Polymerization and copolymerization of vinyl carbamates and vinyl carbonates

Poly(vinyl carbamates) and poly(vinyl carbonates) of high molecular weight have been obtained by polymerization of the corresponding monomers prepared from vinyl chloroformate. Poly(vinyl carbonates) can also be prepared by chemical modification of poly(vinyl chloroformate) with alcohols and phenols. Copolymerization parameters of phenyl vinyl carbonate with vinyl acetate have been determined in methylene chloride, at 35°C, with dicyclohexyl peroxydicarbonate as initiator.     

Preferential adsorption behaviour of several vinyl polymers in poly(ethylene glycol)(1)/THF(2)

Summary The preferential sorption coefficient in the ternary systems vinyl polymers (3)/Poly (ethylene glycol) (1)/THF(2) has been determined in dilute solutions by dialysis equilibrium differential refractometry at 633 nm and 298 K. A series of vinyl polymers of different side groups (Polystyrene, Poly (p-iodostyrene), Poly (n-vinyl carbazole), Poly (vinyl chloride) and Poly (methyl methacrylate)) has been studied.The results indicate that polymer side group play a fundamental role in the solvation behaviours of vinyl polymers. The characteristics of the polymer side group influences the kind and intensity of the polymer-binary solvent interactions and so, the rest of solution properties of these systems.     

A comparative study on water-based coatings prepared in the presence of oligomeric and conventional protective colloids

Poly(vinyl acetate-co-butyl acrylate) latexes were prepared by using semi-continuous emulsion polymerization method in presence of two different protective colloids which were oligomeric N-methylol acrylamide and conventional poly(vinyl alcohol). The effects of these protective colloids on colloidal, surface and film properties of latexes were examined. Poly(vinyl acetate-co-butyl acrylate) synthesized with oligomeric N-methylol acrylamide, which was characterized by FT-IR, NMR and MALDI-TOF MS, was found to have lower viscosity, finer particle size, better latex stability, lower polydispersity, higher T_g and better film forming behavior compared to those synthesized from the poly(vinyl alcohol).     

Poly(Vinyl Alcohol)/Graphene Oxide Mixed Matrix Membranes for Pervaporation of Toluene and Isooctane

Poly(vinyl alcohol)/graphene oxide mixed matrix membranes have been prepared and applied for the pervaporation of isooctane (aliphatic) and toluene (aromatic) mixtures. Characteristics of the membranes such as crystallinity, morphology, and swelling have been investigated, and the results have been used to describe pervaporation performance. Experimental tests evidenced that incorporation of low content of graphene oxide nanoplates (0.5?wt%) in poly(vinyl alcohol) increases affinity of the membrane to aromatics by S and π bonds and selectivity increase to about four times. Moreover, interaction of graphene oxide with toluene results in increasing of swelling and decreasing of permeation flux.     

Preparation,glass transition temperature,and δ relaxation effect of poly(vinyl isonicotinate)

Poly(vinyl isonicotinate) was prepared by esterification of poly(vinyl alcohol) with isonicotinoyl chloride in pyridine solution. Poly(vinyl nicotinate) was also prepared. Density, refractive index, and glass transition of the polymers were determined. The low temperature dynamic mechanical properties of poly(vinyl isonicotinate) are characterized by a relaxation effect which is associated with thermally excited motions of the pyridine rings (δ relaxation). The strong displacement of such a phenomenon toward higher temperatures, with respect to poly(vinyl benzoate), is interpreted as due to the elevated polarity of the pyridine ring.     

聚乙烯醇改性及降解研究进展

从材料学的改性技术和环境学的相容性两个角度综述了国内外聚乙烯醇生物降解的研究概况。通过聚乙烯醇溶液及薄膜的降解过程的介绍,指出化学改性和微生物降解的结合将是今后处理含聚乙烯醇类废水和固体废弃物的主要方法。     

Head to head polymers

Pure head to head (H–H) addition polymers, such as H–H polyolefins, H–H acrylates and H–H poly(vinyl halides), have been of interest for the understanding of the structure/properties relationship of addition polymers. These polymer structures have provided challenges of synthesis, characterization and of the measurements of their mechanical and rheological properties. H–H polymers have never been prepared by direct synthesis and indirect polymerization techniques have to be used. Some of the H–H polymers, the polyolefins, were made by polymerization of properly substituted dienes followed by hydrogenation. The H–H polyacrylates were synthesized by copolymerization followed by polymer reactions and the poly(vinyl halides), by halogenation of poly(1,4-butadiene). Improved halogenation techniques for poly(1,4-butadiene) have made H–H poly(vinyl chloride) and H–H poly(vinyl bromide) accessible in larger quantities and have allowed an extensive characterization of these polymers.

Blends of H–H with H–T polymers as well as H–H polymers with other polymers were studied. H–H Poly(vinyl chloride) or poly(vinyl bromide) blends with polycaprolactone and poly(methyl methacrylate) were also investigated. The thermal behavior and the thermal degradation behavior of these blends were investigated. The most striking result of these investigations was that H–H and H–T poly(vinyl chloride) are immiscible as is H–H and H–T polyisobutylene over almost the entire range of compositions.     

Release of salicylic acid through poly(vinyl alcohol)/poly(vinyl pyrrolidone) and poly(vinyl alcohol‐g‐N‐vinyl‐2‐pyrrolidone) membranes

A controlled release profile of salicylic acid (SA) for transdermal administration has been developed. Poly (vinyl alcohol) (PVA) and Poly(vinyl alcohol)/Poly(vinyl pyrrolidone) (PVP) blended preparations were used to prepare the membranes by solvent‐casting technique. The release of the drug from the membranes was evaluated at in vitro conditions. The effects of PVA/PVP (v/v) ratio, pH, SA concentration and temperature were investigated. 60/40 (v/v) PVA/PVP ratio was found to be the best ratio for the SA release. Increase in pH and temperature was observed to increase the transport of SA. Instead of blending PVA with PVP, N‐Vinyl‐2‐pyrrolidone (VP) was grafted onto the PVA and the delivery performance for SA was compared with that of the blended PVA/PVP membranes. Grafted membranes gave higher transport percentages than the blended membranes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1244–1253, 2006     

Molecular dynamics modelling for the analysis and prediction of miscibility in polylactide/polyvinilphenol blends

This paper analyzes the miscibility state of Poly(L-Lactide) (PLLA) and Poly(DL-Lactide) (PDLLA) with Poly(styrene) (PS) and Poly(vinyl phenol) (PVPh) by means of Molecular Dynamics (MD) simulations performed using the COMPASS force-field. Immiscibility was found in polylactide/PS blends while miscibility was the result in polylactide/PVPh blends, both previsions agreeing with the experimental behaviour. The values calculated for the Flory-Huggins interaction parameter, χ, have been compared with the experimental results and with estimations based on existing miscibility models. Even though the dependence of χ with composition and the prediction of miscibility is correct, both the solubility parameters and the interaction parameters obtained prove that molecular modelling tends to underestimate the strength of the interactions. The observed differences are explained in terms of the absence of cooperativity effects for oligomeric chains used in molecular modelling of high molecular weight polymer blends.     

Thermal degradation of poly(vinyl chloride) blends

Poly(vinyl chloride) was mixed with various poly(methacrylate)s and polycarbonates by combined precipitation from common solutions. The thermal stability of the samples was measured at 180°C under nitrogen, the HCl evolved was detected by conductometry. UV-Vis-spectra of degraded samples were measured to investigate the influence of the poly(methacrylate)s on the lengths of polyenes formed during the degradation of poly(vinyl chloride). The experiments show that the nature of the ester group is the dominating factor for the thermal stability of poly(vinyl chloride) in these blends. Poly(n-butylmethacrylate) exhibits the best stabilization for poly(vinyl chloride) in this series. Polycarbonates with a higher glass transition temperature than the temperature of degradation destabilize poly(vinyl chloride). Stabilization experiments with dibutyltin-bis(isooctylthioglycolate) show a costabilizing effect of the poly(methacrylate)s and polycarbonates.     

UV stabilizers: Their effects on vinyl compounds

Poly(vinyl chloride) (PVC) is the polymer of choice in a wide variety of applications on account of its comparatively low cost, high chemical resistance, good mechanical properties and electrical insulating capabilities. The even wider application of the material has been restricted by its low thermal and photolytic stability. This paper reviews the various light degradation and stabilization mechanisms that have been postulated recently for PVC. The importance of the thermal stabilizer system to the photostabilization of the material is also stressed. Finally the market opportunity for a cost effective UV stabilizer system for rigid PVC is discussed emphasizing the versatility that such a product would give to the vinyl siding manufacturer.     

吸水膨胀弹性体PVA-g-PBA的研究

在水介质中.在氮气保护下以硝酸铈铵(CAN)为引发剂,将丙烯酸丁酯(BA)接枝到聚乙烯醇(PVA)上,制得水膨胀弹性体PVA—g—PBA。通过红外光谱证实了接枝物的形成。讨论了PVA浓度、单体浓度、引发剂浓度和反应温度对接枝物接枝率(G％)的影响。结果表明随PVC浓度增大,接技率降低.[PVA2.5×10-4mol/L.[BA]0.702mol/l、[CAN]0.01mol/L45℃接枝率较高.接枝率越高其吸水膨胀率越低,8h达吸水平衡,最大吸水率为165.1％。     

Turbidimetric and intrinsic viscosity study of EVA copolymer–solvent systems

Both Hansen solubility parameter and Flory–Huggins interaction parameter of two EVA [Poly(ethylene-co-vinyl acetate)] copolymers with different vinyl acetate content have been obtained by means of intrinsic viscosity measurements. To calculate this last parameter it was also necessary to determine the theta solvent at different temperatures of the two EVA copolymers with turbidimetric measurements. The results indicate that the vinyl acetate content is a variable which influences the composition of the theta solvent and Flory–Huggins parameter (the higher the vinyl acetate content, the lower the Flory–Huggins parameter), although its influence over the Hansen solubility parameter is almost negligible.     

两亲性接枝共聚物PVA-g-PBA的合成与表征

以过硫酸钾 (KPS)为引发剂 ,将丙烯酸丁酯 (BA)接枝到聚乙烯醇 (PVA)上 ,制得两亲性接枝共聚物 PVA-g-PBA。用红外光谱、X射线衍射表征了接枝物 ,研究了引发剂浓度、单体浓度及反应时间对单体转化率、接枝率和接枝效率和接枝率对共聚物吸水性能的影响。结果表明在水介质中 ,氮气保护下 ,70℃时 ,以过硫酸钾 (KPS)为引发剂 ,将丙烯酸丁酯 (BA)接枝到聚乙烯醇 (PVA)上 ,[PVA]为 2 .5× 1 0 -4mol/ L,[BA]为 0 .63 mol/ L、[KPS]为 5 .5 5× 1 0 -4时 ,反应 5 h,能获得较高 CM、G和 Ge的接枝物。接枝物的接枝率越高 ,吸水率越低 ,吸水 1 0 h达平衡 ,最大平衡吸水率为 1 88.8%。     

Achieving miscible ternary polymer blends with hydrogen bonding

Poly(vinyl phenol) (PVPh) has previously been found to be successful in making immiscible poly(methyl methacrylate) (PMMA)/poly(vinyl acetate) (PVAc) miscible. Poly(ethyl methacrylate) (PEMA) with one more methyl group than PMMA is also immiscible with PVAc. PEMA and PVAc are miscible with PVPh according to the literature. To determine whether PVPh can also cosolubilize PEMA/PVAc, PVPh samples of two different molecular weights have been mixed in this study with PEMA and PVAc to produce a ternary blend. On the basis of the calorimetry data, the ternary PEMA/PVAc/PVPh blend, regardless of the molecular weight of PVPh, has been determined to be miscible. The reason for the observed miscibility is probably that the interactions between PVAc and PVPh are similar in magnitude to those between PEMA and PVPh. A modified Kwei equation based on the binary interaction parameters proposed previously is used to describe the experimental glass‐transition temperature of the miscible ternary blend almost quantitatively well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 643–652, 2006     

New modifications of poly(vinyl alcohol)s and their applications

Poly(vinyl alcohol) (PV-OH), prepared from poly(viny) acetate), is used widely in many industries. Various grades have been produced, with different degree of polymerization and degree of hydrolysis. Recently, novel modified (PV-OH)s with anion, cation, silanol or hydrophobic groups have been studied and developed. They have new properties in addition to those of ordinary PV-OH and have new applications. The methods of modification and the characteristics and some applications of the modified polymers are described.     

Studies on the preparation and properties of conductive polymers. IX. Using photographic developer to prepare metallized conductive polymer films

Poly(vinyl alcohol) metal chelate solutions were prepared by mixing silver nitrate with solutions of poly(vinyl alchol), and films wee prepared from these solutions. These poly(vinyl alcohol) metal chelate films were reduced by photographic developer. The silver ions in poly(vinyl alcohol) films were reduced to silver on the surface, and conductive polymer films were obtained. © 1996 John Wiley & Sons, Inc.     

Poly(vinyl chloride)–polyol (AB)x block copolymers: Synthesis,characterization, and mechanical properties

Poly(vinyl chloride)–polyol (AB)_x block copolymers have been prepared by the condensation polymerization of low-molecular-weight hydroxy-terminated poly(vinyl chlorides) (PVC) and diisocyanate-capped polyester and polyether diols. The difunctional poly(vinyl chlorides) were synthesized by ozonization of commercial resin followed by metal hydride reduction. The (AB)_x block copolymers, which contained 3000 or 4300 molecular weight PVC block sizes and 1000–2000 molecular weight polyol segments, had a wide range of mechanical properties, depending on overall polymer structure. Tensile strengths ranged from 7.8 to 31.5 MPa, elongations from 125% to 610% and torsional stiffness temperatures (T_f) from 25°C to ?22°C.     

Thermal characteristics of poly(ethylene terephthalate) fiber grafted with poly(vinyl acetate) and poly(vinyl alcohol)

Poly(ethylene terephthalate) (PET) fibers were grafted with poly(vinyl acetate) (PVAc) and poly(vinyl alcohol) (PVA). The effects of graft copolymers PVAc and PVA on morphological properties of PET were evaluated by differential thermal analysis, differential scanning calorimetry, and thermogravimetric analysis. Melting temperature, heat of fusion, and mass fractional crystallinity of PET was not affected by graft PVAc and PVA. No individual glass transition and melting points corresponding to the graft PVAc and PVA were observed, indicating thereby that graft copolymer mainly exists in the form of free chains inside the PET matrix. Poly(vinyl alcohol) graft copolymer degraded at much lower temperatures than poly(vinyl alcohol) in powder form. Thermal stability of PET fiber was not affected by graft PVAc, where as PET–g–PVA showed an additional degradation point at 360°C.     

Miscibility of some hydroxyl-containing polymers with poly(acetonyl methacrylate), poly(tetrahydropyranyl-2-methacrylate), and poly(cyclohexyl methacrylate)

Poly(tetrahydropyranyl-2-methacrylate) (PTHPMA) was found to be miscible with Poly(vinyl phenol) (PVPH), Poly(hydroxy ether of bisphenol A) (Phenoxy), and Poly(styrene-co-allyl alcohol) (PSAA). However, Poly(cyclohexyl methacrylate) (PCHMA) is immiscible with all these three hydroxyl-containing polymers. Poly(acetonyl methacrylate) (PACMA) was found to be miscible with PVPH but immiscible with Phenoxy and PSAA. Miscible PTHPMA-Phenoxy blends showed lower critical solution temperature behavior.