Electrical Conductivity in Poly(vinyl Chloride)

Conductivity and Seebeck coefficient measurements have been made on commerically-available molded PVC samples containing a range of impurities and on much purer specimens recast from tetrahydrofuran solution. Activation energies measured in the latter materials were not very reproducible; it seems likely that the evaporation of gold electrodes thermally initiates a dehydrochlorination reaction which renders the samples unstable. A range of activation energies from 1.4 to 1.8 eV was observed in the impure samples. The Seebeck coefficient measurements indicated that the majority carriers were negatively charged; the linearity of the current-voltage relationship up to applied field strengths of 80,000 V/cm then suggested an electronic conduction mechanism, although considerable polarization effects were observed in both pure and impure samples. The Seebeck coefficient results also showed that even the purest PVC obtainable is unlikely to be an intrinsic semiconductor, and that the electron transport mechanism probably corresponds more closely to the small polaron hopping model than to the conventional energy-band formation model commonly applied to inorganics.     

Structure and Dehydrochlorination of Poly(vinyl Chloride)

The wide applicability of poly(vinyl chloride) (PVC), a tough thermoplastic resin, is due to a combination of moderate cost with the following characteristics [1]: (i) good general properties as a plastic material: (ii) great variation in properties, e.g., increase in heat distortion temperature, resistance to hot melt flow, improvement in mechanical, electrical properties, and processability of unplasticized PVC through external plasticization, block and graft copolymerization (internal plasticization), and chemical modification, e.g., chlorination, Friedel-Crafts, and cross-linking reactions: and (iii) processing versatility including injection molding, extrusion, blow molding, calendering, and lamination to produce many products of potential uses.     

Hydrogen Halide-Catalyzed Thermal Decomposition of Poly(vinyl Chloride)

The thermal decomposition of solid PVC was studied in the presence of added hydrogen chloride and hydrogen bromide over the temperature range 170–210°C. Under certain conditions the decomposition was shown to be dependent in a first-order manner on the hydrogen halide pressure. These gases acted as catalysts, increasing the rate of HCl evolution and the degree of discoloration but not producing longer polyene sequences. Activation energy for the HCl-catalyzed process was found to be similar to that of the uncatalyzed decomposition of PVC. A unified mechanism is presented for an overall process consisting of three steps: random generation of a single carbon-carbon double bond in the cis configuration; 1,4-elimination of HCl via a six-centered transition state yielding a polyene; HCl- or HBr-catalyzed isomerization of the polyene formed by HC1 elimination to regenerate the initial structure. Hydrogen chloride catalysis is seen as an integral part of the overall process.     

Characterization of Polyene Sequences in Poly(vinyl Chloride)

Some aspects of the formation and propagation of polyene sequences during the thermal degradation of PVC have been discussed. The average polyene sequence length occurring in a suspension polymerized PVC, degraded in nitrogen at 190°C, was determined to ca. 10 units. The results were somewhat dependent on the type of analysis employed. The formation of internal polyene sequences was characterized by three stages. After an initial period, where the number of internal sites remained constant, new sites were rapidly formed. The high rate of formation then gradually decreased with increasing conversion. Degradation mechanisms explaining this behavior were suggested.     

新型软质抗静电聚氯乙烯材料的研究

合成了一种长链季铵盐类化合物, 将其用作抗静电剂添加到软质聚氯乙烯(PVC)材料中, 测试了材料的表面电阻、力学性能, 并采用扫描电子显微镜测试研究了其结构. 结果表明: 随合成长链季铵盐的添加量增大, PVC材料的表面电阻率降低, 较小的添加量(4.5%)即可使材料的表面电阻率降低至3.0×10⁸ Ω以下, 达到了煤矿行业对高分子材料抗静电性能的要求. 在上述抗静电PVC材料中添加一定量的聚氧化乙烯(PEO), 可以降低抗静电材料对环境湿度的依赖性, 并提高PVC材料的力学性能和抗静电性能.     

氯化镁增塑改性聚乙烯醇

以氯化镁为增塑剂, 采用流延法制备了增塑改性聚乙烯醇(PVA). 研究了氯化镁与PVA的相互作用以及氯化镁增塑改性PVA的结晶性能、 热性能和机械性能. 研究结果表明, 氯化镁能与PVA大分子发生较强的相互作用, 从而破坏PVA分子链内和链间的氢键, 降低PVA的结晶度. 氯化镁对PVA的热性能影响显著, PVA在加入氯化镁后的热分解过程由纯PVA的两段失重过程转变成三段失重过程. 氯化镁可有效增塑PVA, 其玻璃化转变温度降低, 拉伸强度下降, 断裂伸长率上升, 储能模量下降.     

聚偏二氯乙烯构象分布的理论研究

在MP2/6-311++G**水平下, 对2,2,4,4-四氯戊烷与2,2,4,4,6,6-六氯庚烷旋转异构体构象进行几何优化和能量计算. 结果表明, 对于2,2,4,4-四氯戊烷, 采用gauche-gauche排列的旋转异构体的能量较低; 2,2,4,4,6,6-六氯庚烷旋转异构体中, 采用trans-gauche-trans-gauche排列的构象能量较低. 反之, 完全采用trans-trans排列的旋转异构体构象能量较高, 不稳定. 通过比较模型分子不同旋转异构体构象的能量差值可以得到一级和二级特征的相互作用能差, 进而计算统计权重参数. 在此基础上, 应用计算得到的模型分子的几何构型与统计权重参数, 分别构建针对—CH2—和—CCl2—中心的聚偏二氯乙烯的6态旋转异构态模型. 通过旋转异构态模型可以计算聚偏二氯乙烯分子中各种构象的分布.     

聚氯乙烯薄膜的压电性研究

系统地研究了极化条件、热历程、增塑作用等与聚氯乙烯薄膜压电性的关系,并且讨论了聚氯乙烯薄膜压电性对时间的稳定性。研究结果表明,极化聚氯乙烯薄膜的压电应变常数d_(33)值为2.1×10~(-12)C/N,压电电压常数g_(33)达到73.9×10~(-3)V·m/N,与经典的压电材料石英晶体的压电性相当。     

Miscibility Studies on Chitosan/Poly(vinyl alcohol) Blends

Miscibility studies of chitosan (CHI)/poly(vinyl alcohol) (PVA) blend in buffer solution were carried out in several blend compositions (10/90, 20/80, … , 90/10). Viscosity, ultrasonic velocity, density and refractive were measured at 30, 40 and 50°C, respectively. Using viscosity data, the interaction parameters μ and thermodynamic parameter α were computed to determine the miscibility of the blend in solution. These values revealed that the blend is miscible when the chitosan content is more than 60% in the blend. The obtained results were further confirmed by the ultrasonic velocity, density and refractive index study.     

Dynamic and Isothermal Thermogravimetric Degradation of Poly(vinyl Chloride)/Chlorinated Poly(ethylene) Blends

The thermal degradation of poly(vinyl chloride)/chlorinated poly(ethylene) (PVC/CPE) blends of different compositions was investigated by means of dynamic and isothermal thermogravimetric analysis in flowing atmosphere of nitrogen. Kinetic parameters (the apparent activation energy E, and pre-exponential factor Z) were calculated after Flynn-Wall-Ozawa method for the first stage of dynamic degradation of PVC/CPE blends, and after Flynn method for the isothermal degradation. In both cases, there is the compensation dependence between the values E and logZ. The values of compensation ratios as well as the characteristics of TG and DTG curves, confirm the stabilizing effect of CPE on PVC dehydrochlorination. This revised version was published online in July 2006 with corrections to the Cover Date.     

Conformational properties of polar polymers. I. Poly(vinyl chloride)

A recently developed method for including polar bonds in conformational energy calculations is applied to poly(vinyl chloride). Inductive effects on dipole moments and the effects of intervening atoms on electrostatic interaction energies are represented by polarizability centers in conjunction with bond centered dipoles. Solvation energies are estimated by means of a continuum dipole–quadrupole electrostatic model. Calculated energies of a number of conformations of meso and racemic 2,4-dichloropentane and the iso, syndio, and hetero forms of 2,4,6-trichloroheptane give satisfactory representations of isomer and conformer populations. Electrostatic effects are found to be quite important. However they appear to be effectively of sufficiently short range that the calculated conformer energies are found to be fit well by a linear combination of interaction parameters (consisting of gauche, skew chlorine, four-bond CH₂…CH₂, CH₂…Cl, and Cl…Cl interactions) conventional to vinyl polymers and a special four-bond interaction that arises when the bond sequence Cl? CH? CH²? CH? Cl is (nearly) coplanar. These interaction parameters when assembled into statistical weight matrices lead to calculated values of both the characteristic ratio and the dipole moment ratio in satisfactory agreement with experiment. Least energy paths for transitions between the most stable conformations are also calculated.     

The Thermal Stability of Poly(vinyl Chloride) Prepared by Radiation Polymerization

The thermal stability of poly(vinyl chloride) prepared by radiation polymerization has been examined by thermogravimetric analysis, hydrogen chloride evolution, and visible spectra measurements in films and solutions. Radiation polymerized PVC, prepared with relatively high radiation doses, is much less stable than a commercial suspension polymerization PVC. On the other hand, the stabilities of radiation polymerized PVC, prepared with relatively high radiation doses, is much less stable than a commercial suspension polymerization PVC. On the other hand, the stabilities of radiation polymerized samples, which had received less than 0.45 Mrad, are comparable with commercial PVC. It is suggested that the allylic chlorine atoms produced in the radlysis of the polymer, concurrent with its formation, are chiefly responsible for the instability of the high doses samples.     

Photo-Oxidative Degradation of Poly(vinyl Chloride) Based Nanocomposites Under Ultraviolet Irradiation

The poly(vinyl chloride) based nanocomposites with 3.0% weight content of the photo-active zinc oxide (ZnO) nanoparticles or the photo-inert calcium carbonate (CaCO₃) nanoparticles was prepared by the solution mixing method, respectively. Their photo-oxidative degradation under ultraviolet irradiation (365 nm) at room temperature were compared with the pure poly(vinyl chloride) via Fourier transform infrared spectroscopy, Thermogravimetric analysis and x-ray photoelectron spectroscopy analyses. The results showed that the photo-inert calcium carbonate (CaCO₃) nanoparticles hampered the photo-degradation of poly(vinyl chloride), whereas the photoactive zinc oxide (ZnO) nanoparticles accelerated the photodegradation of poly(vinyl chloride). Furthermore, the ZnO nanoparticles also favored the crosslinking reaction of the dehydrochlorinated poly(vinyl chloride).     

Structural Defects in Poly(vinyl chloride) and the Mechanism of Vinyl Chloride Polymerization: Comments on Recent Studies

Investigations in the title areas within the past ten years are summarized and critiqued. The polymerizations studied were performed by conventional free-radical methods. A new mechanism, not yet confirmed, is suggested to explain a reported enhancement in the chloromethyl branch concentration of poly(vinyl chloride) (PVC) prepared at high conversions of monomer. This mechanism involves an intramolecular 1,5 hydrogen shift in a 1,3,5,6-tetrachlorohexyl radical. Evidence showing that most of the internal double bonds in PVC are not formed via intermolecular H abstraction from internal monomer units is tentatively rationalized, in part, by hydrogen transfer via at least one cyclic transition state containing more than eight members. The absence of free chlorine atoms from polymerizations of vinyl chloride (VC) is reaffirmed, and the copolymerization of VC with the chloroallylic chain ends of PVC is argued to be insignificant. New information in the literature does not invalidate the currently accepted mechanism of vinyl chloride polymerization.     

TG and Flammability Studies on Polymer Blends Containing Acrylonitrile–butadiene–styrene and Chlorinated Poly(vinyl Chloride)

The effects which an iron(III) based smoke suppressing compound have on the thermal stability of some acrylonitrile–butadiene–styrene/chlorinated poly(vinyl chloride) (ABS/CPVC) polymer blends have been investigated. Thermogravimetric analysis (TG) experiments have shown that there are three distinctive stages occurring during the thermal breakdown of these blends both when the iron compound is absent and present in the polymer formulations. The most important effect which the iron compound has when it is present in these blends is to modify the decomposition chemistry which takes place and the effect becomes more pronounced as the concentration of CPVC present in the blends increases. Other important effects are that the iron compound stabilises the blends so that mass loss is significantly reduced (by up to 50% in some cases) and the onset temperature of decomposition is raised. Flammability data generated during earlier work is supported by the TG results obtained in this work especially in the important area of smoke formation and suppression. This revised version was published online in August 2006 with corrections to the Cover Date.     

The Kinetics and Mechanism of the Thermal Dehydrochlorination of Poly(vinyl Chloride)

Poly(vinyl chloride) degrades thermally by an acceleratory reaction in which the rate of hydrogen chloride evolution is slow at the beginning, increases with time (passing through a maximum), and then decreases. A kinetic model based on the zipper mechanism shows excellent agreement with observed data from the initial to the final stages of each dehydrochlorination. Hydrogen chloride is shown to be essential for the initiation of zip chains and may or may not be essential for the zip reaction. When hydrogen chloride is removed in a stream of inert gas, as it is in some tests purported to study the kinetics of degradation, the initiation of zip chains is significantly inhibited. The zip reaction, once it has been initiated, is not inhibited or stopped even by long exposure to atmospheric conditions.     

Factors that Influence the Kinetics of the Degradation of Poly(vinyl Chloride)

The degradation of five samples of PVC having different degrees of polymerization has been studied by a technique that permits a precise measurement of the rate of hydrogen chloride elimination as % HCl/min. All samples followed acceleratory kinetics at both low and high conversions. The conversion rate, which changed from the beginning to the end of a degradation, depended primarily upon the fraction of chains producing hydrogen chloride. The fraction of producing chains and the kinetic pattern were influenced by the presence of hydrogen chloride, the physical state of the sample, the previous degradation history, and the presence of intentionally added substances. Zipper kinetics permit the reproduction of kinetic data in terms of three parameters: k₁, the fraction of chains initiating per second, k₂, the fraction of a zip chain that zips per second, and k₃, an arbitrary parameter that accounts for residual hydrogen chloride after degradation has ceased.     

TG/FT-IR Studies of Poly(Vinyl Chloride) Blends

Thermogravimetry coupled with Fourier transform infrared spectroscopy (TG/FT-IR) was used to investigate the stabilizing action of 3-(2,4-dibromophenylazo)-9-(2,3-epoxypropane)carbazole on the degradation of poly(vinyl chloride) (PVC). It was found that this secondary stabilizer increases the initial temperature of hydrogen chloride evolution (the main process responsible for PVC decomposition), thereby allowing its application for novel PVC systems with enhanced thermal stability. The application of TG/FT-IR technique for study of the thermal properties of polymeric materials offers additional characterization options in comparison with thermogravimetry, if used alone. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Comparative Studies on Hydrophilic and Hydrophobic Segments Grafted Poly(vinyl chloride)

Poly(vinyl chloride) (PVC) is one of the mostly produced plastics in the world and is widely used in single-use medical devices.However,the additives that are often necessary for PVC arouse concerns of its safety,thus quests the modifications of PVC itself.In this study,poly(ethylene glycol) (PEG) and polydimethylsiloxane (PDMS) segments were grafted onto PVC backbone in similar ways,and the chemical structures of the modified PVCs were characterized by Fourier transform infrared spectra,X-ray photoelectron spectra,thermogravimetric analysis and differential scanning calorimetry.Moreover,the water contact angle,protein adsorption,platelet adhesion,cell attachment and proliferation on different material surfaces were studied and compared.It was found that both PEG and PDMS grafting yielded improvement on biocompatibility compared with bare PVC,while hydrophobic PDMS grafted PVC showed more effective on cell attachment and proliferation than that of hydrophilic PEG grafted PVC.