The Rate of Degradation by Ultrasonation of Polystyrene in Solution

Abstract

The rate of degradation by ultrasonation of polystyrene in tetrahydrofuran solutions has been measured at various concentrations, temperatures, and irradiation intensities. As reported earlier, the course of the changes in molecular weight distributions is independent of the molecular weight (MW) of the initial polymer and of the degradation conditions. Therefore, the time dependence of the extent of the degradation can be meaningfully compared for various reaction conditions and for polymers with different original MWs. The extent of the scission process was expressed in terms of the degradation index (DI), the ratio of the number of chain bonds broken to those initially present. The problem of the existence of a minimum MW required for sonic scission is considered and arguments are advanced in favor of the assumption of a minimum degradable chain length for the purpose of evaluation of degradation data. This minimum MW was found to be about 30,000. DI values were corrected for the “unbreakable” chain ends.

It was observed that curves representing the time dependence of DI were linear on double logarithmic plots for all experiments, DI being proportional to t^0.85. By shifting these lines along the time axis a master curve was obtained representing all data for all experimental conditions over almost three decades of DI. Thus the time-dependent rate of scission of any run relative to that under reference conditions can be expressed by a single value of the time transposition factor, a measure of the shift. This transposition factor provides a simple method for assessing the effects of experimental conditions. Some data are reported expressing the effect of MW of the initial polymer, concentration, temperature, and irradiation intensity on degradation rate.     

本体溶液法合成超高分子量聚苯乙烯

对２，３－二氰基－２，３－二苯基丁二酸二乙酯引发苯乙烯本体溶液聚合，合成超高分子量聚苯乙烯的宏观动力学进行了研究。结果表明，这种引发剂在苯乙烯中引发聚合性能温和，在一定条件下，随反应时间的增长，聚合产物的分子量不断增高，可形成超高分子量聚合物。     

Analysis of the Molecular Weight Distribution of Polystyrene

In this paper are reported molecular weight distributions (MWD) of polystyrenes obtained by bulk free-radical polymerization of styrene under isothermal conditions. MWD of polystyrenes were determined by gel-permeation chromatography. From analysis of the results it is apparent that samples synthesized at 80 °C and 90 °C have a bimodal MWD whereas those obtained at 100 °C and 110 °C have unimodal MWD. By two-peak deconvolution of experimental curves (at 80 °C and 90 °C) it is possible to separate the contribution of polystyrene obtained before and after onset of the gel effect.     

分散聚合法制备窄分子量分布的聚苯乙烯微球

以无水乙醇为反应介质,以聚乙烯吡咯烷酮(PVP)为分散剂,偶氮二异丁腈(AIBN)为引发剂,采用分散聚合法制备分子量分布较窄的聚苯乙烯(PS)微球。研究了反应温度及反应时间、引发剂浓度和单体浓度对苯乙烯转化率和PS分子量分布的影响,采用SEM、GPC、FT-IR和TG对产物的形貌、分子结构和性能等进行了表征。结果表明:单体浓度为20%,引发剂用量为单体总量的0.7%,75℃下反应13h后,聚合反应的单体转化率可达87.8%,所制得的PS球形度较好,重均分子量为16.6万,分子量分布1.21,且具有优异的热稳定性。     

用GPC研究壳聚糖氧化降解过程中的分子量及其分布

用凝胶渗透色谱法跟踪研究了过氧化氢对壳聚糖氧化降解过程中壳聚糖的分子量及其分布的影响,结果表明,反应温度、时间和过氧化氢用量对壳聚糖的降解程度及降解产品质量均有影响。     

Study of the Degradation of High Molecular Weight Polystyrene in the Course of Size Exclusion Chromatography (SEC)

Abstract

The possibility of degradation of large macromolecules in their motion through a porous medium in the course of SEC decreases considerably the range of application of this highly productive and highly selective analytical method for the determination of the MWD of polymers. In fact, the MWD determined by SEC with the existence of degradation is mainly the distribution according to degradation fragments and does not reflect the initial molecular characteristics of the polymer.

The dependence of the degree of degradation of maccromolecules on the main parameters of the chromatographic experiment: the rate of the eluent flow, the size and shape of sorbent particles and the size of their pores was studied in detail. A non-monotonic change in the degree of degradation with increasing flow rate of the eluent was detected.

It is shown that the degree of degradation increases with decreasing particle size and the size of their pores. A new concept of the degradation of high polymers in SEC is formulated. It is related mainly not to the existence of local rate gradients in the interparticle volume but, rather, to the entire combination of hydrodynamic and adsorption effects accompanying the process of interaction between the macromolecules and the surface of sorbeiit particles. Practical recomendations are given for carrying out SEC, including that of super-high molecular weight samples under “non-degrada- tive” condritions.     

凝胶色谱法测定顺丁橡胶平均分子量及其分布的研究

通过一系列的条件试验,包括样品浓度、样品量及流动相流速对柱效的影响,确定了最佳的凝胶色谱（ＧＰＣ）试验条件;采用普适校正法将聚苯乙烯（ＰＳ）标定曲线转换成顺丁橡胶（ＰＢ）标定曲线,并对Ｍａｒｋ－Ｈｏｕｗｉｎｋ方程式中Ｋ,α值的选择进行了讨论;采用４种分子量加宽方程对色谱柱加宽效应进行改正计算,通过比较,选定适合本试验系统的加宽效应的改正方法;用粘度法测得的顺丁橡胶特性粘度（η）吻合ＧＰＣ所测得特性粘度值,证明了方法的可靠性。     

Olefin Polymerizations and Copolymerizations with Aluminum Alkyl-Cocatalyst Systems. V. The Molecular Weight and Molecular Weight Distribution of Polystyrene

Abstract

The polymerization of styrene with the cationic initiator system AlR₂Cl/RCl was investigated further. Earlier conclusions [1] were corroborated and expanded by an analysis of the number and weight average molecular weights. Alkyl halides with low (high) R?Cl bond dissociation energies are efficient (poor) coinitiators of the polymerization of styrene. In the presence of efficient RCl coinitiators, the molecular weights strongly decrease and the molecular weight distributions strongly increase with increasing conversions (Fig. 1). With poor cointiators, only low conversions are obtained even in the presence of large amounts of AlEt₂Cl. The data are discussed in terms of a previously proposed mechanism [1].     

复合茂钛催化剂制备宽分子量分布间规聚苯乙烯的研究

采用新型茂钛化合物Cp^*Ti(O-Ph-OCH3)3(A)／CpTi(O-Ph-OCH3)3(B)和Cp^*Ti(O-Ph-OCH3)3(A)／Cp^*Ti(O-Ph-F),(C)作为复合催化剂,在甲基铝氧烷(MAO)、三异丁基铝(TIBA)激活下进行苯乙烯间规聚合。采用A／B复合催化剂可通过调节两种茂钛催化剂的摩尔配比,得到宽分子量分布的间规聚苯乙烯(s-PS);而采用A／C复合催化剂得到的产物分子量分布基本不变。对不同聚合条件下得到的s-PS产物进行了GPC分析。     

Molecular Weight and Dynamic Properties of Polystyrene Solutions

Eight fractions of polystyrene with linear structure and different molecular weights were prepared by fractional precipitation with methanol from a solution of polystyrene in chloroform. The polystyrene fractions were dissolved in toluene to prepare solutions with different concentrations for dynamic property studies. The dynamic shear modulus and the tangent of the mechanical loss angle for these solutions were measured by the acoustic-resonance method.     

Molecular Weight Effect on Latex Film Formation from Polystyrene Particles: A Photon Transmission Study

The photon transmission method was used to probe the time evolution of film formation from latex particles. Two different latex films were prepared from high molecular weight (HM) and low molecular weight (LM) polystyrene particles at room temperature and were annealed at various temperatures in 2.5-min time intervals above the glass transition. The increase in the transmitted photon intensity (Itr) is attributed to the increase in "crossing density" at the junction surface. The Prager-Tirrell model was employed to interpret the increase in crossing density at the junction surface. The back and forth activation energies were measured for HM and LM films and found to be around 59 and 87 kcal/mol for a reptating polymer chain across the junction surface. Monte Carlo simulations were performed for photon transmission through a rectangular lattice. The number of transmitted photons (Ntr) was calculated as a function of the mean free path of photons. It was observed that Ntr, similar to Itr, increases as the square of the mean free path of photons is increased. Copyright 1999 Academic Press.     

利用流变仪测定聚苯乙烯的分子量和分子量分布的研究

用先进流变扩展系统ARES（Advanced Rheology Expanded System）对聚苯乙烯的分子量和分子量分布进行了测定,并且将所得的结果与GPC的结果进行了比较,发现误差非常小．因此认为用ARES进行特定聚合物的分子量及分子量分布测定,是一种快速、准确的测定方法,对生产的质量控制有一定的帮助．     

超高分子量聚苯乙烯的性能测定

聚苯乙烯(PS)制成高定向薄膜后可用于电视机、雷达、高频率电线等电器部件和发泡材料。其主要缺点是耐冲击强度低、耐温性差。大量的改性工作主要是通过混炼或共聚等方法制成非均聚物,其结果透明性不佳,而且生产工艺复杂、成本高。聚苯乙烯改性的另一个途径是提高其分子量,使_w达到4.0×10~5以上,形成超高分子量聚苯乙烯(UHMW PS)。     

壳聚糖锰(Ⅱ)配位与氧化控制降解寡糖的分子量分布

Complexes of chitosan with Mn(Ⅱ) were prepared by adding Mn(OAc)₂·4H₂O to Chitosan solution. IR, elemental analysis and TG analysis were used to character the complex. The results showed that there were coordinate bands formed. H₂O₂ was used to degrade chitosan-Mn(Ⅱ) complex, and the molecular distribution of degraded products were investigated after eliminating Mn(Ⅱ) ions using the cation exchange resin column. The result suggested that the Chitosan could be degraded rapidly, the degradation started from higher molecular weight range, the molecular weight distribution of oligosaccharides was much more narrower than that of degradated products from common methods such as hydrolysis, acidic and oxidizing methods. The index of molecular weight distribution was changed with the average degradability. When exceeding 10 oligosaccharides, the smaller of the DP, the smaller of the index.     

粘度法和超离心沉降法测定环型聚苯乙烯分子量

本文介绍了测定环型聚苯乙烯分子量的两个计算关系式。     

New Half‐Metallocene Catalysts Generating Polyethylene with Bimodal Molecular Weight Distribution and Syndiotactic Polystyrene

A new type of half‐metallocene catalyst for the polymerization of ethylene and styrene, Cp*M((O)₃O₉Si₇(c‐C₅H₉)₇) (M = Ti ( 1) ; Zr ( 2 )), is prepared by the reaction of (HO)₃O₉Si₇(c‐C₅H₉)₇ with Cp*MCl₃ in the presence of triethylamine. Complex 1 is stable to heat and air, but its heavier congener 2 is slightly air‐sensitive. The catalytic systems 1 /MMAO and 2 /MMAO, in which MMAO is modified methylaluminoxane, show good activities in ethylene polymerization, with that of 2 /MMAO greater than that of 1 /MMAO. Polyethylenes with bimodal molecular weight distributions were obtained. In addition, the catalytic system 1 /MMAO shows fairly good activities for the syndiospecific polymerization of styrene.     

交联高分子的分子量分布

从概率母函数出发,利用Lagrange展开,导出了起始分子为Flory和Poisson分布的交联高聚物的分子量分布函数,并用以描述交联分子结构的溶胶分数。     

Simulation of Molecular Weight Distribution After Polymer Breakdown. II. Degradation of cis-Polyisoprene by Ultrasound and Ozonolysis

czs-Polyisoprene was degraded by two different methods, ultrasound and ozonolysis. Monte Carlo simulation of the molecular weight distribution after breakdown gave very poor fits to the observed data when the extent of degradation was estimated from number-average molecular weight data. Much improved fits were obtained when the degradation index was estimated by a least-squares method.     

超高效凝胶色谱法测定聚乙二醇衍生物的分子量及其分布

采用超高效聚合物色谱(APC)技术,以单甲氧基聚乙二醇丙醛(m PEG_p ALD)为代表,测定了聚乙二醇衍生物的相对分子质量及其分布和杂质含量,优选了色谱柱和流动相,考察了样品质量浓度变化以及溶解时间等对测定结果的影响。优化后3根超高效凝胶色谱柱串联,在柱温40℃,流动相95%甲醇,流速0.5m L/min,示差折光检测条件下,对m PEG_p ALD的分子量及其分布进行测定,同时得到杂质的相对含量。结果测得m PEG_p ALD主成分的重均分子量(Mw)为19 444,分布指数(D)为1.01;杂质1的Mw为38 703,D为1.01,含量为1.31%;杂质2的Mw为61 036,D为1.00,含量为0.70%。与常规凝胶渗透色谱(GPC)相比,该方法分辨率高,分析速度快,能快速测定m PEG_p ALD的相对分子量及其分布,并能得到其纯度和杂质含量,为其工艺研发、质量控制提供了科学的依据,同时也可用于其它PEG衍生物的相对分子量及其分布和纯度的测定。     

降冰片烯开环易位聚合反应的分子量及分子量分布控制

使用Grubbs催化剂催化降冰片烯单体进行开环易位聚合反应, 研究了催化剂搅拌溶解时间、聚合反应的溶剂极性和三苯基膦的加入等反应条件对降冰片烯单体ROMP反应分子量及分子量分布的影响, 从而得到降冰片烯ROMP反应的最佳条件.