可逆加成-断裂链转移聚合制备聚氯乙烯-b-聚乙二醇-b-聚氯乙烯共聚物

合成了含黄原酸酯端基的聚乙二醇（X-PEG-X）大分子链转移剂,并以其为可逆加成-断裂链转移试剂调控氯乙烯（VC）溶液和悬浮聚合,合成聚氯乙烯-b-聚乙二醇-b-聚氯乙烯（PVC-b-PEG-b-PVC）三嵌段共聚物。X-PEG-X调控VC溶液聚合得到的共聚物的分子量随聚合时间增加而增大,分子量分布指数小于1.65。X-PEG-X具有水/油两相分配和可显著降低水/油界面张力的特性,以X-PEG-X为链转移剂和分散剂,通过自稳定悬浮聚合也可合成PVC-b-PEG-b-PVC共聚物,共聚物颗粒无皮膜结构,分子量随聚合时间增加而增大;由于VC悬浮聚合具有聚合物富相和单体富相两相聚合特性,共聚物分子量分布指数略大于溶液聚合共聚物。通过乙酸乙烯酯（VAc）扩链反应进一步证实了PVC-b-PEG-b-PVC的“活性”,并合成PVAc-b-PVC-b-PEG-b-PVC-b-PVAc共聚物。水接触角测试表明PVC-b-PEG-b-PVC的亲水性优于PVC。     

可逆加成-断裂链转移聚合制备聚氯乙烯-b-聚乙二醇-b-聚氯乙烯共聚物

合成了含黄原酸酯端基的聚乙二醇(X-PEG-X)大分子链转移剂,并以其为可逆加成-断裂链转移试剂调控氯乙烯(VC)溶液和悬浮聚合,合成聚氯乙烯-b-聚乙二醇-b-聚氯乙烯(PVC-b-PEG-b-PVC)三嵌段共聚物。X-PEG-X调控VC溶液聚合得到的共聚物的分子量随聚合时间增加而增大,分子量分布指数小于1.65。X-PEG-X具有水/油两相分配和可显著降低水/油界面张力的特性,以X-PEG-X为链转移剂和分散剂,通过自稳定悬浮聚合也可合成PVC-b-PEG-b-PVC共聚物,共聚物颗粒无皮膜结构,分子量随聚合时间增加而增大;由于VC悬浮聚合具有聚合物富相和单体富相两相聚合特性,共聚物分子量分布指数略大于溶液聚合共聚物。通过乙酸乙烯酯(VAc)扩链反应进一步证实了PVC-b-PEG-b-PVC的"活性",并合成PVAc-b-PVC-b-PEG-b-PVC-b-PVAc共聚物。水接触角测试表明PVC-b-PEG-b-PVC的亲水性优于PVC。     

低分子量AN/AA共聚物的制备

以过硫酸钾—亚硫酸氢钠的氧化还原体系为引发剂,采用水相沉淀聚合法制备了AN/AA共聚物,用不同链转移剂控制共聚物的分子量。研究了反应时间、引发剂含量、链转移剂含量对聚合物转化率以及聚合物分子量的影响。结果表明,选用N,N-二乙基羟胺为链转移剂,其用量为5%,反应时间为2 h时,共聚物分子量最小,控制在15000左右。     

低分子量聚苯醚的制备与表征

采用再分配反应制备了低分子量聚苯醚,通过在反应体系中加入链转移剂,探究链转移剂对聚苯醚再分配反应的影响。采用红外光谱、核磁共振波谱、飞行时间质谱及热重分析对低分子量聚苯醚的结构、分子量及其他性能进行了表征。实验结果表明,加入链转移剂制备得到的聚苯醚产品具有更大的特性黏度、更少的易挥发组分和更少的小分子量分子链。     

链转移剂对聚丙烯酰胺产品分子量和不溶物的影响

以丙烯酰胺(AM)、丙烯酸(AA)为原料,采用低温复合引发剂体系(叔丁基过氧化氢-硫酸亚铁与偶氮引发剂)制备了高分子量阴离子聚丙烯酰胺产品.探讨了不同链转移剂及其使用量对聚丙烯酰胺产品分子量和不溶物的影响.实验结果表明,次亚磷酸钠的链转移效果较好,在使用量为20×10-6时,所得聚丙烯酰胺产品分子量接近1900万,不溶物小于0.3％.     

制备聚丙烯酸钠分散剂的最佳工艺条件探究

以丙烯酸为单体,采用过硫酸铵和亚硫酸氢钠为氧化还原引发剂,同时亚硫酸氢钠又作为链转移剂来制备低分子量的聚丙烯酸钠.研究了单体浓度、引发剂用量、链转移剂用量以及反应温度对分子量和分散性的影响.通过正交设计实验确定了最佳反应条件:过硫酸铵用量为5.56%,亚硫酸氢钠为4.44%,单体浓度为33.3%,温度70℃,反应时间为3h.     

制备聚丙烯酸钠分散剂的最佳工艺条件探究

以丙烯酸为单体,采用过硫酸铵和亚硫酸氢钠为氧化还原引发剂,同时亚硫酸氢钠又作为链转移剂来制备低分子量的聚丙烯酸钠.研究了单体浓度、引发剂用量、链转移剂用量以及反应温度对分子量和分散性的影响.通过正交设计实验确定了最佳反应条件过硫酸铵用量为5.56%,亚硫酸氢钠为4.44%,单体浓度为33.3%,温度70℃,反应时间为3h.     

链转移剂调控DMDAAC均聚物分子量

以工业级二甲基二烯丙基氯化铵(DMDAAC)为反应单体、甲酸钠或甲醇为链转移剂,选择过硫酸铵-亚硫酸氢钠氧化还原引发体系,采用水溶液聚合法得到分子量在800～9000的PDMDAAC.通过正交实验考察了单体质量分数、聚合温度、聚合时间、聚合体系pH值、引发剂用量、还原剂用量和链转移剂用量对聚合产物特性粘数和单体转化率的影响.研究了链转移剂对PDMDAAC分子量的调控作用及其用量对聚合物特性粘数和单体转化率的影响规律.     

低分子量聚丙烯酸钠的合成与分析

低分子量的聚丙烯酸钠具有良好的分散性能,本文以丙烯酸为单体,过硫酸铵为引发剂,异丙醇为链转移剂,通过中和法合成了低分子量的聚丙烯酸钠,用端基法测得其数均分子量。通过改变单体浓度、引发剂用量、链转移剂用量和反应温度等反应条件,得出了各合成因素对聚丙烯酸钠分子量影响的趋势。     

简讯

低聚合度聚氯乙烯制造方法 已知往聚合体系加入链转移剂可以得到聚合度较低的聚氯乙烯。 这些链转移剂是含有巯基(氢硫基—SH)和羟基(—OH)或羧基(—COOH)的有机化合物,少量加入便有效果,对环境卫生影响不大。但问题是,这种有机化合物要在聚合前加入,造成聚氯乙烯粘度调节上有困难,即生成的聚氯乙烯的粒度分布宽。     

ACR中壳层PMMA相对分子质量对PVC／ACR共混物性能的影响

采用种子乳液法制备了核壳型聚丙烯酸酯(ACR),并分别采用十二烷基硫醇和正辛基硫醇作为链转移剂对 ACR壳层的聚甲基丙烯酸甲酯(PMMA)进行相对分子质量调节,并用于PVC共混改性。黏度法对PMMA的相对分子质量测定表明,正辛基硫醇的相对分子质量调节能力较强。采用差示扫描量热分析测定PMMA的玻璃化转变温度(Tg),并对共混树脂进行动态力学性能测试。当ACR壳层PMMA平均相对分子质量低于12×104时,PVC/ACR 共混树脂的缺口冲击强度大大提高。与纯PVC相比,共混树脂的Tg均略有提高,其增量随ACR壳层PMMA平均相对分子质量的降低而减小。动态力学性能测试结果表明,ACR壳层聚合物平均相对分子质量越低,共混物分子链段运动活化能提高越少。     

S-500型低聚合度PVC树脂的开发研究

研究了S-500型低聚合度PVC树脂的合成技术,确定了使用链转移剂合成S-500型PVC树脂的聚合配方和工艺条件。结果表明:S-500型PVC树脂相对分子质量分布集中,颗粒规整度好,粒度分布集中,熔体流动速率较高,加工塑化性能良好。     

Controlled free‐radical polymerization of vinyl chloride

Owing to the importance of poly(vinyl chloride) (PVC) as the second‐largest plastic in volume after the polyolefins and above styrene polymers, the control of the free‐radical polymerization of vinyl chloride (VC) is of high industrial and academic interest. But still the term “controlled” polymerization is not yet clearly defined. Often it is used for quasi‐living polymerizations with equilibrium reactions in the initiation and/or termination step or for the control of the molecular weight distribution (MWD), but it can also be applied to several structural aspects such as stereochemistry, branching, or special technical properties. In the present article, the control of chain growth and chain transfer is discussed. It has been well known for many years that the propagation step in the VC polymerization is terminated to a large degree by the rather frequent and temperature‐dependent chain transfer of the growing macromolecules to the monomer. Therefore, the degree of polymerization is strongly governed by the polymerization temperature. However, this transfer step does not result in a controlled or a narrow MWD. By means of free‐radical nitroxide‐mediated polymerization of VC in suspension, PVC with a narrower MWD can be obtained also at higher polymerization temperatures. The resulting PVC with nitroxide end groups can act as a macro‐initiator for various monomers, resulting in two‐block copolymers, which are, e.g., interesting compatibilizers in blends with PVC. J. VINYL ADDIT. TECHNOL., 11:86–90, 2005. © 2005 Society of Plastics Engineers     

黄原酸酯调控的氯乙烯的可逆-加成断裂链转移聚合

以三种不同结构的黄原酸酯为调控剂,进行氯乙烯（VC）溶液和细乳液可逆加成-断裂链转移（RAFT）聚合,发现O-乙基黄原酸丙酸乙酯对VC聚合的调控效果良好,氯乙烯RAFT细乳液聚合速率明显大于溶液聚合,VC聚合12 h转化率大于90%,但聚氯乙烯（PVC）的分子量分布宽于溶液聚合产物。核磁共振和紫外可见吸收光谱分析证明合成的PVC具有黄原酸酯基端基结构,结构缺陷少。含黄原酸酯基PVC可进一步调控VC及醋酸乙烯酯聚合,进行扩链或得到嵌段共聚物。结合聚合动力学,说明黄原酸酯调控的氯乙烯聚合具有活性特征。     

Modeling of molecular weight distribution of gas‐phase polymerization of butadiene

A mathematical model of the molecular weight distribution (MWD) based on a multilayer model and an improved intrinsic kinetics model was proposed to simulate the MWD of the gas‐phase polymerization of butadiene with a heterogeneous catalyst. Intrinsic kinetics and heat and mass‐transfer resistances based on the multilayer model of a polymeric particle were considered in the modeling of the MWD. The effects of the reaction conditions, catalyst particle size, mass‐transfer resistance, deactivation of active sites, and transfer of the polymer chain on the molecular weight and MWD were simulated. The results show that the effects of the deactivation of active sites and transfer of the polymer chain on the average molecular weight are significant and that the effect of the catalyst particle size on the MWD is not significant. The simulation results of the molecular weight and MWD are compared with the experimental results. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 88–103, 2003     

溶解时间对凝胶渗透色谱法测定PVC分子质量的影响

介绍了应用凝胶渗透色谱法测定PVC分子质量的方法,讨论了常温下四氢呋喃溶解PVC时间对PVC分子质量及分子质量分布测定结果的影响。结果表明：PVC的溶解时间越长,测得的数均分子质量和重均分子质量越大,分子质量分布越窄;聚合度低的PVC比聚合度高的PVC受溶解时间影响更大些。     

低分子量聚N-乙烯基甲酰胺-co-乙烯胺的合成

以N-乙烯基甲酰胺为单体,N,N-二甲基甲酰胺和乙酸乙酯为混合溶剂,偶氮二异丁腈为引发剂,十二硫醇为链转移剂,通过沉淀聚合法制备了低分子量的聚N-乙烯基甲酰胺。详细研究了单体质量分数、混合溶剂配比、引发剂用量、链转移剂用量、反应温度及反应时间对聚合反应的影响。在最佳聚合条件下,聚合物收率可达93.1%、聚合物的数均分子量(Mn)为2 975.2,PDI=2.64,且聚合残液可循环利用。然后将所得聚合物在酸性条件下水解,制备了不同胺化度的聚N-乙烯基甲酰胺-co-乙烯胺,产品的数均分子量为1 000~1 400,PDI为1.34~1.40。     

四氟乙烯等的水相沉淀调聚反应的聚合度方程及其模拟

对于非衰减或弱衰减的＂理想链转移体系＂,考虑生成的聚合物对气相空间的压缩作用,导出了采用稀水溶液沉淀聚合工艺（俗称的分散聚合和悬浮聚合）制备低分子质量聚四氟乙烯等一类调聚反应中的瞬时和累积数（质）均聚合度随聚合转化率变化的方程,并进行了讨论和模拟。结果显示：在恒压聚合期,聚合度可以呈逐渐升高的趋势,但也可以维持恒定或逐渐降低,链转移剂浓度则呈与此相反的变化;阐明了此类反应的链转移剂或聚合压力的选择原则为：CS/[M]g=Mr,M/ρp,一般CS〈〈1;降压聚合期间,因CS〈〈1,链转移剂相对含量大幅度提高,聚合度急剧下降。贯穿整个聚合周期生成的聚合物粒子呈一种内外分子质量有别的核壳结构。结果有望对此类低分子质量聚合物的合成起到一定的理论指导作用,但对强衰减链转移体系可能误差较大。     

Modeling of molecular weight distribution of propylene slurry phase polymerization on supported metallocene catalysts

A mathematical model of the molecular weight distribution (MWD) based on a particle growth model and the kinetic scheme is developed to simulate the MWD of the slurry phase propylene polymerization on a silica-supported metallocene catalyst by means of the equations of moments. The model is used to predict molecular weight distribution, including the number-average molecular weight, the weight-average molecular weight, and the polydispersity index. The results show that the mass transfer has great influence on the polymerization reaction, and it can broaden the MWD especially; moreover, the MWD can be evaluated by simulation; the average molecular weight increases as pressure or temperature, and MWD shifts to long chain lengths as the effective diffusion coefficient increasing thought the influence is not remarkable; furthermore, the MWD's simulation results are calculated, which fit greatly with the experimental data.     

Prediction of molar mass distribution,number and weight average degree of polymerization and branching of low density polyethylene

An extended mathematical model of an autoclave reactor for the high pressure polymerization of ethylene is presented. It allows one to predict not only the conversion but also the molar mass distribution, short and long chain branching, number and weight average degree of polymerization as a function of the synthesis conditions. The model includes the initiation step, chain growth, chain termination by disproportionation and combination, chain transfer to the monomer, polymer and modifier, and intramolecular chain transfer in the polymer radical. Number and weight average degrees of polymerization were computed by means of generating functions. For the calculation of the molar mass distribution recursion formulae are given. The performance of the model is shown by the good agreement of the predicted values with the experimental data.