Combustion of PVC: Summary of Main Lecture'

Although polyvinyl chloride) is resistant to ignition due to its chemical structure and its mode of decomposition, it will undergo thermal degradation under high thermal or fire exposure. While considerable literature exists on the mechanism of decomposition of PVC, more recent analytical studies have focused on the forced combustion of PVC and the toxicity of those combustion products. Our analytical studies have involved the analysis of combustion products from rigid PVC, flexible PVC, modified flexible PVC, and PVC-wood mixtures. While analytical studies like this cannot predict biological response, they do demonstrate the nature of experimental problems and experimental design in biological testing.     

Thermal degradation studies in poly(vinyl chloride)/poly(methyl methacrylate) blends

The miscibility, morphology, and thermal properties of poly(vinyl chloride) (PVC) blends with different concentrations of poly(methyl methacylate) (PMMA) have been studied. The interaction between the phases was studied by FTIR and by measuring the glass transition temperature (T_g) of the blends using differential scanning calorimetry. Distribution of the phases at different compositions was studied through scanning electron microscopy. The FTIR and SEM results show little interaction and gross phase separation. The thermogravimetric studies on these blends were carried out under inert atmosphere from ambient to 800 °C at different heating rates varying from 2.5 to 20 °C/min. The thermal decomposition temperatures of the first and second stage of degradation in PVC in the presence of PMMA were higher than the pure. The stabilization effect on PVC was found most significant with 10 wt% PMMA content in the PVC matrix. These results agree with the isothermal degradation studies using dehydrochlorination and UV-vis spectroscopic results carried out on these blends. Using multiple heating rate kinetics the activation energies of the degradation process in PVC and its blends have been reported.     

纳米二氧化硅粒子对聚氯乙烯膜的表面结构及浸润性能的调控作用

报道了一种简便的调控聚合物材料表面结构及浸润性能的方法.利用流延成膜和纳米二氧化硅粒子的印迹修饰作用,制备出3种具有不同表面结构的聚氯乙烯(PVC)膜,膜的浸润性能表现为与水的接触角从103°的疏水性变为65°的亲水性,再改变至130°的疏水性.扫描电镜结果表明印迹修饰后的PVC膜具有纳米和微米尺寸的凹凸表面结构.通过对比实验证实了溶剂氯仿和NaOH溶液并不影响膜表面的疏水性能.     

Particle structure of suspension poly(vinyl chloride) and its origin in the polymerization process

The initial stage of the suspension polymerization of poly(vinyl chloride) (PVC) is characterized by the formation of colloidally stable micron-sized grains of PVC inside the polymerizing ca. 150 μm vinyl chloride droplets. The fate of these micron-sized PVC grains depends upon the agitation conditions. If no agitation is employed, they serve as growth centers for further polymerization to give a final particle possessing a uniform internal bead morphology. In agitated systems, these grains coagulate early in the conversion to give a more irregular structure in the interior of the PVC particle. The formation of these stable growth centers appears to be unique to PVC. The polymerization of acrylonitrile, also insoluble in its monomer, is characterized by rapid agglomeration of the precipitated polymer throughout the polymerization. In PVC, the colloidal stability of the polymerizing grains is demonstrated to be electrical in nature. A pericellular membrane or skin formed by polymerization in both the water and vinyl phase completely surrounds the polymerizing droplet after about (1–2)% conversion. This skin is responsible for the charge retention of the PVC grains inside the polymerizing monomer droplets.     

Effect of oxygen plasma treatment on surface charge and wettability of PVC blood bag—In vitro assay

Wettability and zeta potential studies were performed to characterize the hydrophobicity and surface charge of PVC blood bag samples and evaluate the effect of these properties on fibroblast cells growth. The surface properties of PVC and plasma treated PVC were compared by water drop contact angle and zeta potential measurement. Light microscopy was used to study the behavior of cell attachment and growth on these surfaces. Water drop contact angle measurement shows that the plasma treated PVC becomes more hydrophilic and wettability increased. Zeta potential and in vitro cell culture measurements noticed that the plasma treated PVC surface is more negatively charge and consequently attachment of the L929 fibroblast cells decreased on this surface.     

聚合物材料的吸音系数-温度-频率三元关系的研究

用驻波管技术研究了聚甲基丙烯酸乙酯（ＰＥＭＡ）和聚氯乙烯（ＰＶＣ）的吸声系数。结果表明,在玻璃化转变区域材料的吸声系数较高,ＰＥＭＡ和ＰＶＣ均具有特征吸收频率。当乍于玻璃化转变区域时,ＰＥＭＡ和ＰＶＣ的特征吸收峰的数目增加,用自由体积理论对此进行了解释。得到ＰＥＭＡ和ＰＶＣ的吸声系数－温度－频率的三维关系图。     

Fourier-transform infrared studies of polymer blends. II. Poly(ϵ-caprolactone)–poly(vinyl chloride) system

Fourier-transform infrared (FTIR) studies of the poly(?-caprolactone) (PCL)–poly(vinyl chloride) (PVC) blend system are presented. The results indicate that there are specific interactions between the PCL and PVC in both the molten and solid states which could be responsible for the apparent compatibility of the amorphous component of these blends. Additionally, FTIR difference spectra are presented to illustrate the potential of this technique for following the kinetics of crystallinity in polymer blend systems.     

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．     

High-temperature pyrolysis of poly(vinyl chloride): Gas chromatographic-mass spectrometric analysis of the pyrolysis products from PVC resin and plastisols

A pyrolysis–gas chromatographic–mass spectrometric technique for analyzing the pyrolysis products from polymers in an inert atmosphere is described. Initial studies encompassing the pyrolysis of poly(vinyl chloride) homopolymer and a series of PVC plastisols (based on o-phthalate esters) have provided a complete qualitative and semi-quantitative analysis of the pyrolysis products from these materials. PVC resin yields a series of aliphatic and aromatic hydrocarbons when pyrolyzed at 600°C; the amount of aromatic products is greater than the amount of aliphatic products. Benzene is the major organic degradation product. A typical PVC plastisol [PVC/o-dioctyl phthalate (100/60)] yields, upon pyrolysis, products that are characteristic of both the PVC matrix and the phthalate plasticizer. The pyrolysis products from the plasticizer dilute those from the PVC portion of the plastisol and are, in turn, the major degradation products. There are no degradation products resulting from an interaction of the PVC with the plastisol. The pyrograms resulting from pyrolysis of the various plastisols of PVC can be used for purposes of “fingerprinting.” Identification of the major peaks in a typical plastisol pyrogram provides information leading to a precise identification of the plasticizer. The pyrolysis data from this study were related to a special case of flammability and toxicity.     

Suspension polymerization of vinyl chloride and the processibility of poly(vinyl chloride)

The most important technological procedure in the production of PVC is the suspension polymerization of vinyl chloride, as processibility of the polymer may be influenced to a considerable extent by the choice of polymerization conditions. Structure heterogeneities in PVC powders manifest themselves in plasticized PVC by the occurrence of “fish eye” particles. This review concerns the formation and properties of these particles and discusses the causes of their difficult processibility. Also, the relation between polymerization process and PVC dehydrochlorination is discussed and a new mechanism of its initiation based on the reactivity of cisoid enone structures is proposed. These structures catalyze elimination of hydrogen chloride from regular units of PVC by an interchain enzyme-like mechanism giving rise to chloroallyl structures.     

Sum frequency generation and coherent anti-Stokes Raman spectroscopic studies on plasma-treated plasticized polyvinyl chloride films

Polyvinyl chloride (PVC) is a widely used polymer to which various phthalates are extensively applied as plasticizers. PVC materials are often treated with plasma to vary the hydrophobicity or for cleaning purposes, but little is known of the nature of the surface molecular structures after treatment. This research characterizes molecular surface structures of PVC and bis-2-ethylhexyl phthalate (DEHP)-plasticized PVC films in air before annealing, after annealing, and after exposure to air-generated glow discharge plasma using sum frequency generation (SFG) vibrational spectroscopy. In addition, we compare the vibrational molecular signatures on the surfaces of PVC with DEHP (at a variety of percent loadings) to those of the bulk detected using coherent anti-Stokes Raman scattering (CARS). X-ray photoelectron spectroscopy (XPS) and contact angle measurements have been used to analyze PVC surfaces to supplement SFG data. Our results indicate that DEHP was found on the surfaces of PVC films even at low weight percentages (5 wt %) and that DEHP segregates on surfaces after annealing. The treatment of these films with glow discharge plasma resulted in surface-sensitive reactions involving the removal of chlorine atoms, the addition of oxygen atoms, and C-H bond rearrangement. CARS data demonstrate that the bulk of our films remained undisturbed during the plasma treatment. For the first time, we probed the molecular structure of the surface and the bulk of a PVC material using combined SFG and CARS studies on the same sample in exactly the same environment. In addition, the methodology used in this research can be applied to characterize various plasticizers in a wide variety of polymer systems to understand their surface and bulk structures before and after systematic applications of heat, plasma, or other treatments.     

Compatibility studies on polyblends of PVC with chlororubber-20 and its graft polyblends by ultrasonics

Compatibilities of various PVC blends with chlororubber-20 and its graft polyblends have been studied on the basis of our previous findings. It has been found that chlororubber-20 makes compatible blends with PVC, while grafting of styrene, ethyl acrylate or acrylonitrile onto chlororubber-20 generates heterogeneity in their blends with PVC. The behaviour of these blends at the molecular level is reflected in the changes of ultrasonic velocity and absolute viscosity with composition.     

Analysis of poly(vinyl chloride) additives by supercritical fluid extraction and gas chromatography

The use of supercritical fluid extraction (SFE) is growing, with an expanding range of applications in many different fields as a consequence of its advantages compared with traditional extraction methods. In order to develop an analytical method to determine dibutyl phthalate (DBP) and dioctyl phthalate (DOP) traces (<20 ppm) in flexible poly(vinyl chloride) (PVC) formulations, a maximum efficiency in the extractive process and an adequate separative system are needed to avoid interferences between these two plasticizers and other additives that could be present at high concentrations in flexible PVC formulations. In order to determine the optimum SFE conditions, the extraction time, temperature and pressure were controlled. The separation and quantitation of individual components in the PVC extracts were carried out off-line by using a semicapillary column in gas chromatography (GC). Samples with different DOP content (41.18%, 33.33% and 23.08%) and DBP content (41.18%), as well as samples with both plasticizers (20.59% DOP and 20.59% DBP) were prepared. Some other samples were also prepared to study detection limits for these two PVC additives. Recoveries and reproducibilities were studied in every sample. Finally, this method was compared with Soxhlet liquid extraction. Determination by gravimetric analysis of the total extracted material was found to be particularly suitable for PVC. This study demonstrates the potential of SFE to shorten extraction times with similar or even better extraction efficiencies compared with traditional liquid methods.     

Effect of Solvent (Plasticizers) on PVC Degradation

Both plasticized (semi-rigid and flexible) PVC materials as well as PVC in solutions, the rate of their thermal degradation and effective stabilization are caused by essentially different fundamental phenomena in comparison to aging of PVC in absence of the solvent. Both structure and macromolecular dynamics render the significant influence on its stability, i.e. chemical nature of the solvent (plasticizer), its basicity, specific and non-specific solvation, degree of PVC in a solution (solubility), segmental mobility of macromolecules, thermodynamic properties of the solvent (plasticizer), formation of associates, aggregates, etc. The chemical stabilization of PVC plays a less significant role. The effect of above factors on stability (behavior) of semi-rigid and flexible PVC will be done on quantitative level. It will be described effect of “echo”-type of stabilization on the stability of PVC in the presence of plasticizers. If we would like to have stable material from PVC we should make stabilization of plasticizers as more reactive chemical compounds.     

DC Electrical Study of Modified PMMA,PVC and their Blend

Summary: Thin films of high molecular weight PMMA, PVC and their blend were prepared with solution cast method. Further they were modified by adding Camphor Sulphonic Acid (CSA) to them. DSC studies indicate single glass transition temperature (Tg) for unmodified as well as modified blends indicating the miscibility of polymers. FTIR studies show the interaction between CSA-PVC, CSA-PMMA, CSA-(PVC+PMMA) blend. The D.C. electrical study was carried out at various temperatures from room temperature (307 K) to 373 K. After modification the variation of DC conductivity (σ) is found to decrease in PVC and the PVC-PMMA blend whereas it is found to increase in PMMA with rise in temperature.     

Modification irréversible de la morphologie de films de poly(chlorure de vinyle) greffés d'acide acrylique sous l'action de solvants et de la température

PVC films grafted with acrylic acid were prepared with grafting ratios as high as 160% and their swelling in N/10 KOH, was measured. An earlier observation was confirmed showing that, when the films are heated in the swollen state, they undergo an irreversible transformation which leads to an increase of their swelling ratio. A study with scanning and transmission electron microscopes showed that rigid PVC as well as PVC grafted with acrylic acid up to 27% did not exhibit any specific microstructure. At high magnifications, fibrils characteristic of fragile fractures clearly appeared on the SEM pictures. For grafting ratios of 67% or more, segregated microphases of PVC and poly(acrylic acid) are clearly seen. The size of these microphases increases after the grafted films are swollen in KOH at 60°. A systematic study with PVC films grafted to 160% showed a steady evolution of the size of the microdomains during swelling in KOH. The results explain the variations of a macroscopic property of the film (its extent of swelling) by a modification of their microstructure.     

Thermal degradation of poly(vinyl chloride) synthesized with a titanocene catalyst

PVC was synthesized using a trichloroindenyltitanium-methylaluminoxane catalyst at room temperature, and its degradation was monitored along with a commercial sample at 160, 170 and 180 °C under air or nitrogen atmosphere. The process was followed by HCl evolution, yellowing index, colour formation and thermogravimetric analysis. The produced polymer had a lower molecular weight and higher surface area, compared with a commercial PVC, while ¹H NMR and T_g values show minimal differences between materials. The HCl evolution degradation studies indicate that produced PVC has a lower thermal resistance than commercial PVC, while TGA reveals the opposite behaviour. Yellowing index and colour evaluation give evidence that nitrogen atmosphere and high surface area in produced PVC allow the polyene growth, whereas low surface area and air atmosphere generate shorter polyenes and chromophoric species. Differences in degradation performance are thought to be due to chemical origin, inherent morphology and differences in instrumentation.     

Radiation-Induced Grafting of Ethyl Vinyl Ether onto Polyvinyl Chloride)

The radiation-induced graft polymerization of ethyl vinyl ether (EVE) onto polyvinyl chloride) (PVC) was studied under a variety of conditions. Graft copolymer and homopoly(EVE) were formed in all cases. The presence of water reduced overall polymerization rates, percentage grafting, and homopoly(EVE) molecular weights. With “superdry” EVE, grafting reached 29% at a total dose of 6.9 Mrad. Grafting to PVC films was less efficient than grafting to PVC powder. Application of a relatively poor swelling agent for PVC resulted in an increase in the efficiency of grafting. From a comparison of studies of radiation-induced EVE homopolymerization and the present work, it was concluded that dry and superdry EVE are grafted to PVC by a cationic mechanism and wet EVE is grafted mainly by a free-radical mechanism.     

A possible mechanism to explain the synergistic effects exhibited by mixtures of alkyltin mercaptoesters as stabilisers for PVC

The phenomenon of synergism observed with mixtures of mono- and dialkyltin stabilisers for PVC has been recognised and exploited for many years, but remains largely unexplained. Whilst a similar effect in mixed metal (Ba/Cd or Ca/Zn) carboxylate stabilisers has been explained, mechanistic studies of the organotin systems have not appeared. Infra-red spectroscopy has now been used to study the Cl/mercaptoester exchange equilibria of alkyltin mercaptoester (isooctylthioglycollate) chlorine compounds which are undoubtedly produced when the organotin mercaptoesters act as PVC stabilisers. The exchange process is shown to be facile, even at ambient temperatures, and a regenerative mechanism, based on these observations, is proposed to explain the synergistic effect.     

Structure and properties of poly(vinyl chloride)/graphene nanocomposites

The goal of the paper was to investigate the influence of graphene (GN) on properties and structure of suspensive poly(vinyl chloride) (PVC). PVC/GN nanocomposites were obtained by the solvent evaporation method, and their structures were evaluated using optical microscopy, SEM, FT-IR, XRD and Raman spectroscopy methods. Thermal properties of the obtained materials were studied by TGA. Electrical properties and swelling behaviour were also determined.The microscopic observations confirm a uniform distribution of graphene in the PVC matrix. The investigations carried out indicated an effect of graphene on a decrease in resistivity to a value which enabled to include the PVC/GN nanocomposites into anti-static materials group. On the basis of swelling studies, it has been found that the PVC/GN nanocomposites have a higher chemical resistance against acetone while compared to pure poly(vinyl chloride). The properties of the obtained materials depend significantly on content and dispersion level of graphene in the PVC matrix. An impact of GN on the acceleration of the PVC degradation process was found.