three different ordered chain structures possible for ordinary PVC. Extended and folded conformations for the syndiotactic structure and a helical structure for the isotactic molecule obey different selection rules and have different dichroic properties in the infrared and Raman spectra. The observed Raman spectrum is consistent with the model of the extended syndiotactic conformation for crystalline PVC. With the new Raman data some additional assignments can be made in the vibrational spectra of PVC.     

溶剂对聚氯乙烯-聚乙二醇-KOH体系脱氯行为的影响

废旧塑料的回收利用是当今研究的热点之一.据报道,2007年中国聚氯乙烯(PVC)产量高达960万吨[1],如何合理利用相应产生的废旧PVC是一个十分重要的课题.     

Determination of branching in polyethylene and poly(vinyl chloride) using pyrolysis gas chromatography

A series of polyethylenes (PE), reduced poly(vinyl chlorides), and precursor poly(vinyl chloride) (PVC) systems were studied by pyrolysis–gas chromatography (PGC) and by pyrolysis–hydrogenation–gas chromatography (PHGC). The branch content of these polymers has been interpreted on the basis of previously established literature information. Low-density PE (LDPE) was found to contain a significant number of ethyl branches. The pyrolysis results on an LAH-reduced PVC series gave significant insight on PVC microstructure. It was determined that the short-chain branches in PVC are mainly one carbon long. Some ethyl side chains and virtually no butyl branches were found in this experimental PVC series. The effect of chain branching on the pyrolysis of PVC is to increase fragmentation. The benzene/toluene ratio, along with relative amounts of benzene and naphthalene formed, may be used to indicate the relative degree of branching in this system. The application of PGC and PHGC have thus been shown to successfully extend analytical work on PE and PVC and to provide microstructural information.     

Preparation and degradation of head-to-head PVC

The course of the chlorination reaction of cis-1,4-polybutadiene is dependent on the choice of solvent. When methylene chloride is used, a pure addition reaction of chlorine leads to a polymer with the structure of head-to-head, tail-to-tail PVC. The thermal stability of the head-to-head PVC polymer has been studied by thermal volatilization analysis, thermogravimetry, and evolved gas analysis for hydrogen chloride, and the changes in the ultraviolet (UV) spectrum of the polymer during degradation have been investigated. The head-to-head polymer has a lower threshold temperature of degradation than normal PVC, but reaches its maximum rate of degradation at a higher temperature for powder samples of the polymer under programmed heating conditions. Blends of head-to-head PVC with poly(methyl methacrylate) have also been degraded, and the presence of the head-to-head polymers, like that of normal PVC, results in depolymerization of the PMMA as soon as the dehydrochlorination reaction commences. The mechanism of degradation of head-to-head PVC is discussed.     

氧化镁对聚丙烯/聚氯乙烯脱氯行为的影响

对废旧塑料的回收利用是近年来人们一直关注和不断研究的一个重要课题。将废塑料热裂解为燃料油或单体被认为是最具前景的处理方法之一[1]。当含有PVC的废旧塑料裂解时产生氯化氢气体,严重腐蚀设备;同时也会产生含氯的有机化合物,从而使其裂解生成的液体作为燃料使用时会生成有     

EVA-g-VC的结构和动态粘弹性

本文研究了聚乙烯-醋酸乙烯酯(EVA,VAc:14％)与氯乙烯(VC)接枝共聚物(EVA-g-VC)的相结构和分子结构。接枝物EVA-g-VC由游离EVA、均聚PVC和EVA-VC接枝高分子三者组成,EVA呈连续相,PVC呈分散微粒。EVA-g-VC中EVA的含量越高,PVC粒子体积越小。实验结果表明,接枝物中“凝胶”的EVA玻璃化温度,随投料比(VC/EVA)的减小而升高;另外随VC/EVA减小,凝胶中PVC的含量和PVC的分子量也减小。这些结果说明,VC/EVA较小时得到的接枝物中,EVA上VC接枝点的数目较多,而PVC接枝链的长度较短。EVA-VC是不相容两相——EVA和PVC的“粘着剂”,其作用表现在:VC/EVA越小,接枝物中EVA和PVC的玻璃化温度越靠近。     

PVC/MMT nanocomposites

Poly(vinyl chloride) (PVC) nanocomposites with sodium montmorillonite (Na-MMT) and organically modified MMT (O-MMT) have been prepared by melt processing using mixing and extrusion techniques. The differential scanning calorimetry (DSC) with stochastic temperature modulation (TOPEM?) results show that the glass transition temperature (T _g) of PVC is slightly higher than T _g of PVC/Na-MMT and PVC/O-MMT which would indicate that MMT plays a role of an internal plasticizer that increases the distance between the PVC macrochains. The DSC TOPEM non-reversing heat flow profiles show enthalpy relaxation effects, and the lowest value has been found for pristine PVC—the presence of MMT (both Na+ and ammonium salt modified) may generate a certain orientation level of PVC macrochains during the extrusion process. Specific heat vs temperature dependencies at different frequencies revealed that the best fit to the single profile was found for PVC/Na-MMT nanocomposite, and this observation may be related to internal stability of the composite material as confirmed by analysis of the change in the specific heat (Δc _p).     

History of Vinyl Chloride Polymers

In 1926 Semon tried to dehydrohalogenate high molecular weight poly(vinyl chloride) (PVC) in a high boiling solvent to get an unsaturated polymer which might bond rubber to metal. Unexpectedly, he obtained plasticized PVC, a flexible product inert both electrically and chemically. This discovery opened the door to the commercialization of PVC, a plastic with an annual United States production now exceeding 6 billion pounds. Special PVC's and PVC products have been developed taking advantage of the many favorable properties. Rigid structural products from house siding to pipes are becoming of increasing importance. Two main types of polymers have been utilized: 1) one prepared by suspension polymerization, and 2) a special variety prepared by colloidal polymerization and spray drying. This latter material has been especially useful for making plastisols. Plasticizers and stabilizers were developed to maximize useful and nontoxic properties. Vinyl chloride monomer (VCM) production and co-polymerization evolved as lower cost processes, higher quality products, and greater manufacturing safety were introduced. Recent challenges for the industry have included pollution and carcinogenic hazards which have been overcome by imaginative new technologies. The rate of growth of the industry is shown graphically.     

Polymer blends—I. Mechanical and morphological behaviour of polyethylene/polyvinyl chloride blends

As part of a fundamental study of the behaviour of mixed plastics during reprocessing and in service, blends of low density polyethylene (LDPE) and polyvinyl chloride (PVC) have been investigated. It was found that Young's modulus increased steadily from pure LDPE to pure PVC whereas both tensile strength at break and elongation at break passed through a minimum at about 5% PVC. Optical and scanning electron microscope studies have related this mechanical behaviour to morphological changes in the two phase system under stress.     

聚ε-己内酯/聚氯乙烯球晶表面的XPS研究

聚合物薄膜在微电子领域中的应用日益增加.聚ε-己内酯/聚氯乙烯（PCL/PVC）是研究得最广泛的聚合物共混薄膜之一.PCL与PVC以一定比例混合时,可以形成环带球晶；同时,体系分为结晶PCL相及PCL/PVC非晶混溶相.用XPS和成象XPS分析技术,对PCL/PVC膜的表面化学组成和元素分布情况进行了研究.观察到PCL在薄膜表面富集.此外,成象XPS表明,PVC在球晶边界处富集,且球晶边界宽度约15 μm.