用DSC研究线形多嵌段聚氨酯与聚氯乙烯、氯化聚氯乙烯共混相容性

用示差扫描量热法（DSC）研究了线形多嵌段聚氨酯（PU）与聚氯乙烯（PVC）、氯化聚氯乙烯（CPVC）共混相容性，说明了PU／VC、PU／CPVC的相容是由于共混物中形成了新的氢键的缘故．聚酯型聚氨酯与PVC、CPVC的相容性要好子聚酸型聚氨酯，CPVC与PU的相容性又要好于PVC．聚氨酯中硬段的引入不利于PU／PVC、PU／CPVC的相容性．     

PVB存在下PVC化学法脱氯化氢的研究

ＰＶＢ存在下ＰＶＣ化学法脱氯化氢的研究刘恒＊李大成陈朝珍（四川联合大学化工学院成都６１００６５）关键词聚氯乙烯，脱氯化氢，聚乙烯醇缩丁醛１９９６－０９－０８收稿，１９９７－０５－２６修回国家教育委员会留学归国人员资助费资助课题近年来在ＰＶＣ脱氯化氢制...     

用FTIR研究线形多嵌段聚氨酯与聚氯乙烯、氯化聚氯乙烯共混相容性

用溶液法得到线形多嵌段聚氨酯（PU）与聚氯乙烯（PV）、氯化聚氯乙烯（CPVC）的共混物。用FTIR研究PU/PVC、PU／CPVC共混物的相容性，发现PVC、CPVC的加入破坏了PU中原来的氢键，并且PU中的炭基（C=0）与PVC、CPVC中的α－H形成了新的氢键，因而说明了PU／PVC、PU／CPVC共混物具有良好的相容性。     

Thermal properties of poly(vinyl chloride)/polyurethane blends

Blends of poly(vinyl chloride) and a polyurethane elastomer were investigated by DSC and tensile testing. Up to 30 wt% single glass transition was found. It was concluded that the polyurethane forms partly a true blend and is partly disperged in the continuous blend phase.     

Novel preparation of electrically conducting poly (vinyl chloride) by photo-dehydrochlorination from poly (vinyl chloride)/polypyrrole composite film

Polypyrrole (PPy) was deposited electrochemically on a platinum plate from a nitric acid solution of pyrrole. The PVC/PPy composite film was finally obtained by casting poly(vinyl chloride) (PVC) onto the PPy electrode from a tetrahydrofuran solution of PVC. The prepared composite film was irradiated at 90°C with a low-pressure mercury lamp in the stream of hydrogen gas saturated with steam, and the PVC film was dehydrochlorinated, leading to the formation of conjugated polyene. The electrical conductivity (σ) of the PVC film in the irradiated composite film was reveled: σ=2.51 × 10^?5S cm^?1. By iodine doping, σ was further enhanced up to 5.04 X 10^?3 S cm^?1. The tensile strength of the irradiated composite film became larger than that of the original PVC film; i.e., the stress at break was: 461 (composite film); 401 kg cm^?2 (PVC). These results were brought about by the doping of radical species to the conjugated polyene. The anion, NO^?₃, doped during the electrodeposition of PPy was photodecomposed to generate radical NO₂ and this species was doped to the polyene, resulting in the formation of electrically conductive PVC and mechanically improved composite film. © 1994 John Wiley & Sons, Inc.     

改性聚氯乙烯絮凝剂的合成及其性能的研究

采用乙醇胺为亲核试剂对聚氯乙烯进行改性,控制胺化反应条件可以得到不同氮含量的产物.确定了最佳反应条件：温度80℃,PVC结构单元与乙醇胺的摩尔比1/1,反应时间小于36h,反应压力2.8MPa;用红外光谱表征了产物的结构、用元素分析测定了产物中N、H、C、Cl的含量;以ω=0.03的硅藻土水悬浮液模拟污水,考察了产物的絮凝性能.     

Radiation effects on the thermal degradation of poly(vinyl chloride) and poly(vinyl alcohol)

Radiation effects on the formation of conjugated double bonds in the thermal degradation of poly(vinyl chloride) (PVC) and poly(vinyl alcohol) (PVA) were investigated. Thin films of PVC and PVA were either irradiated with γ-rays at ambient temperature (pre-irradiation) and then subjected to thermal treatment, or irradiated at elevated temperatures (in situ irradiation). An extensive enhancement of the thermal degradation was observed for the pre-irradiation of the PVC films, which was more effective than the effect of the in situ irradiation at the same absorption dose. For the PVA degradation, however, the effect of the in situ irradiation was larger than that of the pre-irradiation. The results were explained and related mechanisms were discussed based on radiation-induced chemical reactions and their individual contributions to the thermal degradation behaviors of the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3089–3095, 1998     

聚氯乙烯表面共价键合肝素及抗凝血性的研究

采用Ar等离子体引发聚乙二醇(PEG)在聚氯乙烯(PVC)表面固定化,进一步对固定PEG后的PVC进行肝素化处理,以改善PVC材料的抗凝血性能。探讨了PEG浓度对Ar等离子体固定化反应效果的影响。通过X射线光电子能谱(XPS)、衰减全反射红外光谱(ATR-FTIR)、扫描电镜(SEM)和接触角测定研究了固定PEG前后PVC的表面性能和表面形貌的变化。XPS分析证实肝素已成功地共价键合于PVC表面。采用体外凝血时间测定和血小板粘附实验对材料的抗凝血性能进行评价,结果表明,被修饰PVC材料的抗凝血性能显著提高。     

Electrical conductivity of poly(vinyl chloride) obtained by photodehydrochlorination from laminated poly(vinyl chloride)/polypyrrole films

Poly(vinyl chloride) (PVC) has been converted to an electrically conductive structure by combined electrochemical and photochemical methods. PVC was cast on a polypyrrole (PPy) film electrode which had been electrochemically prepared. The PVC layer in the laminated PVC/PPy films was first dehydrochlorinated under the illumination of UV light, and the generated polyenes were subsequently doped with I₂ and FeCl₃. The maximum electrical conductivity achieved for such PVC film was 2.51 X 10^?2 and 8.63 10^?2 S cm^?1 after I₂ and FeCl₃ doping, respectively. The temperature dependence of the electrical conductivity showed different behavior in higher and lower temperature ranges. In the former (T > 243 K), the T^?1 law held, and the activation energy and bandgap were estimated as 0.25 and 0.49 eV, respectively. In the latter (T < 243 K), the conductivity mechanism followed the variable range hopping model (T^?1/4 law) in which the radius of the localized state wave function and the density of the localized states at the Fermi level were 1.25 × 10³ Å and 1.03 X 10¹⁵ eV^?1 cm^?3, respectively. © 1995 John Wiley & Sons, Inc.     

A Density Functional Theory Study of Poly (vinyl chloride) (PVC) Free Radical Polymerization

Summary: Quantum chemistry was applied to the free radical polymerization of Vinyl Chloride with the aim of elucidating the reaction kinetics and especially the formation of structural defects and low molecular weight polymer. The radical reactions were studied using the Density Functional Theory. All calculations were performed with B3LYP functionals and in particular the 6-31G(d,p) basis set was selected to evaluate the exchange and correlation energies. The computational method was first validated by predicting the rate constant of the propagation step and comparing the calculated values to experimental ones. Then intramolecular chain transfer, β-scission and branching reactions were also investigated, due to their direct connection with the production of defects in the growing chains. A comparison of the evaluated kinetic constants of such secondary reactions with other computational evaluations and experimental data was finally made.     

Migration of Additives from Poly(vinyl chloride) (PVC) Tubes into Aqueous Media

The stability and migration product of medical PVC tubes plasticized with polyadipates were investigated by ageing in phosphate buffer at pH 1.679 and water at different temperatures. Changes in the PVC tubes were studied by water absorption, weight loss, Fourier infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The low molecular weight migration product that was released was extracted and silylanized before gas chromatography/mass spectroscopy (GC/MS) identification and quantification. After 70 days, the weight loss was less than 0.5% and only a small amount of adipic acid migrated when a tube was aged at 37°C in water and phosphate buffer (pH 1.679), and at 70°C in water after 56 days. However, when aged at 70 and 110°C, gradual deactivation of heat stabilizer after 21 days of ageing in buffer solution and separation of plasticizer from PVC matrix occurred. When the tube was aged at 110°C, significant degradation of both polyadipates and PVC were observed. Adipic acid and 1,4-butanediol monomers and oligomers of polyadipate were the major migration products from polyadipates in the water ageing solution, while only a relatively high amount of adipic acid was identified as the main product in the buffer ageing solution.     

偶联剂对聚氯乙烯－聚丙撑碳酸酯共混体系力学性能的影响

偶联剂对聚氯乙烯－聚丙撑碳酸酯共混体系力学性能的影响王胜杰，黄玉惠，丛广民（中国科学院广州化学研究所广州５１０６５０）关键词聚氯乙烯，聚丙撑碳酸酯，偶联剂，丁腈胶，过氧化苯甲酰，共混聚氯乙烯（ＰＶＣ）是用量巨大的通用塑料，其软性制品需用大量的增塑剂，...     

Diffusion of small molecules through modified poly(vinyl chloride) membranes

The transport properties of a set of four copolymers based on poly(vinyl chloride) (PVC) have been studied. The nucleophilic substitution of chlorine atoms with 4‐mercaptophenol sodium salt, 2‐thionaphthalene, 4‐(1‐adamantyl) thiophenol, and thiophenolate sodium salt as the nucleophiles has been performed, from low conversion levels (3%) to high levels (40%), and the permeability, solubility, and diffusivity of oxygen, nitrogen, carbon dioxide, and methane have been measured. The introduction of bulky groups to the PVC chain leads to chain separation and results in large increases in the free volume at conversions up to 10%. This brings about a 5‐fold increase in the diffusion coefficients that is almost independent of the bulkiness of the substituent. Solubility is little affected and instead tends to decrease as substitution progresses. The substitution of more than 10% of the chlorine atoms does not result in an improvement in the transport properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 964–971, 2002     

弹性体偶联剂结构对PVC/PPC性能的影响

NBR－PPC弹性体偶联剂能促进PPC（聚丙撑碳酸酯）与PVC（聚氯乙烯）之间的相容性，改善共混物的力学性能，并在共混体系中产生轻度交联。偶联剂组成在NBR／PPC比例为70／30，NBR（丁腈橡胶）含腈量为34％，BPO过氧化苯甲酸用量为2．5份时，共混物的综合力学性能最佳，但偶联剂预先硫化时间不宜过长．     

Curcuma longa L. Rhizome Extract as a Poly(vinyl chloride)/Graphene Nanocomposite Green Modifier

In this work, a method to increase the dispersion of graphene (GN) in the matrix of rigid poly(vinyl chloride) (PVC) by using a natural plant extract from Curcuma longa L. (CE) is proposed. Currently, despite the increasing number of reports on the improvement of GN dispersion in PVC blends, still there is a need to find environmentally friendly and economical dispersion stabilizers. We proposed a stabilizer that can be easily obtained from a plant offering thermal stability and high effectiveness. PVC/GN nanocomposites stabilized with the proposed extract were investigated by SEM, AFM (structure), TGA, and Congo red test (thermal properties). Additionally, static and dynamic mechanical properties and electrical resistivity were measured. The use of CE as a graphene dispersant improved its dispersion in the PVC matrix, influenced tensile properties, increased the storage modulus and glass transition temperature, and extended the thermal stability time of nanocomposites. In this work, a CE extract is proposed as an efficient eco-friendly additive for the production of nanocomposites with an improved homogeneity of a nanofiller in the matrix and promising characteristics.     

离子交联聚氯乙烯的结构与性能

由氯乙烯/丙烯酸悬浮共聚合成了不同羧基含量的PVC树脂,采用溶液反应和熔融加工法制备离子交联PVC,对其结构和性能进行了研究.结果表明,共聚物中羧基主要以二聚体形式存在,用金属离子中和能形成部分络合结构;用Ca²⁺、Mg²⁺离子络合的羧基含量较高的VC/AA共聚物存在离子对聚集态结构;离子对含量、金属离子种类和增塑剂浓度影响离子聚集相的比例和稳定性,离子聚集具有热可逆性;离子交联使PVC的T_g、熔体粘度和回弹性提高.     

Poly(vinyl chloride) on the way from the 19th century to the 21st century

Despite all the technical and economic problems and the public discussions on the environmental dangers and hazards of chlorine chemistry, poly(vinyl chloride) (PVC) is the second most produced plastic (with a worldwide capacity of about 31 million tons), placing after polyolefins and before styrene polymers. Presently, PVC production worldwide is growing at a rate of more than 4% per year. The application of PVC was first described in a patent in 1913, but only after 1930 did a sustained interest in PVC arise in several industrial laboratories. The most remarkable milestones in PVC history and their importance to the development of macromolecular chemistry are briefly described, and some present PVC research and industrial applications, with respect to polymerization, stabilization, bulk property modification, and chemical and material recycling of PVC waste, are discussed. Some actual selected topics include the emulsion polymerization of vinyl chloride with polymeric surfactants and controlled free-radical polymerization with nitroxyls, whereas ionic and metal organic initiators have not found any technical applications. Chemical reactions offer many possibilities for the modification of PVC, but they have been not used on a technical scale yet. Much work has been done on stabilization with nontoxic or metal-free systems. The bulk properties of PVC can be influenced by impact modification through the addition of graft copolymers or by blending with other polymers. Also presented are some problems and recent developments in PVC recycling. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 578–586, 2004     

Dielectric investigation of the glass relaxation in poly(vinyl acetate) and poly(vinyl chloride) under high hydrostatic pressure

Measurements of the complex relative permittivity of poly(vinyl acetate) from 35 °C to 190 °C and poly(vinyl chloride) from 90 °C to 150 °C in the frequency range 10^–2 –10⁷ Hz and the pressure range 1–5000 bar are reported. Details of the pressure generating system and of the dielectric equipment are described.