Electrical conductivity of modified poly(vinyl chloride)

Chemical modification of poly(vinyl chloride) (PVC) by dehydrochlorination with ethanolic KOH is found to yield modified PVC with conjugated polyene sequence. The semiconducting nature of ethoxide-modified PVC is illustrated with temperature dependence of conductivity (σ). The relative ratios (r) of conductivity,σ _modifiedpvc /σ _{unmodifiedpvc} , are greater than unity in the temperature range 50° to 180°C,r being maximum in the vicinity of glass-transition temperature (T _g).T _g inferred from conductivity-temperature profiles is found to be greater for modified PVC relative to unmodified PVC, which is explicable in terms of restricted free rotation limiting segmental motion. For comparison with the conductivity andT _g of ethoxide-modified PVC, LiCl-modified PVC and (aniline + S₂O ₈ ²⁻ )-modified PVC have also been studied.     

Thermomechanical properties of poly(vinyl alcohol) plasticized with varying ratios of sorbitol

The objective of this work is to study the thermal and mechanical properties of films based on blends of poly(vinyl alcohol) (PVA) with different weight percent of sorbitol. Solid-state PVA/sorbitol polymer membranes were prepared by a solution casting method. The characteristic properties of these polymer membranes were examined by thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC), nanoindentation methods and by Fourier Transform Infrared (FTIR) spectroscopy. It was found that the thermal properties (glass transition, T_g, melting point, T_m and decomposition temperature, T_d) for PVA blends showed a decrease proportional to the sorbitol concentrations. The hardness and elastic modulus obtained from nanoindentation test were also found to decrease with increase in plasticizer concentration. FTIR confirmed the reduction in hydrogen bonding between PVA chains in favour of formation new bonding between the plasticizer and the PVA chains.     

Optimization of pH and direct imaging conditions of complexed methylene blue sensitized poly(vinyl chloride) films

Significant results of our experimental investigations on the dependence of pH on real time transmission characteristics on recording media fabricated by doping PVC with complexed methylene blue are presented. The optimum pH value for faster bleaching was found to be 4.5. In typical applications, the illumination from one side, normal to the surface of this material, initiates a chemical sequence that records the incident light pattern in the polymer. Thus direct imaging can be successfully done on this sample. The recorded letters were very legible with good contrast and no scattering centres. Diffraction efficiency measurements were also carried out on this material.     

Effect of a phase-transfer catalyst on the chemical modification of poly(vinyl chloride) by substitution with thiocyanate as a nucleophile

This study examined the effect of the phase-transfer catalysts tetrabutylammonium bromide (TBAB) and tetrabutylammonium hydrogen sulfate (TBAHS) on the chemical modification of poly(vinyl chloride) (PVC) by substitution with thiocyanate as a nucleophile. TBAB accelerated the dechlorination of PVC in SCN/ethylene glycol (EG) solution. Furthermore, the addition of TBAB to SCN/EG solution improved the substitution of the Cl in PVC with SCN in solution. The addition of TBAB or TBAHS to SCN/H₂O solution promoted the dechlorination of PVC, whereas dechlorination did not occur without the catalyst. The catalysts preferred substitution to the elimination of HCl in SCN/H₂O solution, and TBAB was slightly superior to TBAHS in terms of the degree and selectivity of the substitution. The addition of nitrobenzene to SCN/H₂O solution with TBAB increased the degree of substitution. Consequently, phase-transfer catalysts, particularly TBAB, were very effective at promoting the substitution of Cl in PVC with SCN in solution.     

接枝共聚改性型医用聚氯乙烯

本文对增塑剂渗出性小或亲水性、生物相容性优异的接技共聚改性医用聚氯乙烯的研究进展进行了综述     

Chemical modification of flexible and rigid poly(vinyl chloride) by nucleophilic substitution with thiocyanate using a phase-transfer catalyst

The purpose of this study was to examine the effect of a phase-transfer catalyst on the chemical modification of flexible and rigid poly(vinyl chloride) (PVC) by substituting chloride with thiocyanate (SCN) in order to develop a new process for recycling PVC. The effects of temperature and time on the reaction of a SCN/ethylene glycol (EG) solution on PVC were investigated in the presence and absence of tetrabutylammonium bromide (TBAB) as a phase-transfer catalyst. TBAB was found to accelerate the dehydrochlorination of both flexible and rigid PVC, thus allowing the reaction to take place over shorter reaction times. The substitution yield and substitution/dehydrochlorination ratio were higher in the presence of TBAB than in its absence. By reducing the reaction temperature, the substitution/dehydrochlorination ratio increased, and substitution occurred more rapidly when TBAB was present. The differences between flexible and rigid PVC were negligible. Together, these results indicate that the phase-transfer catalyst TBAB is effective in accelerating the substitution of chloride by SCN. This two-phase reaction allows for the easy separation of the polymer from the solvent without using other chemicals or thermal processes.     

红外光谱法快速鉴别PE和PVC保鲜膜

利用傅立叶变换红外光谱仪直接采集PE和PVC食品保鲜膜的红外投射光谱,比较了两种食品保鲜膜的红外光谱特征,明确了各自主要特征峰的归属.通过检索标准谱库与标准谱图进行对照,对两种保鲜膜进行了定性鉴定.该方法不需要任何样品前处理过程,具有快速、方便、准确的优点,是对市场上两种食品保鲜膜进行快速定性鉴别的理想方法之一.     

聚氯乙烯/聚醚砜共混小孔超滤膜的研制

聚氯乙烯与聚醚砜属部分相容体系。采用溶胶-凝胶相转化法,改变聚合物共混比例、混合溶剂、添加剂用量,制备了一系列聚氯乙烯/聚醚砜(PVC/PES)共混超滤膜。通过调配铸膜液中聚合物共混比例,可大大提高共混膜的强度和韧性。其水通量和截留率与同类日本产高分子分离膜相比,均有较大提高。     

镀Ag玻璃微珠-膨胀石墨/聚氯乙烯导电复合材料的制备与表征

采用一种无Pd无SnCl₂化学镀Ag新工艺对空心玻璃微珠（HGB）表面进行化学镀Ag,然后通过熔融共混方法制备镀Ag玻璃微珠（Ag-GB）-膨胀石墨（EG）/聚氯乙烯（PVC）复合材料。借助SEM、EDS和XRD测试手段对Ag-GB镀层的表面形貌与结构进行了表征,研究了Ag-GB和EG作为复合填料对Ag-GB-EG/PVC复合材料导电和力学性能的影响。结果表明:预处理的HGB的表面更易于Ag层的沉积,镀覆的镀层更为均匀、致密;Ag-GB表面的Ag层质量分数为81.15%;固定Ag-GB的质量分数为15%,随着EG质量分数的增加,Ag-GB（15%）-EG/PVC复合材料的体积电阻率呈非线性降低趋势,当EG的质量分数达到逾渗阈值12%时,Ag-GB（15%）-EG/PVC复合材料的体积电阻率为2.18×103 Ω·cm,满足抗静电PVC材料的应用要求。添加质量分数为12%的EG,Ag-GB（15%）-EG/PVC复合材料的体积电阻率与单独填充质量分数为50%的Ag-GB时Ag-GB/PVC复合材料的体积电阻率相当,此时其拉伸强度达到最大值。      

NMR analysis of poly(ethylene naphthalate) + poly(butylene terephthalate) blends

Melt blends of poly (butylene terephthalate) (PBT) and poly (ethylene naphthalate) (PEN) with 30, 40, 50, 60 and 70 wt% PEN were prepared using a single screw extruder and injection moulding machine. ¹³C and ¹H nuclear magnetic resonance (NMR) spectra were obtained with a Bruker DRX-400 instrument, on solutions prepared by dissolving samples of the homopolymers and each blend in deuterated trifluoroacetic acid + chloroform mixtures (1:1 by volume). The absence of new signals in ¹H and ¹³C spectra, that would be expected to result from transesterification reactions in the PBT + PEN blend system, provides convincing evidence that such reactions do not occur in these blends under the melt processing conditions that were used. In the light of published work on solid-state NMR studies of these and related blend systems, and our observations of partial miscibility with a very small domain size, together with substantial enhancement of the mechanical properties of PBT by blending with PEN, we conclude that the improvement in mechanical properties arises from molecular scale mixing of the homopolymers and strong but non-covalent bonding interactions over the very large interfacial area between the PBT-rich and PEN-rich phases.     

Thermal conductivity and mechanical properties of high density polyethylene composites filled with silicon carbide whiskers modified by cross-linked poly (vinyl alcohol)

A thin layer of poly (vinyl alcohol) (PVA) was coated on the surface of silicon carbide whiskers (SCWs) and crosslinked by glutaraldehyde, and then these modified whiskers (mSCWs) were incorporated into high density polyethylene (HDPE) to prepare HDPE/mSCW composites with a high thermal conductivity. The thermal conductivity, mechanical properties, heat resistance, thermal stability and morphology of HDPE/mSCW and HDPE/SCW composites were characterized and compared. The results reveal that the thermal conductivity of both HDPE/SCW and HDPE/mSCW composites increases with the increase of filler loading, and reaches a maximum of 1.48 and 1.69?W/(m?K) at 40?wt% filler loading, which is 251.2% and 300.75% higher than that of HDPE, respectively. Significantly, HDPE/mSCW composites have a higher thermal conductivity than their HDPE/SCW counterparts with the same filler loading. In addition, the heat resistance, Young’s modulus and yield strength of both HDPE/SCW and HDPE/mSCW composites are also improved compared with that of HDPE. mSCW can be homogenously dispersed in the HDPE matrix, which contributes to the formation of thermally conductive networks by the inter-connection of mSCWs.     

聚乙烯醇缩苯甲醛的合成与热稳定性研究

以聚乙烯醇（PVA）和苯甲醛为原料,二甲基亚砜为溶剂,对甲基苯磺酸为催化剂,采用均相工艺合成得到聚乙烯醇缩苯甲醛（PVB）。通过衰减全反射-傅里叶红外光谱（ATR-FT-IR）、紫外-可见光谱（UV-Vis）、核磁共振氢谱（1 H NMR）、核磁共振碳谱（13C NMR）等测试手段对聚乙烯醇缩苯甲醛结构进行了表征。利用差式扫描量热仪（DSC）测定了聚乙烯醇缩苯甲醛的玻璃化温度（Tg）。采用差热分析（DTA）和热重分析（TGA）对聚乙烯醇缩苯甲醛热稳定性进行了研究。DSC结果表明聚乙烯醇缩苯甲醛的玻璃化温度为106.0℃。DTA和TGA结果表明聚乙烯醇缩苯甲醛热稳定性良好,在空气中150℃仍未见分解。     

蓖麻油基阻燃增塑剂的合成及在聚氯乙烯中的应用

为了进一步利用可再生资源为原料合成环保增塑剂,文中以蓖麻油和自制的含磷阻燃剂为原料合成了一种含磷阻燃增塑剂,再将其环氧化得到蓖麻油基含磷阻燃增塑剂(P-ECO)。采用傅里叶变换红外光谱、核磁共振氢谱和核磁共振磷谱对产物的结构进行表征。将其与聚氯乙烯(PVC)热塑共混成型,通过动态力学性能、拉伸性能测试、热重评价了蓖麻油基含磷增塑剂应用于PVC的增塑效果;随着P-ECO含量的增加,体系的Tg从41℃下降到9℃,拉伸强度随之下降到10.17 MPa,而断裂伸长率由146.22%增加到197.31%。通过测试极限氧指数、锥形量热仪测试其阻燃性能,氧指数达到28.1%,热释放速率最高为280.46kW/m2。     

Preparation and characterization of chitosan/poly(vinyl alcohol)/poly(vinyl pyrrolidone) electrospun fibers

Ultrafine fibers of chitosan/poly(vinyl alcohol)/poly(vinyl pyrrolidone) (CS/PVA/PVP) were prepared via electrospinning. The structure and morphology of CS/PVA/PVP ultrafine fibers was characterized by the Fourier transform infrared (FT-IR) spectroscope and scanning electron microscope (SEM). Furthermore, the effects of the concentration of PVA, PVP and the electrospinning voltage on the morphology of ultrafine fibers were investigated the the SEM. When the concentration of PVA was at the range of 30wt%–40wt%, ultrafine fibers could be obtained. The diameter distributions of ultrafine fibers decreased when the electrospinning voltage increased from 20 to 30 kV. The rough surface fibers could be obtained after etching with CHCl₃.     

Transparent and high gas barrier films based on poly(vinyl alcohol)/graphene oxide composites

Composites of poly(vinyl alcohol) (PVA) and graphene oxide (GO) were synthesized by a modified Hummers method and a solution-mixing method. GO was fully exfoliated in the PVA/GO composites. GO did not affect the crystallization of PVA during solvent evaporation. GO is itself an excellent gas barrier without any chemical reduction. The oxygen permeability of the PVA/GO (0.3 wt.%) composite coated film was 17 times lower than that of the pure poly(ethylene terephthalate) (PET) film, with 92% light transmittance at 550 nm. Composites of PVA and reduced graphene oxide (RGO) were synthesized by performing chemical reduction using hydrazine monohydrate. The oxygen permeability of the PVA/RGO (0.3 wt.%) composite coated film was 86 times lower than that of the pure PET film, with 73% light transmittance at 550 nm. The reduction of oxygen permeability was mainly attributed to the reduced oxygen solubility in the PVA/GO composite film, while it was attributed to both the reduced oxygen diffusivity and solubility in the PVA/RGO composite film.     

One-step preparation of poly(vinyl alcohol)-protected Pt nanoparticles through a heat-treatment method

A heat-treatment method for the preparation of well-stable, polymer-protected Pt nanoparticles in the range of 2-7 nm in diameter is demonstrated. The formation of Pt nanoparticles occurs in a single step process, carried out by heating an aqueous solution containing a poly(vinyl alcohol) polymer and H₂PtCl₆, with the use of PVA to serve as both a reducing reagent and a protective reagent. The Pt nanoparticles were characterized by UV-vis absorption spectra, transmission electron microscopy (TEM), and X-ray photoelectron spectrum (XPS) and the Pt nanoparticle formation process was further investigated by in situ UV-vis experiment.     

一种新型ZHS-MF复合阻燃剂的制备及其在软质PVC中的应用

采用化学沉淀法合成了纳米羟基锡酸锌(ZHS), 然后以纳米ZHS为无机核, 以三聚氰胺-甲醛树脂(MF)为有机壳层, 构筑了一种新型的ZHS-MF复合阻燃剂, 并将其用作软质聚氯乙烯(PVC)的阻燃添加剂进行了阻燃性能研究。XRD、TEM、FTIR、TG测试结果表明, 所制备的产物为MF包覆ZHS的复合结构, ZHS质量分数约为35%。极限氧指数(LOI)测试结果表明, 随着阻燃剂ZHS-MF添加量的增加, PVC的LOI逐渐上升, 由纯PVC的23.8%上升到29.6%, 表明ZHS-MF对PVC具有很好的阻燃效果。在相同LOI条件下ZHS-MF中ZHS实际含量比实际需要的ZHS明显减少, 说明MF的包覆层与ZHS起到了协同阻燃作用。烟密度等级(SDR)测试结果表明, 在ZHS-MF添加量为15%时, 经MF包覆的ZHS对PVC的抑烟性能优于未包覆的ZHS, 说明MF的包覆层与ZHS起到了协同抑烟作用。     

Properties of hot-melt extruded theophylline tablets containing poly(vinyl acetate)

The objectives of this study were to investigate the properties of poly(vinyl acetate) (PVAc) as a retardant polymer and to study the drug release mechanism of theophylline from matrix tablets prepared by hot-melt extrusion. A physical mixture of drug, polymer, and drug release modifiers was fed into the equipment and heated inside the barrel of the extruder. The cylindrical extrudates were either cut into tablets or ground into granules and compressed with other excipients into tablets. Due to the low glass transition temperature of the PVAc, the melt extrusion process was conducted at approximately 70°C. Theophylline was used as the model drug in this study. Theophylline was present in the extrudate in its crystalline form and was released from the tablets by diffusion. The Higuchi diffusion model and percolation theories were applied to the dissolution data to explain the drug release properties of the matrix systems. The release rate was shown to be dependent on the granule size, drug particle size, and drug loading in the tablets. Water-soluble polymers were demonstrated to be efficient release rate modifiers for this system.     

聚氯乙烯/氧化石墨烯薄膜的力学性能和热稳定性能

通过溶液共混法制备了氧化石墨烯(GO)分散均匀的聚氯乙烯(PVC)/GO纳米复合薄膜,研究了薄膜的力学性能和热稳定性能。结果表明,微量GO能大幅度提高PVC的模量和拉伸强度,且保持较高的断裂伸长率。在PVC中添加质量分数为0.12%的GO,PVC的拉伸强度提高63%,杨氏模量提高20%;添加量为0.60%时,PVC的拉伸强度提高125%,杨氏模量提高126%.添加GO还能提高PVC的起始分解温度、最大分解温度以及PVC的成碳量。GO片层具有较高的强度和模量、GO在高分子基体内的均匀分散、GO和PVC之间较强的相互作用、GO与PVC的层状结构,是其力学性能提高的主要原因.