高分子量聚醋酸乙烯酯的醇解研究

探讨了催化剂浓度、醇解温度和反应时间等对高分子量聚醋酸乙烯酯醇解的影响,得出高分子量聚醋酸乙烯酯醇解的适合条件。     

Miscibility of C60-end-capped poly(ethylene oxide) with poly(vinyl chloride)

The miscibility of blends of single [60]fullerene (C₆₀)-end-capped poly(ethylene oxide) (FPEO) or double C₆₀-end-capped poly(ethylene oxide) (FPEOF) with poly(vinyl chloride) (PVC) has been studied. Similar to poly(ethylene oxide) (PEO), both FPEO and FPEOF are also miscible with PVC over the entire composition range. X-ray photoelectron spectroscopy showed the development of a new low-binding-energy Cl2p doublet and a new high-binding-energy O1s peak in FPEO/PVC blends. The results show that the miscibility between FPEO and PVC arises from hydrogen bonding interaction between the α-hydrogen of PVC and the ether oxygen of FPEO. From the melting point depression of PEO, FPEO or FPEOF in the blends, the Flory-Huggins interaction parameters were found to be −0.169, −0.142, −0.093 for PVC/PEO, PVC/FPEO and PVC/FPEOF, respectively, demonstrating that all the three blend systems are miscible in the melt. However, the incorporation of C₆₀ slightly impairs the interaction between PEO and PVC.     

The thermal degradation of poly(vinyl acetate) measured by thermal analysis-Fourier transform infrared spectroscopy

The elimination process which occurs during the thermal degradation of poly(vinyl acetate) has been studied using thermal analysis-Fourier transform infrared spectroscopy. It was found that elimination of acetate groups initially began slowly, but increased as degradation proceeded due to an additional process. The increase in rate was found to depend on the concentration of unsaturated groups in the polymer chain. The activation energy for the initial step was found to be 190 kJ mol⁻¹, while that for the additional process was 130 kJ mol⁻¹. The additional process of elimination was considered to be due to a four-membered transition state, activated by double bonds adjacent to the acetate unit.     

Studies on the miscibility and phase structure in blends of poly(epichlorohydrin) and poly(vinyl acetate)

The miscibility of atactic poly(epichlorohydrin) (aPECH) with poly(vinyl acetate) (PVAc) was examined under two different conditions: (i) in dilute solution, using vicometeric measurements and (ii) as cast films, using differential scanning calorimetric (DSC) and FT-infrared spectroscopy. Phase separation on heating, i.e. lower critical solution temperature (LCST) behavior of the aPECH/PVAc blends was examined by the measurement of transmitted light intensity against temperature. From viscosity measurements, the Krigbaum-Wall polymer-polymer interaction (ΔB) was evaluated. The DSC results show that the aPECH/PVAc blends are miscible as evidenced by the observation of a single composition-dependent glass-transition temperature (T_g) which is well described by the Couchman and Gordon Taylor models. The Flory-Huggins interaction parameter (χ₁₂) calculated from the T_g-method was negative and equal to −0.01, indicating a relatively low interaction strength. The FT-IR results match very well with those of DSC. The cloud point phenomenon is thermodynamically driven but phase separation, once taken place, is diffusion controlled in normal accessible time.     

Preparation and characterization of composite resin by vinyl chloride grafted onto poly(BA-EHA)/poly(MMA-St)

Crosslinked poly(butyl acrylate-co-2-ethylhexyl acrylate)/poly(methyl methacrylate-co-styrene) (ACR I) latex was synthesized by multi-stage emulsion polymerization. A series of grafting vinyl chloride (VC) composite latices were prepared by emulsion copolymerization in the presence of core-shell ACR I latex. The effects of ACR I amount and its core/shell ratio on particle diameters of the composite latices and mechanical properties of the prepared materials were investigated. The grafting efficiency (GE) of VC grafted onto ACR I increases with an increasing ACR I content. Transmission electron microscope (TEM) study indicates that ACR I latex particles have a regular core-shell structure obviously. However, when styrene content in the shell of ACR I is more than 70 percent of the shell by weight, ACR I latex particles have an irregular core-shell morphology like sandwich. The composite latex particles synthesized by core-shell ACR I latex grafting VC have a clear three-layered core-shell structure. Dynamic mechanical analysis (DMA) study reveals that the compatibility between ACR I and PVC is well improved. With increasing ACR I content, the loss peak in low temperature range for every composite sample becomes stronger and stronger and gradually shifts to a higher temperature. Scanning electron microscope (SEM) graphs showed that the fractured surface of the composite sample exhibited better toughness of the material. TEM graphs showed that ACR I was uniformly dispersed in the PVC matrix.     

Photooxidative degradation of carboxylated poly(vinyl chloride)

Thin films of poly(vinyl chloride), PVC, and carboxylated poly(vinyl chloride), C-PVC, containing 1.8% of carboxyl groups were exposed to high energy ultraviolet radiation (λ = 254 nm) in laboratory conditions. The photochemical reactions in irradiated samples were studied by FTIR and UV–Vis spectroscopy, gel permeation chromatography and gravimetric estimation of insoluble gel. It was found that photodegradation and photocrosslinking in C-PVC is accelerated, whereas photodehydrochlorination is retarded comparing to these processes in PVC. Photooxidation investigated on the base of reaction leading to formation of hydroxyl groups is also more efficient in modified PVC. However, the total amount of carbonyl groups is much lower in UV-irradiated C-PVC than that in PVC. It indicates that competitive reactions (destruction of carboxyl groups and formation of new carbonyls) occur simultaneously in C-PVC chains. The influence of carbonyl groups on photochemical processes can be explained by an efficient Norrish I and II reactions as well as by energy transfer from absorbing species to weak chemical bonds.     

Miscibility and hydrogen bonding in blends of poly(vinyl acetate) with phenolic resin

The miscibility of phenolic resin and poly(vinyl acetate) (PVAc) blends was investigated by differential scanning calorimeter (DSC), Fourier transform infrared spectroscopy (FT-IR) and solid state ¹³C nuclear magnetic resonance (NMR). This blend displays single glass transition temperature (T_g) over entire compositions indicating that this blend system is miscible in the amorphous phase due to the formation of hydrogen bonding between hydroxyl groups of phenolic resin and carbonyl groups of PVAc. Quantitative measurements on fraction of hydrogen-bonded carbonyl group using both ¹³C solid-state NMR and FT-IR analyses result in good agreement between these two spectroscopic techniques. According to the proton spin-lattice relaxation time in the rotating frame (T_1ρ^H), the phenolic/PVAc blend is intimately mixed on a scale less than 2-3 nm. Furthermore, the inter-association equilibrium constant and its related enthalpy of phenolic/PVAc blends were determined as a function of temperatures by infrared spectra based on the Painter-Coleman association model.     

Preparation of a super-hydrophobic poly(vinyl chloride) surface via solvent-nonsolvent coating

A new simple approach was developed to obtain a super-hydrophobic PVC surface via solvent-nonsolvent coating without addition of low-surface-energy compounds. Also, the PVC film is nearly or still maintains its super-hydrophobicity when contacting with acid, alkali or salt solutions. SEM shows that compared with common smooth PVC surface, a lotus-like structure with micro- and nano-papillae was obviously observed on the hydrophobic PVC surfaces. Such a special surface microstructure may result in the super-hydrophobicity. A brief explanation to the formation of the special microstructure was put forward on the basis of diffusion, tension break and micro- and nano-phase separation.     

Modification of poly(vinyl chloride) by IPN formation with poly(ethyl acrylate)

Semi‐1 and semi‐2 interpenetrating polymer networks (IPNs) of poly(vinyl chloride) (PVC) and in situ formed poly(ethyl acrylate) (PEA) have been synthesized using diallyl phthalate and ethylene glycol dimethacrylate as the crosslinkers of PVC and PEA, respectively. These two types of IPNs have been compared with respect to their physical, mechanical, and thermal properties and an endeavor has been made to find a correlation of these properties with the morphology generated in these systems. The semi‐1 IPNs displayed a decrease in their tensile strength and modulus while in contrast; the semi‐2 IPNs exhibited a marginal increase with increasing crosslinked PEA incorporation. The semi‐1 and semi‐2 IPNs containing 10 and 30 wt % of PEA displayed a two‐stage degradation typical of PVC in their thermogravimetric and DSC studies while confirming the increased stability of the samples with higher percentages of PEA. The softening characteristics as detected by the extent of penetration of the thermomechanical probe as has been detected by thermomechanical analysis are in conformity with their mechanicals. The biphasic cocontinuous systems as explicit from the morphological studies reveal fibrillar characteristics in both the systems. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Fibrous membranes of cellulose acetate and poly(vinyl pyrrolidone) by electrospinning method: Preparation and characterization

Fibrous membranes of cellulose acetate (CA), poly(vinyl pyrrolidone) (PVP) and composite membranes of these polymers, were obtained by the electrospinning method. Using systematic method, the optimal conditions for preparation of fibrous membranes were found. Both CA and PVP a concentration of 8% weight was found. The CA was dissolved in a acetone:water solution, volume ratio 80 : 20 and the PVP is dissolved in ethanol:water solution, ratio volume 85 : 15. The flow rate for both polymers was 1.5 mL h^?1. The same applied voltage value and the distance between the needle and collection plate were for polymer both, 15 kV and 15 cm respectively. The morphology of fibrous membranes and composite membranes were evaluated by scanning electron microscopy (SEM). The CA fibers showed ribon morphology, while the PVP fibers were cilindric, in both cases with diameters in the micrometer range. Thermogravimetric analysis showed that CA had a complete degradation to 445°C, while the fibrous membranes PVP required a value of temperature for degradation of up to 571°C. Fibrous composite membrane PVP/CA/PVP shows a higher value of strain at break (%), and a lower value of tensile strength (MPa) compared to CA/PVP/CA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Reduction of poly(vinyl chloride) with tri-n-butyltin hydride

Reduction of PVC with tributyl-tin-hydride (Bu₃SnH) was studied in order to optimize the method. The reactions were carried out in mixtures of xylene and tetrahydrofuran, chlorine content was determined by ¹H n.m.r. spectroscopy, and the melting behaviour by d.s.c. It was possible to obtain a product with less than 0.1% chlorine in less than 6 h. The ¹³C n.m.r. spectrum showed that the product contained about 4 methyl branches per 1000 monomer units and gave no evidence of chlorinated structures.     

Stabilization of poly(vinyl chloride) by elemental sulfur

The process of stabilization of a poly(vinylchloride) elemental sulfur in thermal and thermooxidative destruction conditions is investigated. The high stabilizing efficiency of elemental sulfur is revealed at the destruction of plasticized poly(vinylchloride) compared with the efficiency of phenolic antioxidants. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Manufacturing and characterizations of flexible poly(dimethylsiloxane)/poly(vinyl acetate)/polythiophene ternary composite films

ABSTRACT

In this study, polythiophene and poly(dimethylsiloxane)/poly(vinyl acetate)/polythiophene ternary composites were synthesized. The new ternary composites obtained in powder and film forms were characterized using various techniques. Magnetic properties of all the materials were analyzed by Gouy balance measurements, and it was found that their conductivity mechanism is of polaron nature. The surface structure, surface roughness, and thermal properties of the prepared samples were identified by Scanning Electron Microscopy, Atomic Force Microscopy, and Thermogravimetric Analysis, respectively. The tensile-tension test studies were performed for mechanical properties. The PDMS/PVAc/PT (6%) composite demonstrated about 50% of the maximum strain value (%) of vulcanized natural rubber.     

Modification of poly(vinyl chloride) films by aliphatic amines to prepare anion-exchange membranes for Cr (VI) removal

ABSTRACT

A method for the synthesis of anion-exchange membranes by the grafting of ethylenediamine (EDA), diethylenetriamine (DETA) or pentaethylenehexamine (PEHA) onto poly(vinyl chloride) (PVC) film has been presented. The chemical structure was determined by means of Fourier Transform Infrared Spectroscopy (FTIR) and the membranes were characterized by ion-exchange capacity, chloride and nitrogen contents, water regain and surface energetics. The obtained membranes were evaluated in the Donnan dialysis (DD) of hexavalent chromium solutions. Among the membranes, those modified with EDA and DETA showed the best separation features: high flux and high recovery factor (RF). The highest degree of recovery was observed for membranes prepared by the casting of PVC solution in (THF), followed by grafting EDA.     

聚醋酸乙烯乳液保护胶体的改性

介绍了聚醋酸乙烯乳液保护胶体改性的一些现状和进展。包括聚乙烯醇的缩醛化、酰基化、烷基化、醋酸乙烯共聚物皂化、添加剂改性等方法以及其他保护胶体的应用。     

Hydrophilic surface modification of poly(vinyl chloride) film and tubing using physisorbed free radical grafting technique

The grafting of hydrophilic monomers from the surface of PVC films and complex geometries, such as tubing, was executed by a novel two-step process: physisorption of a hydrophobic free radical initiator onto a polymer surface followed by radical polymerization with hydrophilic monomers. The key step is creating a hydrophobic/hydrophilic diffusional barrier that promotes radical generation upon heating at the polymer surface. Transmission infrared spectroscopy, X-ray photoelectron spectroscopy, surface wettability and capillary rise, gravimetric analysis, UV-vis spectroscopy and gel permeation chromatography were utilized to prove successful covalent grafting of poly(hydroxyethylmethacrylate), poly(dimethylacrylamide), poly(hydroxyethylacrylate), poly(dimethylaminoethylmethacrylate), poly(acrylic acid), and poly(4-vinyl pyridine).     

Polyhedral oligomeric silsesquioxane as a novel plasticizer for poly(vinyl chloride)

This study focuses on investigating the use of polyhedral oligomeric silsesquioxanes (POSS) to plasticize poly(vinyl chloride) (PVC). Conventional organic plasticizers for PVC, such as dioctyl phthalate (DOP), are somewhat volatile, leading to plasticizer loss and unwanted deterioration of the material properties over time. Previous experimental results indicate that methacryl-POSS, which is much less volatile due to its hybrid organic-inorganic structure, has the ability to plasticize PVC. Methacryl-POSS is miscible in the PVC only up to 15 wt%, thereby limiting its suitability as a plasticizer. However, through the use of ternary compositions it is possible to increase the proportion of methacryl-POSS in PVC substantially. The T_g of appropriately formulated ternary PVC/POSS/DOP compounds can be reduced to near room temperature, and these materials exhibit desirable ductile behavior. Binary (PVC/DOP) and ternary (PVC/POSS/DOP) compounds formulated to the same T_g values showed considerably different mechanical properties. Such findings reveal the possibility of using POSS to engineer the mechanical properties of plasticized PVC.     

The influence of poly(vinyl alcohol) suspending agents on suspension poly(vinyl chloride) morphology

The requirements for PVC suspension resin have changed considerably in the last few years, so much so that few companies have products on their ranges that are more than 4 or 5 years old. The suspending agent has a crucial influence on the morphology of the resin, so the changes in resin characteristics have largely been achieved by changes in the suspending agent systems. After a brief review of the mechanism of PVC suspension polymerisation, the properties of polymers made using PVOH suspending agents are related to changes in the latter. The effect of variations in PVAc degree of hydrolysis and viscosity are related to changes in surface tension. Methods of achieving higher porosity by using low hydrolysis co-suspending agents are described. It is shown that higher bulk densities can be achieved by delayed addition of the PVOH. Levels of conjugated unsaturation and copolymer distributions are also shown to have important influences.     

Blends of plasticized poly(vinyl chloride) and waste flexible poly(vinyl chloride) with waste nitrile rubber powder

Blends of poly(vinyl chloride) (PVC) with varying contents of plasticizer and finely ground powder of waste nitrile rubber rollers were prepared over a wide range of rubber contents through high‐temperature blending. The effects of rubber and plasticizer (dioctyl phthalate) content on the tensile strength, percentage elongation, impact properties, hardness, abrasion resistance, flexural crack resistance, limiting oxygen index (LOI), electrical properties, and breakdown voltage were studied. The percentage elongation, flexural crack resistance, and impact strength of blends increased considerably over those of PVC. The waste rubber had a plasticizing effect. Blends of waste plasticized PVC and waste nitrile rubber showed promising properties. The electrical properties and LOI decreased with increasing rubber and plasticizer content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1552–1558, 2004     

Soiling of plasticized poly(vinyl chloride)

The effects of three plasticizers and two plasticizer concentrations on the topography and soiling of poly (vinyl chloride) (PVC) were studied. Palmitic acid and triolein were chosen to represent solid and liquid soils. The feasibility of using infrared spectroscopy to quantify the amount of soil on PVC was examined. The structure of the solid model soil on plasticized PVC was studied with optical microscopy and atomic force microscopy. Palmitic acid formed two different structures on the PVC surface. Both the type and concentration of the plasticizer influenced the structure of the oily soil on plasticized PVC. The wetting of plasticized PVC with the liquid oily soil was compared to wetting with water through the measurement of the contact angles. Plasticized PVC was hydrophobic and oleophilic. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007