Redox-Initiated Grafting of Acrylic Monomers onto Poly(vinyl Alcohol)

Loss of capacity of magnetic micro ion-exchange resins has been suggested to be caused by cleavage of unstable linkages formed during the graft polymerization reaction. The nature of the grafting process was investigated by using a series of model compounds having the same structural features as the glutaraldehyde-crosslinked poly(vinyl alcohol) core matrix. These compounds were then subjected to hydrogen peroxide oxidation, followed by the addition of monomer in the presence of iron(II). The identity and extent of peroxidation of the intermediate compounds was determined. In each of the peroxidation reactions the tertiary acetal hydrogen was oxidized to a hydroperoxy derivative. Some of these derivatives were able to dimerize to form peroxy compounds. The reactions occurred rapidly at room temperature when an acetal compound was shaken with hydrogen peroxide. Good yields could be obtained by precipitation of the sodium salts of the hydroperoxides. The hydroperoxy derivatives were shown to initiate polymerization of methyl acrylate, acrylic acid, and acrylamide when in the presence of iron(II).     

Ceric Ion Initiated Graft Polymerization onto Poly(vinyl Alcohol)

This paper describes the kinetics of the ceric ion-initiated graft co-polymerization of vinyl acetate-acrylonitrile to poly(vinyl alcohol). The graft copolymerization rate R_p was found to be first order with respect to the total concentration of the comonomer mixture [M], the concentration of vinyl alcohol repeating units [PVA], and the mole fraction of vinyl acetate in the comonomer feed mixture. R_p was independent of cerous ion. The grafting rate was independent of ceric ion above a ceric concentration of 0.0020 M but first order in ceric ion below that concentration. Rp initially increased rapidly with [H⁺] to a maximum and then decreased and levelled off at hgher [H⁺]. The rate of ceric ion disappearance was first order in [PVA], independent of [MI, and increased with increasing [H⁺] with a leveling off at high [H⁺]. A reaction mechanism.     

FTIR Study of the Thermal Degradation of Poly(vinyl Alcohol)

The degradation of poly(vinyl alcohol) was investigated using TG analysis and Fourier transform infrared spectroscopy to determine the effect of atmosphere on the process of degradation. In the spectra, four vibrational modes were identified that characterised the major steps of the degradation process. These were the O-H, C-H, C=O and C=C stretching modes. The mechanism observed for degradation in an inert atmosphere was in accordance with the accepted mechanism of elimination followed by pyrolisation. Evidence of conjugated polyenes, however, was not observed. For the air atmosphere, oxidation in both steps of the degradation process was observed. This revised version was published online in July 2006 with corrections to the Cover Date.     

The Mechanism of Reaction between Poly(vinyl Alcohol) and Phosphorous Acid

The reaction mechanism of phosphorous acid and poly(vinyl alcohol) is presented. It has been found that there during this reaction mono- and diesters are formed in which most of the acid radicals are in the phosphonic form. To confirm the presence of this form in the product obtained, reactions with diethyleneamine and chloral have been carried out as characteristic tests for phosphonic groups. The occurrence of C—P bonds resistant to hydrolysis has been also found in the reaction product.     

Preparation of Colloidal Rhodium in Poly(vinyl Alcohol) by Reduction with Methanol

Refluxing of a solution of poly(vinyl alcohol) and rhodium(III) chloride in methanol-water gives a colloidal dispersion of rhodium which is an effective catalyst for hydrogenation of cyclohexene in methanol at 30°C under atmospheric hydrogen pressure. Formaldehyde is produced quantitatively with the reduction of rhodium(III) chloride to metallic rhodium. The rhodium particles in the colloidal dispersion are found to consist of two kinds of particles, about 8 and 40 Å in diameter by electron microscopy. The sizes of the small (8 Å) and large (40 Å) particles are almost constant during the course of refluxing. The number of small particles, which is the great majority of particles at the early stage of refluxing, gradually decreases; concurrently the number of large particle increases on prolonged refluxing. An absorption peak appears at 260 nm at the early stage of refluxing. The presence of the 260 nm peak, which indicates the coordination of poly(vinyl alcohol) to rhodium(III) ion, is indispensable for the formation of a homogeneous colloidal dispersion of rhodium. The addition of ethylenediamine inhibits the formation of colloidal rhodium in refluxing. The catalytic activity of colloidal dispersion of rhodium is dependent upon the concentration of rhodium(III) chloride charged and is independent of that of poly(vinyl alcohol). The formation mechanism of colloidal rhodium is discussed.     

Surface Modification of Carbon Nanotube by Poly(ethylene glycol) for the Preparation of Poly(vinyl alcohol) Nanocomposite

Herein, PEGylated multi-walled carbon nanotube (MWNT) was prepared for the successive fabrication of poly(vinyl alcohol) PVA/MWNT nanocomposite film by solution casting. The surface modified MWNT showed a good colloidal stability in a polar solvent, i.e., water. Also, the PEGylated MWNT had an improved dispersion stability in aqueous PVA solution. The mixture of PEGylated MWNT and PVA dissolved in water was film casted and the dispersion uniformity and corresponding improvement of electrical conductivity were investigated. The electrical conductivity of PVA/modified MWNT composite film was three-fold higher than that of PVA/pristine MWNT composite film due to the much improved distribution uniformity of modified MWNT in PVA matrix.     

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...     

Poly(vinyl chloride-g-butyl rubber)

The synthesis of poly(vinyl chloride-g-butyl rubber) and some of its physical properties are described. The key to the synthesis involves copolymerization initiation of an isobutylene–isoprene charge by a PVC/Et₂AlCl initiator system with 1,2-dichloroethane as solvent. The graft is a thermoplastic; cast films are flexible and optically clear. Proof of grafting is the crosslinking with S₂Cl₂ of the pentane-extracted product in THF solution. Crosslinking the butyl rubber moiety in the graft reduces overall stress properties.     

Poly(vinyl chloride) Nanocomposites

Poly(vinyl chloride) is one of the major thermoplastics beside other commodities polymers like polyethylene and polystyrene. However, some of its main characteristics such as plasticity, thermal and photo stability are inferior to other commodity polymers. Adding nano scale inorganic fillers to poly(vinyl chloride) or other polymers in view to obtain polymer nanocomposites with superior properties has drawn the attention of many researchers in the last decades. Poly(vinyl chloride) nanocomposites are obtained mainly by in situ polymerization, solution based or mixing techniques. The resulting products show improvement of most important properties of poly(vinyl chloride) such as thermal, mechanical, rheological, flammability, antibacterial, etc. This paper presents preparation ways of poly(vinyl chloride) nanocomposites using different nano fillers and the improved properties compared with those of virgin poly(vinyl chloride).     

Development of Nanocomposites from Bacterial Cellulose and Poly(vinyl Alcohol) using Casting-drying Method

Nanocomposites of bacterial cellulose (BC) and poly(vinyl alcohol) (PVA) were prepared by cast-drying method as an easy way in producing nanocomposite films and to expand the use of BC. The contribution of PVA in nanocomposites was evaluated by measurement of cross-sectional surface, moisture uptake and mechanical properties. Morphological analysis shows that PVA covered a number of cellulosic fibres and formed denser material as a function of PVA addition. Based on the tensile test, the addition of PVA causes a very slight reduction compared with bacterial cellulose itself. The BC/PVA nanocomposites still have similar stiffness to BC with elongation at break less than 5%, while PVA film shows ductile properties with elongation at break more than 80%. On the other hand, the presence of BC fibres in the PVA matrix enhanced the tensile strength and the elastic modulus of pure PVA about two to three times, but it decreased the toughness of pure PVA. The highest tensile strength and elastic modulus of the nanocomposites are 164 MPa and 7.4 GPa, respectively at BC concentration of 64%. Increasing BC concentration is proportional to reducing moisture uptake of BC/PVA nanocomposites indicating that the existence of BC fibres inhibits moisture absorption.     

聚癸二酸丙三醇酯对聚乳酸的改性

以丙三醇和癸二酸为单体通过熔融缩聚制得了聚癸二酸丙三醇酯(PGS),并用其预聚物(p-PGS)对聚L-丙交酯(PLLA)进行共混改性.利用傅立叶变换红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)及凝胶渗透色谱(GPC)法对P-PGS的结构进行表征,并研究了改性后材料的力学性能、两相相容性、亲水性能和细胞相容性.结果表明:P-PGS具有支化分子结构,分散系数约为2.7;共混改性后的材料弹性模量和拉伸强度均有所下降,而断裂伸长率从7 %显著提高到150%左右;PLLA/PGS属于海岛式共混结构,PGS以小于10μm的尺寸均匀分布在PLLA基体中;共混后材料的亲水性也有一定的提高,且几乎保持了PLLA原有的细胞相容性.     

Effect of Halide Salts of Alkali Metals on Crystallinity of Poly(vinyl Alcohol) Cryogels

The degree of crystallinity of poly(vinyl alcohol) in cryogels obtained by single freezing at–20°С followed by thawing of 13% aqueous solutions of the polymer bearing dissolved NaCl, KCl, CsCl, KBr, and KI in the concentration of 0.7 mol/kg is determined by attenuated total reflectance Fourier transform IR spectroscopy. It is established that the addition of NaCl, KCl, and CsCl to the poly(vinyl alcohol) solution leads to a substantial increase (by 1.5–1.7 times) in the degree of crystallinity in the cryogel prepared from this solution. The effect of KCl, KBr, and KI on the degree of crystallinity strongly depends on the salt anion. The replacement of the Cl^– anion by the larger Br^– anion reduces dramatically the crystallizing effect of the salt, while the even larger I^– anion, in contrast, reduces rather than increases the degree of crystallinity relative to that of the cryogel without a salt. The effect of the salts on the crystallinity of poly(vinyl alcohol) cryogels is explained by the simultaneous action of two processes. One of them facilitates crystallization and consists in the strengthening of dehydration of poly(vinyl alcohol) owing to competition between the polymer molecules and the salt ions for the liquid water molecules during its freezing. The other process hampers crystallization and is connected with a reduction in the water freezing point under action of the salt ions.     

Synthesis of Modified Poly(vinyl Alcohol)s and Their Degradation Using an Enzymatic Cascade

Poly(vinyl alcohol) (PVA) is a water-soluble synthetic vinyl polymer with remarkable physical properties including thermostability and viscosity. Its biodegradability, however, is low even though a large amount of PVA is released into the environment. Established physical-chemical degradation methods for PVA have several disadvantages such as high price, low efficiency, and secondary pollution. Biodegradation of PVA by microorganisms is slow and frequently involves pyrroloquinoline quinone (PQQ)-dependent enzymes, making it expensive due to the costly cofactor and hence unattractive for industrial applications. In this study, we present a modified PVA film with improved properties as well as a PQQ-independent novel enzymatic cascade for the degradation of modified and unmodified PVA. The cascade consists of four steps catalyzed by three enzymes with in situ cofactor recycling technology making this cascade suitable for industrial applications.     

聚乙烯醇-g-异氰酸酯-脂肪醇梳状接枝共聚物的合成、 结构及热性能

通过甲苯-2,4-二异氰酸酯(TDI)的连接作用, 利用接枝共聚法将具有储热功能的长链脂肪醇[如十八醇(C₁₈OH)、 十六醇(C₁₆OH)和十四醇(C₁₄OH)]接枝到聚乙烯醇(PVA)主链上, 制备出储热能力不同的聚乙烯醇-g-TDI-脂肪醇[PVA-g-TDI-C(n)]梳状接枝共聚物. 通过傅里叶变换红外光谱(FTIR)、 差示扫描量热分析(DSC)、 热重分析(TGA)和X射线衍射(XRD)等方法研究了PVA-g-TDI-C(n)共聚物的热行为和结晶结构. 结果表明, PVA-g-TDI-C(n)共聚物具有良好的储热能力, 储热能力随侧链碳原子数目和侧链接枝度的增加而增大, 但明显低于长链脂肪醇的储热能力. PVA-g-TDI-C(n)共聚物具有良好的热稳定性, 失重温度在324~330 ℃之间. 从侧链受限运动角度探讨了影响PVA-g-TDI-C(n)共聚物热性能和有序堆砌结构的原因.     

Poly(Organophosphazenes): Use in the Improvement of Standard Materials. Application to the Modification of Surface Properties of Poly(Vinyl Alcohol)

Abstract

Modification of surface properties of poly(vinyl alcohol) by grafting of poly(organophosphazenes).     

Poly(vinyl fluoride) solution characteristics

Nine unfractionated poly(vinyl fluoride) samples were characterized for molecular weight and polydispersity by means of sedimentation velocity, osmometry, and viscosity measurements. Molecular weights were in the range of 143,000–654,000 and M _w/M _n = 2.5–5.6. The Mark-Houwink (M-H) relation was established as [η] = 6.52 × 10^?5 M^0.80. The M-H exponent is at the Flory-Fox upper limit (0.80), as is characteristic of extended, polar polymers, in good solvents. The unperturbed chain dimensions, characteristic ratio and steric factor were derived by the methods of Stockmayer and Fixman and Kurata and Stockmayer. The steric factor is 1.7, which agrees with data reported for other poly(vinyl halides).     

Poly(vinyl alcohol) obtained through polymerization of some vinyl esters

Bulk and/or solution polymerizations of a series of vinyl esters, e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, and vinyl benzoate were conducted. Iodine-coloration, 1,2-glycol structure, molecular weight, and tacticity (triad and pentad) were measured for the resulting poly(vinyl alcohol)s (PVAs). The iodine-coloration abilities of PVAs, derived from poly(vinyl ester)s that were obtained through bulk polymerization at 60°C, depended on the starting monomer, increasing in the following order: vinyl benzoate < vinyl acetate < vinyl propionate < vinyl butyrate < vinyl pivalate. In solution polymerizations of vinyl propionate and vinyl butyrate, it was revealed that the tacticity of the derived PVAs apparently depended on the type and amount of polymerization solvent employed, as found previously in the case for vinyl acetate. The iodine-coloration of these PVA samples varied in the same order as their syndiotactic content, while no relationship was observed toward their 1,2-glycol content. The probabilities of the syndiotactic propagation at 60°C were estimated as 0.49 (benzoate), 0.54 (acetate), 0.55 (propionate), 0.56 (butyrate), and 0.60 (pivalate), respectively.     

Electrical Conductivity in Poly(vinyl Chloride)

Conductivity and Seebeck coefficient measurements have been made on commerically-available molded PVC samples containing a range of impurities and on much purer specimens recast from tetrahydrofuran solution. Activation energies measured in the latter materials were not very reproducible; it seems likely that the evaporation of gold electrodes thermally initiates a dehydrochlorination reaction which renders the samples unstable. A range of activation energies from 1.4 to 1.8 eV was observed in the impure samples. The Seebeck coefficient measurements indicated that the majority carriers were negatively charged; the linearity of the current-voltage relationship up to applied field strengths of 80,000 V/cm then suggested an electronic conduction mechanism, although considerable polarization effects were observed in both pure and impure samples. The Seebeck coefficient results also showed that even the purest PVC obtainable is unlikely to be an intrinsic semiconductor, and that the electron transport mechanism probably corresponds more closely to the small polaron hopping model than to the conventional energy-band formation model commonly applied to inorganics.     

Poly (vinyl chloride) decomposition in solution

Thermal degradation of PVC in various solvents at 180° has been observed to be in the following order: benzonitrite > nitrobenzene > cyclohexanone > dioctyl phthalate > α-bromonaphthalane > decahydronaphthalene. The effect has been explained on the basis of β-eliminations of E₁-type favoured by polar solvents. An inhibition in PVC degradation has been observed in nitrobenzene containing stationary hydrogen chloride gas. The deceleration in degradation by predissolved HCl has been accounted for as a Mass Law effect.