三甲基硅化合物复合体系引发1,3-戊二烯阳离子聚合研究

研究了三甲基硅化合物 ,主要是三甲基硅酯和三甲基硅氯化物 (TMSCI)与路易斯酸所形成的复合引发体系引发聚合 ,1,3 戊二烯 (PD)的聚合反应行为 ,考察了引发体系引发PD聚合所得聚合物的产率 ,分子量及分子量分布 ,聚合反应速率和聚合反应机理等 ;研究了多种给电体———醚、酮对聚合反应的影响     

TiCl4共引发异丁烯正离子聚合合成反应活性聚异丁烯

由H2O/TiCl4/甲醇或乙醚体系引发异丁烯在二氯甲烷与己烷混合溶剂中进行正离子聚合,探讨甲醇用量、聚合时间等因素对正离子聚合以及产物分子量、分子量分布和末端基结构的影响,并在此基础上探讨TiCl4共引发混合C4馏分中异丁烯选择性正离子聚合以制备活性聚异丁烯的可行性.结果表明,含氧试剂对聚合反应起到明显的调节作用,可适当稳定碳正离子活性中心,降低链增长速率,降低聚合产物的分子量(Mn=1600~4600),使分子量分布明显变窄(Mw/Mn=1.35~2.05),并可调节大分子链末端基结构及其含量.降低聚合体系中微量单体浓度以及适当延长聚合反应时间,均有利于提高聚异丁烯大分子链末端α-双键结构含量.通过TiCl4共引发异丁烯正离子聚合制备出末端α-双键含量可以达到70%以上的低分子量高反应活性聚异丁烯.此外,该引发体系还可引发混合C4馏分原料中异丁烯进行高选择性正离子聚合,得到Mn=2000、Mw/Mn=2.59、端基α-双键含量为38.9%的聚异丁烯.     

用硅烯醚型引发剂进行的基团转移聚合

本文报道了一类硅烯醚型的基团转移聚合引发剂。并以负离子和HgI_2等为催化剂,进行了甲基丙烯酸酯和丙烯酸酯的基团转移聚合。得到了实测分子量和理论分子量相近且分散性较小的浆合物。进行了甲基丙烯酸甲酯的活性聚合以及其与丙烯酸酯的A-B-A型三嵌段共聚,证实具有活性高分子的特征。探讨了该类引发剂引发基团转移聚合的机理,研究了催化剂和引发剂的配合选择性以及催化剂和引发剂的摩尔比对产物分子量和转化率的影响,发现该类引发剂引发的基团转移聚合是一恒速聚合反应。     

二茂钛/锡/环氧化合物引发苯乙烯活性自由基聚合的研究

采用单茂钛CpTiCl3和二茂钛金属化合物(n-BuCp)2TiCl2,引发剂4-甲氧苯基缩水甘油基醚(I1),1,4-丁二醇二缩水甘油基醚(I2),4,4′-亚甲基二(N,N-二缩水甘油基苯胺)(I4)和苯基缩水甘油基醚甲醛共聚物(I5)及还原剂Sn组成引发体系,引发苯乙烯活性自由基聚合,合成线型和多臂聚合物.探讨了不同茂钛金属化合物、引发剂和还原剂对苯乙烯聚合的影响;并采用13C-NMR和GPC对聚苯乙烯的结构和性能进行了表征.结果表明所得聚合物是无规聚苯乙烯,聚合物分子量高,分子量分布窄.聚合行为属于活性自由基聚合.     

N-乙烯基咔唑与卤代烃引发甲基丙烯酸甲酯聚合的研究

<正> N-乙烯基咔唑(NVC)具有大的共轭结构和中间有一个杂原子氮,而容易与其它试剂反应,形成自由基、阳离子和电荷转移络合物,故是一种活性较高的单体,1970年有人发现NVC与N-C_4H_9NCl_2一起可以引发甲基丙烯酸甲酯(MMA)聚合,此外,文献报道了电子给体如胺与CCl_4体系在二甲亚砜(DMSO)中引发MMA聚合,本文研究了NVC与几种卤代烃所组成的双组分体系对MMA的引发聚合反应;该体系的引发活性和组成与分子量及分子量分布的关系;并探讨了反应机理。     

含氮试剂对P-DCC／AICl3引发异丁烯正离子聚合的影响。

以对-二枯基氯（DCC），Alcl，体系引发异丁烯在二氯甲烷（CH2C12）正己烷（Hex）（40／60，V／V）混合溶剂中进行正离子聚合，探讨了DCC用量、含氮试剂2，6-二叔丁基吡啶（DtBP）和三苯胺（TPA）对异丁烯正离子聚合转化率、产物分子量及其分布的影响．结果表明，DCC和体系中微量水均可与A1C1，产生竞争络合，形成两种活性中心并引起相继的竞争引发，聚合产物的GPC谱图呈双峰分布，分子量分布宽；增加DCC用量有利于DCC与A1C1，的络合，致使链增长反应主要通过DCC与A1C1，络合形成的活性中心引发，但聚合产物分子量相对较低，分子量分布较宽；使用DtBP，可有效地抑制微量水引发及活性链向单体的转移反应，使分子量分布明显变窄，基本实现DCC的控制引发；采用DtBP与TPA共同调节聚合反应，可使聚合产物分子量分布变窄的同时，进一步提高分子量，从而得到相对较高分子量（Mw=103200）和单峰分子量分布（Mw／Mn=2．09）的聚异丁烯产物．     

铈离子与乙酰乙酸乙酯体系引发烯类聚合的研究

<正> 铈离子与醇、醛、酮、α-羟基酸等组成的体系能引发烯类单体进行自由基聚合。关于铈离子与酯类化合物体系文献报道甚少。孙燕慧发现脂肪酸酯或芳香酸酯对铈离子引发丙烯酰胺(AAM)聚合能起促进作用,提高聚合速度只R_(p)但活性较小,相对聚合速度只,为1.3左右。本文研究了二元酸酯、乙酰乙酸乙酯(EACAC)分别与铈离子组成的体系引发AAM聚合,实验结果表明EACAC有很高的活性,它与铈离子组成的体系为一氧化还原引发体系。应用自由基捕捉技术和ESR波谱研究,能检测到由EACAC组分反应产生的自由基,从聚合物端基的FT-IR光谱分析,证实了该自由基能引发单体聚合而成为聚合物的端基。从而讨论了引发机理。     

含氮试剂对p-DCC/AlCl_3引发异丁烯正离子聚合的影响

以对-二枯基氯(DCC)/AlCl3体系引发异丁烯在二氯甲烷(CH2Cl2)正己烷(Hex)(40/60,V/V)混合溶剂中进行正离子聚合,探讨了DCC用量、含氮试剂2,6-二叔丁基吡啶(DtBP)和三苯胺(TPA)对异丁烯正离子聚合转化率、产物分子量及其分布的影响.结果表明,DCC和体系中微量水均可与AlCl3产生竞争络合,形成两种活性中心并引起相继的竞争引发,聚合产物的GPC谱图呈双峰分布,分子量分布宽;增加DCC用量有利于DCC与AlCl3的络合,致使链增长反应主要通过DCC与AlCl3络合形成的活性中心引发,但聚合产物分子量相对较低,分子量分布较宽;使用DtBP,可有效地抑制微量水引发及活性链向单体的转移反应,使分子量分布明显变窄,基本实现DCC的控制引发;采用DtBP与TPA共同调节聚合反应,可使聚合产物分子量分布变窄的同时,进一步提高分子量,从而得到相对较高分子量(Mw=103200)和单峰分子量分布(Mw/Mn=2.09)的聚异丁烯产物.     

新引发剂体系AlCl_3/活化剂/电子给体的α-蒎烯聚合作用研究(Ⅰ)——AlCl_3/SbCl_3/酯体系

研究了一类纯α-蒎烯聚合新引发剂体系AlCl_3/活化剂(A)/电子给体(D),这类体系有很高的引发聚合活性,能获得高分子量产物。其中,AlCl_3/SbCl_3/苯甲酸乙酯(EB)体系,可得软化点128.8℃的树脂,收率达87.3％。本文研究了该引发体系的聚合动力学和聚合物的特性,考察了它的组成配比和外加酯浓度等对聚合的影响。     

苯氧铜/正丁基锂体系引发MMA负离子聚合及其活性特征的研究

采用苯氧铜/正丁基锂(PhOCu/n-BuLi)体系引发MMA聚合, 通过GPC, ¹H NMR对聚合物进行了表征. 实验结果表明, 该体系聚合反应速度较快, 温度、引发体系组成是影响聚合物分子量及其分布、单体转化率、引发剂引发效率、聚合物的立构规整性的主要因素; －40 ℃时分子量分布比较窄, 但引发效率也比较低(大约15%). 低引发效率、宽分子量分布与引发剂的聚集状态有关. 分子量与单体浓度、引发剂浓度的关系说明, 该体系具有一定程度的活性聚合特点.     

Living Carbocationic Polymerization of Isobutylene Using Blocked Dicumyl Chloride or Tricumyl Chloride/TiCI4Pyridine Initiating System

Abstract

Living polymerization of isobutylene was achieved using an initiation system based on either 1,3-di(1-chloro-l-methylethyl)-5-tert-butylbenzene (tert-butyl-dicumyl chloride) or 1,3,5-tris(l-chloro-l-methylethyl)benzene (tricumyl chloride) in conjunction with TiCl₄, and pyridine in hexanes/methyl chloride (60/40, v/v) cosolvents. TiCl₄/pyridine was found to yield narrow molecular weight distribution (MWD ≈ 1.1) and quantitative initiation efficiency (I_eff < 90%). The living nature of the polymerization system was demonstrated by the linearity of molecular weight vs conversion plots and first-order kinetic plots up to about 90% monomer conversion. If polymerization was allowed to proceed further, a departure from first-order kinetics and a broadening of the molecular weight distribution was observed to occur. The living polymerization was investigated as a function of temperature, reaction time, and the concentration of TiCl₄/pyridine. Polymerization rates were observed to increase with decreasing temperature and/or increasing concentration of TiCl₄/pyridine. Number-average molecular weights of the polyisobutylenes ranged from 5,000 to 100,000 under the conditions employed.     

Atom Transfer Radical Polymerization of Butadiene Initiated by Benzyl Chloride/MoCl5 Substituted by 1-octanol/PPh3

A novel initiator system, benzyl chloride/MoCl₅ substituted by 1-octanol/triphenyl phosphine (PPh₃), was applied to the atom transfer radical polymerization (ATRP) of butadiene. The characterization revealed the linear increase of the number average molecular weight with the monomer conversion and the rather wide molecular weight distributions of the polymerization products. The microstructure of the butadiene was detected by IR and ¹H-NMR. The chlorine atom at ω –end group of the polymer and the change of valence states of molybdenum detected by UV–Vis spectra revealed that the polymerization accorded primarily with the mechanism of ATRP.     

Atom transfer radical polymerization of ionic liquid 2‐(1‐butylimidazolium‐3‐yl)ethyl methacrylate tetrafluoroborate

Polymeric forms of ionic liquids may have many potential applications because of their high thermal stability and ionic nature. They are generally synthesized by conventional free‐radical polymerization. Here we report a living/controlled free‐radical polymerization of an ionic liquid monomer, 2‐(1‐butylimidazolium‐3‐yl)ethyl methacrylate tetrafluoroborate (BIMT), via atom transfer radical polymerization. Copper bromide/bromide based initiator systems polymerized BIMT very quickly with little control because of fast activation but slow deactivation. With copper chloride as the catalyst and trichloroacetate, CCl₄, or ethyl α‐chlorophenylacetate as the initiator, BIMT was polymerized at 60 °C in acetonitrile with first‐order kinetics with respect to the monomer concentration. The molecular weight was linearly dependent on the conversion. The monomer concentration strongly affected the polymerization: a low monomer concentration caused the polymerization to be incomplete, probably because of catalyst disproportionation in polar solvents. The addition of a small amount of pyridine suppressed such disproportionation, but a further increase in the amount of pyridine greatly slowed the polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5794–5801, 2004     

聚丙烯酸酯/偏二氯乙烯/蒙脱土复合乳液的制备

以偏二氯乙烯和蒙脱土作改性剂,采用种子乳液聚合方法制备了聚丙烯酸酯 偏二氯乙烯/蒙脱土（PEA VDC/MMT）共聚物复合乳液,研究了蒙脱土质量分数对共聚物乳胶粒径、乳胶膜抗拉强度与断裂伸长率及热稳定性的影响。 结果表明,当蒙脱土质量分数从1%增加至5%时,PEA-VDC/MMT共聚物乳胶的平均粒径从141 nm增至243 nm;在蒙脱土质量分数为2%时, 乳胶膜的拉伸强度和断裂伸长率达到最大值,分别为3.23 MPa和1.330%。 PEA VDC共聚物的成碳率和热分解温度均随蒙脱土质量分数的增加而略有增加。     

H_2O/TiCl_4/Py体系引发苯乙烯正离子聚合

研究了在少量吡啶(Py)存在下由水(H2O)四氯化钛(TiCl4)体系引发苯乙烯于二氯甲烷正己烷中进行碳正离子聚合,分别考察[Py]、[H2O]和[TiCl4]对聚合速率、产物分子量与分子量分布的影响.实验结果表明,少量亲核试剂吡啶(Py)对聚合反应起着重要作用,可有效地降低聚合速率和使分子量分布变窄;随着[H2O]和[Py]降低或[TiCl4]增加,聚合产物的分子量增加,而分子量分布指数(Mw Mn)基本维持在1.8左右;随着[Py]增加,聚合速率降低;随着[H2O]和[TiCl4]增加,聚合速率提高.聚合速率对单体浓度呈一级动力学关系,对Py、H2O和TiCl4的反应级数分别为-0.72、0.72和1.86.聚合速率对TiCl4浓度呈接近二级动力学关系,这可能与体系中TiCl4主要以二聚体形式存在有关.聚合转化率和产物分子量均随着反应时间延长而逐渐增大,PS的数均分子量与转化率呈线性增加关系.     

Suspension Polymerization of Vinyl Chloride with Programmed Temperature: Morphological Characteristics and Thermal Stability of Polyvinyl Chloride)

Polyvinyl chloride) obtained by intermittent polymerization in suspension with temperature programming, has been characterized from the point of view of morphological properties and of thermal stability. The data have been compared with the values of the morphological characteristics and thermal stability for the PVC samples obtained under identical polymerization conditions, but at constant temperature. The polyvinyl chloride) obtained by polymerization with temperature programming has the same properties as the polyvinyl chloride) obtained by simple polymerization at constant temperature, with an identical average molecular weight. However, the former polymer shows improved thermal stability, as well as a decrease in the volumetric properties.     

Polymerization Mechanism of Vinyl Chloride with Trialkylaluminum-Lewis Base Catalyst and Thermal Stability of Poly(vinyl Chloride)

The mechanism of vinyl chloride polymerization by the tri-ethylaluminum-Lewis base-carbon tetrachloride catalyst system and the thermal stability of the resulting polymer were investigated. When the Lewis base is multidentate, the resultant complex with triethylaluminum shows significantly high catalytic activity for radical polymerization of vinyl chloride in the presence of carbon tetrachloride to give a white powder with high molecular weight. Carbon tetrachloride accelerates the rate of polymerization and participates in an initiating process rather than in a propagating step. The thermal stability of the polymer prepared with this catalyst system is much superior to that of commercial polyvinyl chloride), although the numbers of the double bonds in a chain end and of the head-to-head linkage are similar in both samples, suggesting that the thermally unstable structures of the former react with triethylaluminum to give the thermally stable structure on the polymerization process.     

无水FeCl_3存在下丙烯酸甲酯的单电子转移活性自由基聚合动力学

单电子转移活性自由基聚合(SET-LRP)是一种可以对聚合物进行有效分子设计,合成不同拓扑结构并且能够有效调节其相对分子质量和相对分子质量分布的新型聚合方法,具有潜在的应用前景。以2-溴丙酸甲酯作为引发剂,Cu(0)/三(N,N-二甲基氨基乙基)胺(Me6-TREN)为复合催化体系,通过在二甲基亚砜中添加不同摩尔浓度的无水FeCl_3来研究其对丙烯酸甲酯的SET-LRP聚合动力学的影响。结果表明,随着三价铁离子量的增加,其链增长速率常数下降并且出现诱导期延长现象,说明三价铁离子参与了SET-LRP的聚合动力学过程,它和在同样实验条件下二价铜所起的作用截然不同,这可能是由于三价铁离子的氧化导致反应体系中一价铜的浓度降低引起的。此项工作从另外一个角度解释了零价铜催化下SET-LRP聚合诱导期产生的原因。     

烯丙基氯化镁引发己二酸酐开环聚合

以烯丙基氯化镁引发己二酸酐开环聚合制备功能化的聚己二酸酐。考察了引发剂、温度、溶剂对聚合反应的影响.核磁端基分析表明开环聚合反应可能是通过酰氧键断裂,按“配位－插入”机理进行的。     

偏氯乙烯悬浮聚合反应速率模型

通过实验研究了偏氯乙烯悬浮聚合反应动力学,比较了偏氯乙烯与氯乙烯聚合动力学行为的异同.在假定偏氯乙烯聚合反应发生在单体相和液固界面两个区域的基础上,提出了偏氯乙烯沉淀聚合反应速率模型.模型预测的转化率值几乎在全转化率范围内都与本文的偏氯乙烯悬浮聚合实验结果一致.