Preparation and characterization of syndiotacticity-rich ultra-high molecular weight poly(vinyl alcohol)/imogolite blend film

To enhance the physical properties of syndiotacticity-rich (syndiotactic diad content 63·4%) ultra-high molecular weight (UHMW) (number-average degree of polymerization 12300) poly(vinyl alcohol) (PVA) film, it was solution blended with rigid-rod imogolite in dimethyl sulphoxide. In addition, the blend film prepared was stretched using a high-temperature zone drawing technique for effective orientation of the film. Through a series of experiments, it was found that imogolite caused significant changes in the structure and properties of syndiotacticity-rich UHMW PVA film, i.e. imogolite acted as an important agent which increased crystal orientation of syndiotacticity-rich UHMW PVA, resulting in enhanced tensile strength of the film. However, imogolite played a hindering role in raising the amorphous orientation of syndiotacticity-rich UHMW PVA. The maximum tensile modulus of 19·8GPa and maximum tensile strength of 1·8GPa could be obtained at the maximum draw ratio of 7·45 for PVA/imogolite blend film. In the case of PVA homo film, the highest tensile modulus and strength were 25·2GPa and 1·4GPa, respectively. © 1998 Society of Chemical Industry     

Rheological properties of water solutions of syndiotactic poly(vinyl alcohol) of different molecular weights

To precisely identify the effect of the molecular weight of syndiotacticity‐rich poly(vinyl alcohol) (s‐PVA) on the rheological properties of s‐PVA/water solutions, we prepared four s‐PVAs with a syndiotactic dyad content of 57%, a degree of saponification (DS) of 99.9%, and number‐average degrees of polymerization (P_n's) of 300, 1300, 2700, and 4000. Through a series of experiments, we found that the molecular weight of poly(vinyl alcohol) had a significant influence on the rheological properties of s‐PVA/water solutions. Over a frequency range of 10^?1 to 10² rad/s, the s‐PVA/water solution with the highest P_n value showed the largest values of the complex viscosity, storage modulus, and loss modulus at similar syndiotacticity and DS values of s‐PVA, and this suggested that the higher P_n was, the stronger the internal ordered structure was in the molecules. All the s‐PVA/water solutions showed shear‐thinning behavior, which implied heterogeneity. In a modified Casson plot, Bingham flow behaviors, which gave rise to non‐zero yield stress, were evident. This suggested that some pseudostructure existed in the s‐PVA/water solutions. The yield stress increased with P_n, and this implied that the pseudostructure was developed as P_n increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1426–1431, 2004     

Rheological properties of high molecular weight (HMW) syndiotactic poly(vinyl alcohol) (PVA)/HMW atactic PVA blend solutions

To identify the effect of blend ratios of syndiotacticity‐rich poly(vinyl alcohol) (s‐PVA)/atactic PVA (a‐PVA) having similar number‐average degrees of polymerization (P_n)s of 4000 and degrees of saponification (DS)s of 99.9% on the rheological properties of s‐PVA/a‐PVA/water solutions, water‐soluble s‐PVA and a‐PVA with different syndiotactic diad contents of 58.5 and 54.0%, respectively, were prepared by bulk copolymerization of vinyl pivalate and vinyl acetate (VAc) and solution polymerization of VAc, followed by saponifying the corresponding copoly(vinyl pivalate/vinyl acetate) and poly(vinyl acetate). The blend ratios played a significant role in rheological behavior. Over the frequency range of 10^?1–10² rad/s, s‐PVA/a‐PVA blend solutions with larger s‐PVA content show more shear thinning at similar (P_n)s and (DS)s of polymer, suggesting that PVA molecules are more readily oriented as s‐PVA content increases. Yield stress is higher for s‐PVA/a‐PVA blend solutions with larger s‐PVA content at similar (P_n)s and (DS)s of polymer. This indicates that more domains with internal order are produced at larger s‐PVA content in s‐PVA/a‐PVA blend solutions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3934–3939, 2006     

Effects of the molecular weight and concentration of poly(vinyl alcohol) on slot die coating

An experimental study was carried out to investigate the effects of the molecular weight and concentration of aqueous poly(vinyl alcohol) (PVA) solutions on the stable operating window of slot die coating. Various coating defects were observed outside the operating window. The window was found to expand with the PVA concentration and molecular weight increasing at low concentrations and to reach a maximum size at the gel point concentration, which corresponded to a critical Deborah number. Beyond this point, the effect of fluid elasticity became dominant, and the window began to shrink. This phenomenon was in contrast to that observed for low‐molecular‐weight glycerol solutions, in which the operating window was found to contract with the concentration or viscosity increasing. This anomalous behavior was attributed to the stretching or extension of long‐chain PVA molecules, which effectively stabilized the fluid motion in the coating bead region. The maximum coating speed could be correlated with the PVA concentration and molecular weight in terms of the capillary number as a function of the dimensionless concentration. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

塑化聚乙烯醇的流变性能及发泡行为研究

采用毛细管流变仪对PVA流变性能进行了表征,用差示扫描量热仪（DSC）研究了降温速率对PVA结晶性能的影响,通过PVA添加化学发泡剂熔融挤出的方法制备PVA发泡材料,并用扫描电镜和密度测试仪分别对发泡材料的泡孔形态和密度进行了表征。结果表明,PVA对剪切作用非常敏感,在低剪切速率下熔体粘度较大,泡孔分布均匀,材料密度较小,在高剪切作用下熔体强度低,气体容易逃逸,导致发泡材料泡孔破裂或合并;低降温速率下熔体粘度小,泡孔易合并、塌陷,合适的降温速度下,PVA熔体粘度适中,发泡材料气泡尺寸小、分布均匀,较快的降温速度下,由于气体压力过大而造成气泡合并,联通,材料密度大。     

Interpretation of long-chain structure from dilute solution properties of ultrahigh molecular weight polymers

Summary Systematic studies on solution properties of ultrahigh molecular weight polymers showed the existence of some special features as compared to usual length polymers. The paper discusses the possible appearance of branched structures in the polymerization process, structures able to influence the mentioned features. From experimental data on poly(methyl methacrylate), poly(butyl methacrylate) and polyacrylonitrile it appears that branching can be excluded, and the very high molecular weight domain considered may be responsible for the modifications observed in the molecular weight dependences on 2>, A₂ or [].     

Preparation of ultrahigh molecular weight syndiotactic poly(vinyl alcohol) microfibrillar fibers by low‐temperature solution polymerization of vinyl pivalate in tertiary butyl alcohol and saponification

Vinyl pivalate (VPi) was solution polymerized in tertiary butyl alcohol (TBA) and in dimethyl sulfoxide (DMSO) with a low chain transfer constant using a low temperature initiator, 2,2′‐azobis(2,4‐ dimethylvaleronitrile) (ADMVN). The effects of polymerization temperature and initiator concentration were investigated in terms of polymerization behavior and molecular structures of poly(vinyl pivalate) (PVPi) and its saponification product poly(vinyl alcohol) (PVA). TBA was absolutely superior to DMSO in increasing the syndiotacticity and molecular weight of PVA. In contrast, TBA was inferior to DMSO in causing conversion to polymer, indicating that the initiation rate of VPi production in TBA was lower than that in DMSO. These effects could be explained by a kinetic order of ADMVN concentration, calculated by the initial rate method. Low‐temperature solution polymerization of VPi in TBA or DMSO by adopting ADMVN proved to be successful in obtaining PVA of ultrahigh molecular weight [maximum number‐average degree of polymerization (P_n): 13,500–17,000] and of high yield (ultimate conversion of VPi into PVPi: 55–83%). In the case of bulk polymerization of VPi at the same conditions, maximum P_n and conversion were 14,500–17,500 and 22–36%, respectively. The P_n and syndiotactic diad content were much higher and the degree of branching was lower with PVA prepared from PVPi polymerized at lower temperatures in TBA. Moreover, PVA from the TBA system was fibrous, with a high degree of orientation of the crystallites, indicating the syndiotactic nature of TBA polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1992–2003, 2002     

Role of the stereosequences of poly(vinyl alcohol) in the rheological properties of syndiotacticity‐rich poly(vinyl alcohol)/water solutions

Syndiotacticity‐rich poly(vinyl alcohols) (s‐PVAs) with various syndiotactic dyad (S‐dyad) contents were prepared by the copolymerization of vinyl pivalate and vinyl acetate with various monomer feed ratios, which was followed by the saponification of copoly(vinyl pivalate/vinyl acetate) to investigate the effect of the stereosequences of s‐PVA on the rheological properties of s‐PVA/water solutions. Through a series of experiments, we identified that the syndiotacticity had a profound influence on the rheological properties of s‐PVA/water solutions. Over a frequency range of 10^?1 to 10² rad/s, s‐PVAs with higher S‐dyad contents showed larger values of complex viscosity and storage modulus and more shear thinning at similar molecular weights and degrees of saponification of the polymer, suggesting that poly(vinyl alcohol) molecules were stiffer and more readily oriented as syndiotacticity increased. All the yield stresses of s‐PVA represented positive values, and s‐PVAs with higher syndiotacticity showed higher yield stresses. This suggests that as syndiotacticity increased, more pseudostructures were present in s‐PVA/water solutions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1858–1863, 2003     

Syndiotacticity‐rich ultrahigh molecular‐weight poly(vinyl alcohol) film. I. Determination of optimum polymer concentration by zone‐drawing method in film preparation

A new method using a simple zone‐drawing technique has been suggested for determining the optimum initial concentration of a polymer solution that has suitable macromolecular entanglements. This method was developed to replace the incorrect inherent viscosity‐measuring method for syndiotacticity‐rich (syndiotactic diad content of 63.4%) ultrahigh molecular‐weight (number‐average degree of polymerization of 12,300) (UHMW) poly(vinyl alcohol) (PVA) solution. Syndiotacticity‐rich UHMW PVA films were prepared from dimethyl sulfoxide (DMSO) solutions with different initial concentrations: of 0.1, 0.2, 0.3, 0.4, and 0.5 g/dL. In order to investigate the drawing behavior of the syndiotacticity‐rich UHMW PVA films with different solution concentrations, the films were drawn under various zone‐drawing conditions. Through a series of experiments, it was discovered that the initial concentration of PVA solution in DMSO caused significant changes in the draw ratio of the syndiotacticity‐rich UHMW PVA film. That is, the one‐step and maximum zone draw ratios of the film at an initial concentration of 0.3 g/dL exhibited its maximum values and gradually decreased at higher or lower concentrations. Thus, it was disclosed that the initial concentration of 0.3 g/dL is the optimum polymer concentration to produce a maximum draw ratio in this work. Based on the above results, it may be concluded that the optimum concentration of the initial PVA solution can be determined directly by measuring the zone draw ratio. The draw ratio, birefringence, crystallinity, degree of crystal orientation, tensile strength, and tensile modulus of the maximum drawn PVA film were 32.9, 0.0449, 0.61, 0.991, 1.91, and 46.2 GPa, respectively. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 123–134, 2000     

Interpolymer associations between poly(vinyl alcohol) and poly(diallyldimethylammonium chloride) in aqueous dilute solution

This article studied the compatibility of poly(vinyl alcohol) (PVA) with poly(diallyldimethylammonium chloride) (PDADMACl) in a dilute aqueous solution. At a total mixture concentration and a constant molecular weight of PDADMACl, it was found that interpolymer associations increase with the molecular weight and decrease with the degree of hydrolysis of the PVA sample (87–89 and 98–99%). From these results, it can be deduced that the compatibility of PVA and PDADMACl is due to specific intermolecular interactions that could be assigned mainly to electrostatic interactions between hydroxyl groups within PVA chains and ion atoms within PDADMACl. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 433–435, 2002     

Effect of thermal hysteresis on melting of syndiotacticity-rich poly(vinyl alcohol) hydrogel

The melting temperatures (T_M) of hydrogels prepared by chilling aqueous solutions of syndiotacticity-rich poly(vinyl alcohol) (s-PVA) at 0°C were measured rising temperature of gels from the initiative temperature (T_I) of 0–70°C (every 10°C). The apparent enthalpies of fusion of a junction ΔH's were estimated from the relation between the logarithm of polymer concentration (log C) and 1/T_M. ΔH depended on T_I, showing that the melting point of gels depended on a thermal hysteresis. The highest polymer concentration C_H in those of the gels which have no melting point above an initiative temperature was determined and ΔH was estimated from the relation between log C_H and the reciprocal melting point of the gels with C_H, 1/T_IM. The ΔH was 15.1 kJ/mol in the range of higher polymer concentrations and 43.9 kJ/mol in the range of lower concentrations.     

Viscosimetric study of poly(vinyl alcohol)/poly(styrenesulfonic acid) miscibility in dilute aqueous solution

The miscibility of poly(vinyl alcohol) (PVA) and poly(styrenesulfonic acid) (PSSA) in dilute aqueous solutions was studied by a viscosimetric method. At a constant molecular weight of PSSA, it was found that the miscibility of both polymers increases with the molecular weight and the number of acetate groups of the PVA samples (1 and 12% unhydrolyzed sites). Moreover, this miscibility increases slightly with the total mixture concentration in the interval 1–2 g/dL. By comparison of the results of reduced viscosity of PVA/PSSA and PVA/poly(sodium styrenesulfonate) (PSSNa) mixtures, it has been deduced that the miscibility of two polymers is due mainly to intermolecular interactions between the hydroxyl and sulfonic groups of PVA and PSSA, respectively. These groups act as acceptors and donors of hydrogen bonds which are the responsible for polymers' miscibility. © 1996 John Wiley & Sons, Inc.     

稀乙酸对聚乙烯醇水溶液静电纺丝性能的影响

采用质量分数3%乙酸水溶液作为高醇解度聚乙烯醇(PVA)的溶剂,研究了PVA稀乙酸溶液的性质及其静电纺丝工艺。结果表明:加入质量分数3%乙酸,PVA溶液粘度下降,表面张力及电导率提高;纺丝液浓度对PVA稀乙酸溶液的静电纺丝性能影响最大;当PVA稀乙酸溶液质量分数为8%～13%,固化距离15mm,纺丝电压14～18kV时,可制得形态良好的PVA超细纤维无纺毡。     

Effect of molecular weight on the rheological properties of atactic poly(vinyl alcohol)/dimethylsulfoxide/water solution

This article describes the molecular weight effect of atactic poly(vinyl alcohol) (a‐PVA) on the rheological properties of 7.5, 10.0, and 12.5 g/dL solutions of a‐PVA with number‐average degrees of polymerization (P_n) of 4000 and 1700 in dimethylsulfoxide/water mixture. a‐PVA with a P_n of 1700 solutions exhibited almost Newtonian flow behavior, whereas high molecular weight a‐PVA, with a P_n of 4000 solutions, exhibited shear‐thinning behavior. On the plot of storage and loss moduli of a‐PVA with a P_n of 1700 solutions, the dynamic storage modulus of a‐PVA, with a P_n of 1700 solutions, was smaller than the dynamic loss modulus over the frequency range of 10^?1 to 10² rad/s. However, the dynamic storage modulus of a‐PVA, with a P_n of 4000 solutions, was smaller than the dynamic loss modulus in the sol state and, in the postgel state, the dynamic storage modulus became larger than the dynamic loss modulus, indicating the evolution of viscoelastic solid properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 41–46, 2004     

Effect of stereoregularity and molecular weight on the mechanical properties of poly(vinyl alcohol) hydrogel

The effect of the stereoregularity and molecular weight of poly(vinyl alcohol) (PVA) on the mechanical properties of hydrogel was investigated. Compressive strength, creep behavior, and dynamic viscoelasticity were measured on hydrogels of syndiotacticity‐rich PVA derived from poly(vinyl pivalate) (D_p = 1690 diad‐syndiotacticity = 61%, D_p = 8020 diad‐syndiotacticity = 62%) and atactic PVA (D_p = 1750 diad‐syndiotacticity = 54%, D_p = 7780 diad‐syndiotacticity = 54%). Increasing the molecular weight of molecular chains constituting the gel improved the compressive strength of atactic PVA hydrogel. The stereoregularity of PVA had a greater effect than molecular weight on the strength of the hydrogel. Gel prepared from 8.8 g/dL syndiotacticity‐rich PVA had a high compressive modulus of 10 kPa, and the compressive modulus of the gel prepared from 3.3 g/dL was comparable with that of atactic PVA hydrogel prepared with more than 6 g/dL. The dynamic storage modulus of the gel derived from syndiotacticity‐rich PVA was remarkably higher than that of the atactic PVA gel and remained constant up to 60°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚(丙烯腈/醋酸乙烯酯)/蒙脱土纳米复合材料的流变性能

研究了聚(丙烯腈/醋酸乙烯酯)/蒙脱土[P(AN/VAc)/Clay]纳米复合材料的溶解特性及其在二甲基乙酰胺(DMA)溶剂中的流变性能。结果表明,P(AN/VACc)/Clay在溶液纺丝时最佳的溶剂为DMA; P(AN/VAc)/Clay-DMA溶液的非牛顿流动指数小于1,溶液为假塑性流体;当溶液质量分数为12%-13%、温度为130-150℃时,P(AN/VAc)/Clay-DMA溶液的纺丝性能最佳     

Effects of solvent adsorption on solution properties of poly(vinyl alcohol)/dimethylsulfoxide/water ternary systems

In this study, the solvent adsorption phenomena of poly(vinyl alcohol) (PVA) in cosolvent mixtures of dimethylsulfoxide (DMSO; solvent 1) and water (solvent 2) were investigated. Typically, this cosolvent mixture could form hydrogen‐bonded DMSO/(water)₂ complexes, involving one DMSO and two water molecules. Because of the complex formation in the cosolvent mixtures, PVA chains preferentially adsorb water molecules at DMSO mole fraction X₁ < 0.33, but preferentially adsorb DMSO molecules at X₁ > 0.33. The preferential adsorption of DMSO (a good solvent for PVA) could cause the relatively extended conformation of PVA chains in solutions because of the increase in excluded volume effect. Because of various interactions between PVA chains and cosolvent mixtures, the aggregation and gelation behaviors of PVA solutions were significantly affected by the composition of cosolvent mixture. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3211–3217, 2004     

Preparation of high molecular weight poly(vinyl pivalate) with high yield and high molecular weight poly(vinyl alcohol) by emulsion polymerization of vinyl pivalate and saponification

To prepare high molecular weight (HMW) poly(vinyl pivalate) (PVPi) with high yield and high linearity which is a promising precursor for syndiotactic poly (vinyl alcohol) (PVA), vinyl pivalate (VPi) was emulsion polymerized, using 2,2′‐azobis(2‐amidinopropane) dihydrochloride (AAPH) as an initiator and sodium dodecyl sulfate (SDS) as an emulsifier. The effect of the polymerization conditions on the conversion, molecular weight, and degree of branching was investigated. PVA with maximum number‐average degree of polymerization (P_n) of 6200 could be prepared by complete saponification of PVPi, with P_n of 13,300–16,700 obtained at polymerization temperature of 50°C, using SDS and AAPH concentration of 2.0 × 10^?3 mol/L of water and 1.0 × 10^?3 mol/L of water, respectively, and the maximum conversion was about 90%. From the emulsion polymerization of VPi, spherical PVPi with high yield was effectively prepared, which might be useful for the precursor of syndiotactic PVA micro‐ and nano‐spheres with various surface properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 410–414, 2007     

Rheological characterization of ethylene vinyl acetate copolymers

A series of ethylene vinyl acetate (EVA) copolymers was studied by dynamic mechanical spectroscopy to understand the relative influence of composition, structure, and molecular weight distribution on their rheological behavior in the melt. The examination of their viscoelastic properties in a large temperature range showed that the glass transition temperature is nearly independent on their composition because of the statistical nature of the copolymers, though some long sequence of polyethylene homopolymer may exist at low vinyl acetate (VA) content. The successful use of the time temperature superposition for oscillatory experiments in the melt confirmed the previous remarks, because the application of the Williams Landel Ferry (WLF) equation leads to a unique set of WLF coefficient, whatever the composition of the EVA. This enables the comparison of the rheological behavior in the melt at the same temperature, in the same free volume condition, and at last it was shown that in the terminal zone, the molecular weight distribution is more influent on the behavior of EVA copolymers than their composition. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2625–2630, 1999     

Synthesis of poly(vinyl alcohol)s with narrow molecular weight distribution from poly(benzyl vinyl ether) precursors

Summary A series of poly(benzyl vinyl ether)s of low molecular weight (5000 to 15000 g mol^-1) and narrow molecular distribution ( ) have been synthesisedvia the cationic polymerisation of benzyl vinyl ether. Acetylation with acetic anhydride/tin (IV) chloride leads to poly(vinyl acetate), which can be hydrolysed to near-monodisperse water-soluble poly(vinyl alcohol) with an isotacticity of approximately 47%. This polymer was re-acetylated and its molecular weight distribution assessed to confirm that hydrolysis gives minimal chain scission.