Poly(butylene succinate)/poly(vinyl phenol) blends. Part 1. Miscibility and crystallization

Miscibility has been investigated in blends of poly(butylene succinate) (PBSU) and poly(vinyl phenol) (PVPh) by differential scanning calorimetry in this work. PBSU is miscible with PVPh as shown by the existence of single composition dependent glass transition temperature over the entire composition range. In addition, the polymer–polymer interaction parameter, obtained from the melting depression of PBSU using the Nishi–Wang equation, is composition dependent, and its value is always negative. This indicates that PBSU/PVPh blends are thermodynamically miscible in the melt. Preliminary morphology study of PBSU/PVPh blends was also studied by optical microscopy (OM). OM experiments show the spherulites of PBSU become larger with the PVPh content, indicative of a decrease in the nucleation density, and the coarseness of PBSU spherulites increases too with increasing the PVPh content in the blends.     

浓乳液双相聚合制备聚丙烯酸丁酯粒子及其对聚氯乙烯的改性研究

用浓乳液双相法合成PBA，通过在合成过程中添加不同用量的DVB交联剂和MMA硬单体调节PBA粒子的硬度及性能，研究了不同DVB及MMA加入量的PBA对PVC力学性能的影响。并通过复合材料断面微观形态分析验证了实验结果。结果表明：在BA单体中加入硬单体MMA和交联剂DVB均可提高PBA粒子的硬度，当MMA和DVB用量较大时，会导致粒子呈现刚性，不利于PBA对PVC改性；PBA粒子与硬质PVC共混后能较好地分散在PVC中，并能在提高材料冲击强度的同时，拉伸强度也有所改善；DVB和MMA的用量均为2mL时，PBA异形粒子对硬质PVC的改性效果最好。此配方PBA粒子与PVC相容性好、界面结合力强。     

Poly(vinyl alcohol) and poly(vinyl amine) blend membranes for isopropanol dehydration

Blended membranes of hydrophilic polymers poly(vinyl alcohol) (PVA) and poly(vinyl amine) (PVAm) were prepared and crosslinked with glutaraldehyde. The prepared membranes were characterized using infrared (attenuated total reflection mode) spectroscopy, differential scanning calorimetry, X‐ray diffractometry, and scanning electron microscopy measurements. Pervaporation performances of the membranes were evaluated for the separation of water‐isopropanol (IPA) mixtures. As the PVAm content increased from PVAm0 to PVAm1.5, the flux through a 70 μm film increased from 0.023 to 0.10 kg/m² h at an IPA/water feed ratio of 85/15 at 30 °C. The driving force for permeation of water increased due to the temperature but it has no effect on IPA permeation. Activation energies for the permeation of IPA and water were calculated to be 17.11 and 12.46 kJ/mol, respectively. Controlling the thickness of the blend membrane could improve the permeation flux with only a marginal reduction in the separation factor. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45572.     

Properties of Poly(vinyl chloride)/poly(ethylene oxide)/polyaniline Conductive Films: The Effect of Poly(ethylene glycol) Diglycidyl Ether

The effect of polyaniline and poly(ethylene glycol) diglycidyl ether on tensile properties, morphology, thermal degradation, and electrical conductivity of poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films was studied. The poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films were prepared using a solution casting technique at room temperature until a homogeneous solution was produced. Poly(vinyl chloride)/poly(ethylene oxide)/polyaniline/poly(ethylene glycol) diglycidyl ether conductive films exhibit higher electrical properties, tensile strength, modulus of elasticity but lower final decomposition temperature than poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films. Scanning electron microscopy morphology showed that the polyaniline more widely dispersed in the poly(vinyl chloride)/poly(ethylene oxide) blends with the addition of poly(ethylene glycol) diglycidyl ether as surface modifier.     

硅烷交联聚氯乙烯的研究

研究了硅烷的种类,增塑剂,交联时间等因素对PVC交联的影响,结果表明,通过调节硅烷的用量可以制备不同交联度的PVC,交联后的PVC其力学性能,尺寸稳定性,体积电阻率,热主为形温度得到提高。     

低聚合度、低醇解度聚乙烯醇的合成与性能研究——I.低聚合度聚醋酸乙烯酯的合成

以甲醇为溶剂,偶氮二异丁腈(AIBN)为引发剂,采用自由基聚合方法合成了低聚合度聚醋酸乙烯酯,并对其结构进行了表征。讨论了聚合时间、引发剂用量、物料配比、聚合温度等因素对聚合率的影响,获得了相对较佳的工艺参数。     

Physical Properties of Plasticized Poly(vinyl chloride) Blended with Poly(methyl methacrylate) Nanoparticles Synthesized by Differential Microemulsion Polymerization

In this work, poly(methyl methacrylate) (PMMA) nanoparticles synthesized by differential micro emulsion polymerization were used to improve the physical properties of plasticized poly(vinyl chloride) (PVC). PVC, plasticizer (40 phr), heat stabilizer (2 phr), and lubricant (0.2 phr) were melt-mixed with varied amount of the PMMA nanoparticles (3, 5, 7, and 9 phr) on a two-roll mill, followed by compression molding. The results showed that the tensile strength, Young's modulus, tear strength, and thermal stability were improved, but the elongation at break deteriorated with increased PMMA content. Moreover, the flammability of the plasticized PVC was not improved by the PMMA nanoparticles.     

Yttrium fumaropimarat as a novel heat stabilizer for poly(vinyl chloride)

Yttrium fumaropimarat (YFPA) was synthesized with fumaropimaric acid and yttrium acetate as raw materials. The structure of the product was analyzed and characterized by Fourier transform infrared spectrometer, scanning electron microscope, energy dispersive X‐ray microanalysis, and X‐ray diffraction. The results showed that the product was amorphous state, three‐dimensional reticulation compound by the ionic bond of COO^? and Y³⁺. The effect of YFPA on poly(vinyl chloride) (PVC) thermal stability was researched by means of Congo red method and heat oven aging method. The experimental results showed that YFPA was a good long‐term PVC thermal stabilizer and could greatly improve PVC thermal stability and initial stage stainability mixing calcium stearate, zinc stearate, and pentaerythrite. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45015.     

原位聚合聚氯乙烯树脂的合成及性能

研究了氯乙烯悬浮聚合时添加氯化聚乙烯(CPE)冲击改性剂、CaCO3填料、润滑剂及热稳定剂对聚合反应的影响，并对得到的可直接加工的原位聚合聚氯乙烯(RTUPVC)树脂的性能进行了表征。结果发现：CPE和CaCO3的加入均使达到相同压降的聚合时间缩短，氯乙烯聚合转化率相应减小；RTUPVC树脂的粒径随CPE粒径和用量的增大而增大，而CaCO3含量对RTUPVC树脂粒径影响不大；润滑剂和热稳定剂的加入，对聚合反应起延缓作用，但对RTUPVC树脂粒径影响不大；RTUPVC树脂加工塑化时间随CPE含量的增加而减少；相同CPE用量时，RTUPVC树脂的冲击强度和拉伸强度明显高于PVC/CPE共混物。     

Living cationic polymerization of isobutyl vinyl ether (II): Photoinduced living cationic polymerization in a mixed solvent of toluene and diethyl ether

A new method of preparation of living cationic polymer of isobutyl vinyl ether via photoinduced polymerization in the presence of diphenyliodonium iodide (DPII, initiator) and zinc iodide in a mixed solvent of toluene/diethyl ether, which was irradiated at ?78°C for short period, was completed within 15 min. The reaction was allowed for further reaction in the dark until monomer was fully consumed. It was found that increase in the conversion of monomer to polymer during the irradiation is very limited. Confirmation of the linear dependence of number‐average molar mass of resulting polymer on % conversion together with the fact that polymerization proceeds until monomer consumption, and controllability of number‐average molar mass of resulting polymer, depending on the molar ratio of monomer and initiator, strongly suggests the living nature of this polymerization, unless reaction temperature becomes higher than 0°C, i.e., the absence of chain breaking process. The narrow molar mass distribution, whose polydispersity index values are less than 1.2, reveals that the rate of initiation where irradiation is usually completed within 15 min is much faster than that of propagation in cationic nature in this system. Effect of some major factors, such as solvent polarity and temperature, on the living nature of the polymerization was also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3581–3586, 2006     

Poly(vinyl alcohol) as a stabilizer in the suspension polymerization of styrene: The effect of the molecular weight

The interfacial tension of the water-(PVA)/styrene system was measured as a function of the poly(vinyl alcohol) (PVA) concentration and temperature. Average size and particle-size distribution were obtained for a suspension of styrene in water using PVA as a stabilizer. We discuss the interfacial tension through the Zykonski equation to establish the behavior of the adsorption isotherms in unstirred systems and discuss the apparently contradictory results of the stirred experiment. We propose a simple configuration model that is congruent with both results. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 71–77, 1998     

Permeation of Oxygen and Nitrogen Gases through Poly(ethylene-co-vinyl acetate) Membranes

The transport of oxygen and nitrogen gases through uncrosslinked and crosslinked poly(ethylene-co-vinyl acetate) membranes has been analyzed. Poly(ethylene-co-vinyl acetate) was crosslinked by dicumyl peroxide and benzoyl peroxide. Neat sample showed a lower permeation coefficient due to the crystalline nature. The crystalline nature was supported by X-ray diffraction analysis. The difference in the permeation behavior of the two crosslinked samples was correlated with crosslink density. Crosslink density was calculated using equilibrium sorption method. Differential scanning calorimetry analysis also supports the different permeation behavior of the crosslinked samples. The O₂/N₂ selectivity of the membranes was estimated. The influence of the crosslink density and size of penetrants on permeation were analyzed. The effect of free volume on the gas barrier properties was investigated by positron annihilation lifetime spectroscopy.     

Hybrid Hydrogels Based on Poly(vinyl alcohol) (PVA)/Agar/Poly(ethylene glycol) (PEG) Prepared by High Energy Electron Beam Irradiation: Investigation of Physico‐Mechanical and Rheological Properties

A series of hybrid hydrogels based on poly(vinyl alcohol) (PVA)/agar/poly(ethylene glycol) (PEG) prepared by a solution casting method using e‐beam irradiation are investigated to determine the effect of agar and PEG content (1, 2, and 4 wt%) on their physicomechanical and rheological properties. The gel content of the hydrogels decreases with increasing agar and PEG contents. The equilibrium swelling of PVA hydrogel decreases on blending with agar while adding PEG to PVA/agar increases the swelling by about 400%. No obvious change in the dehydration behavior of the hybrid hydrogels is observed on changing agar and PEG contents. The solid‐like rheological behavior of the hydrogels is not significantly affected by agar content, while it approaches a liquid‐like behavior at high PEG loading. The tensile strength of the hybrid hydrogels is improved by increasing agar content, while its elongation‐at‐break is decreased. On the other hand, the opposite results are found regarding the influence of PEG and its content on the mechanical properties of the hybrid hydrogels.

     

聚乙烯醇缩甲醛泡沫塑料的研究进展

概述了聚乙烯醇缩甲醛（PVFM）泡沫塑料的发展现状、性能、制备方法,并详细讨论了聚乙烯醇种类、水的用量、甲醛的用量、酸的用量等工艺条件对PVFM泡沫塑料性能的影响。同时,还介绍了PVFM泡沫塑料的发泡成型方法,包括发泡剂起泡法、机械打泡法和成孔剂发泡法。最后,指出PVFM泡沫塑料目前主要应用领域为清洁和美容材料、过滤和消声材料、功能医用材料、环保和生物载体材料以及可降解复合天然高分子材料。     

A Viscometric Study of the Miscibility Behaviour of Poly(N-Vinyl Pyrrolidone) Blends

The miscibility behaviour of blends of poly(N-vinyl pyrrolidone) (PVP) with poly(vinyl chloride) (PVC), poly(vinyl acetate) (PVAc) and vinyl chloride–vinyl acetate (VCVAc) copolymer has been investigated on the basis of a viscometric approach. PVP is found to be miscible with PVC over the entire composition range, as is evident from the high values observed for the intrinsic viscosity of transfer. This is further supported by the single glass transition temperature observed in differential scanning calorimetry studies of the blend films. Blends of PVP with VCVAc copolymer exhibit microphase separation which is shown clearly in the scanning electron micrographs of the films. PVAc/PVP blends show interaction only at low PVAc contents, but in general are immiscible. © of SCI.     

Poly(1,5-hexadiyne) films prepared using rhodium(i) catalysts

Bis(1,5-cyclooctadiene)dirhodium(I)dichloride and bis(norbornadiene)-dirhodium(I)dichloride are effective catalysts for polymerization of 1,5-hexadiyne. The structure of the polymer obtained and its behaviour towards oxidation and oxidizing agents has been elucidated by means of infrared and ultraviolet spectroscopy. It is proposed that polymerization proceeds with formation of a polymer having a five-membered ring in each of its monomeric units. The polymer is highly conjugated and can be obtained directly during polymerization as film, which has a metallic lustre, is insoluble in common solvents, and shows good resistance to oxidation in air, if sufficiently thick.     

Surface Modification of Poly(vinyl alcohol) Fibers

The surfaces of PVA fibers prepared by in situ fibrillation were modified by first crosslinking using glyoxal and then attaching cationic and anionic groups by grafting. Crosslinking prior to modification was beneficial in minimizing the solubility of the fibers in the aqueous medium in which they were modified. Heterogeneous modification techniques were employed so that fiber properties could be preserved. PAA and PDMC were grafted from the PVA microfibrils using the KPS/NaS₂O₃ redox initiating system. Grafting was confirmed by FTIR and NMR spectroscopy. The modified PVA fibers were also analyzed by DSC, TGA, and SEM.

     

Particle features of poly(vinyl chloride) resins prepared by a new heterogeneous polymerization process

The heterogeneous polymerization of vinyl chloride monomer (VCM), with n‐butane as the reaction medium, was used to prepare poly(vinyl chloride) (PVC) resins. The particle features of the resulting resins and the particle formation mechanism of the polymerization process were investigated. The PVC resins prepared by the new polymerization process had a volume‐average particle size comparable to that of suspension PVC resins and a lower number‐average particle size. From scanning electron micrographs, it could be seen that the new PVC resins had a regular particle shape and a smooth surface with no obvious skin. They also had a high porosity. The new PVC resins were composed of individual and loosely aggregated primary particles. The diameter of the primary particles in the top layer of the grains was smaller than that of the primary particles in the center part of the grains. On the basis of the particle features of these PVC resins, a particle formation mechanism for the new polymerization process was proposed. PVC chains precipitate from a VCM/n‐butane mixed medium to form primary aggregates at a very low conversion, and the primary aggregates of the PVC chains aggregate to form primary particles, which further aggregate to form grains. The primary particles and grains grow by the capture of newly formed PVC chains and their primary aggregates and by polymerization occurring inside the aggregates. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 954–958, 2003     

Poly(vinyl alcohol) modified with carboxylic acid anhydrides: crosslinking through carboxylic groups

The reaction of carboxylic acid anhydride with poly(vinyl alcohol) (PVA) leads to vinyl alcohol—vinyl ester copolymers which contain carboxylic acid groups. Esterification enables degrees of modification to be reached which depend on the chemical structure of the anhydride introduced and the ratio of the reagents in the feed. The copolymers obtained were characterized by spectroscopic techniques, elemental analysis, and thermal methods. These half-esters reacted in a second step with aromatic diglycidyl ethers to obtain tridimensional networks. This crosslinking reaction through the carboxylic groups was studied by differential scanning calorimetry. The water absorption of the linear and crosslinked polymers was determined gravimetrically as a function of time at room temperature. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1643–1651, 1997