Preparation and characterization of colloidal dispersions of vinyl alcohol–vinyl acetate copolymers: application as stabilizers for vinyl chloride suspension polymerization

Well‐defined colloidal dispersions of vinyl alcohol–vinyl acetate copolymers (PVAs) with different degrees of hydrolysis (DH) were prepared by a coacervation technique. Colloidal particles in the size range 150–250 nm, with an acetate‐rich core and a hydrophilic PVA corona, were obtained using a combination of a hydrophobic PVA (PVA II) having an average DH ( ) value of 43 mol% with a ‘blocky’ hydrophilic PVA (PVA I) with a value of 72 mol%. The core–shell structure of these particles was demonstrated using ¹H NMR and using fluorescence‐labelled PVA I. The stabilization efficiency of PVA I and PVA II and their combination was examined for 1‐chlorobutane–water emulsions, as a ‘model solvent’ for vinyl chloride–water emulsions. Preliminary tests of vinyl chloride suspension polymerization confirmed the beneficial effect of PVA I and PVA II combinations as stabilizers on the granulometry and the porosity specifications of the poly(vinyl chloride) grains. Copyright © 2006 Society of Chemical Industry     

Drop coalescence processes in suspension polymerization of vinyl chloride

A tracer dye technique was used to investigate the effect of turbulence intensity, stirring time, and the type and concentration of the suspending agent, partially hydrolyzed poly(vinyl acetate) (PVA), on the coalescence rate of vinyl chloride monomer (VCM) droplets in an agitated liquid–liquid dispersion. It was found that the extent of coalescence rises slowly with mixing time, is roughly proportional to the agitation speed, and decreases sharply when the concentration of stabilizer is increased. Coalescence rate depended on the degree of hydrolysis of the stabilizer. The method of addition of initiator during VC suspension polymerization was also studied and its effects on the polymerization conversion and final PVC particles' properties were determined. It was found that the polymerization reaction occurs more uniformly in all the VCM droplets when the initiator was predissolved in the VCM prior to reaction compared with the case when the initiator was predispersed in the continuous water phase. Also, for the same reaction time, the conversion was higher in the former case. During polymerization, the concentration of PVA in the aqueous phase decreased substantially and the porosity of the polymer particles was reduced. © 1996 John Wiley & Sons, Inc.     

Preparation of novel syndiotactic poly(vinyl alcohol) microspheres through the low‐temperature suspension copolymerization of vinyl pivalate and vinyl acetate and heterogeneous saponification

Syndiotactic poly(vinyl alcohol) (PVA)/poly(vinyl pivalate/vinyl acetate) [P(VPi/VAc)] microspheres, with a skin–core structure, were prepared through the heterogeneous saponification of copolymers of vinyl pivalate (VPi) and vinyl acetate (VAc). For the preparation of P(VPi/VAc) microspheres with various particle sizes and a uniform particle size distribution (which are promising precursors of syndiotactic PVA embolic materials to be introduced through catheters for the management of gastrointestinal bleeders, arteriovenous malformations, hemangiomas, and traumatic rupture of blood vessels), VPi and VAc were suspension‐copolymerized at 30°C with a room‐temperature initiator, 2,2′‐azobis(2,4‐dimethylvaleronitrile). The effects of the polymerization conditions were investigated in terms of the size and size distribution of the suspension particles. P(VPi/VAc) microspheres, with various syndiotactic dyad (s‐dyad) contents, were produced through the control of the monomer feed ratio. In addition, monodisperse P(VPi/VAc) particles of various particle diameters were obtained by the separation and sieving of the polymerization product. Monodisperse P(VPi/VAc) microspheres of various particle sizes were partially saponified in the heterogeneous system, and the effects of the particle size and particle size distribution on the saponification rate were investigated in terms of the tacticity and the saponification time and temperature. Novel skin–core PVA/P(VPi/VAc) microspheres of various s‐dyad contents and degrees of saponification were successfully produced through the control of the various polymerization and saponification parameters. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1539–1548, 2005     

Experimental investigation of vinyl chloride drop behavior during suspension polymerization

The effects of some polymerization conditions on poly(vinyl chloride) (PVC) particles produced by the suspension polymerization process were studied on a laboratory scale. The different stages of vinyl chloride suspension polymerization were investigated experimentally by using an on-line sample withdrawal technique during reaction. It was found that the method of addition of initiator has a great effect on the PVC particle uniformity as well as the size distribution. Furthermore, when the initiator was predispersed in the continuous phase, some latex particles were formed. The effect of the type of stabilizer was also studied with two different types of PVA [partially hydrolyzed poly(vinyl acetate)]. It was found that by changing the stabilizer, the particle size, the porosity, and the morphology could change. When H80 (PVA with a degree of hydrolysis of 80% and a molecular weight of 259,000) stabilizer was used, the rigidity of the PVC particles was weak. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 127–134, 1997     

Biodegradable poly(vinyl alcohol)‐graft‐ poly(ε‐caprolactone) comb‐like polyester: Microwave synthesis and its characterization

Poly(vinyl alcohol)‐initiated microwave‐assisted ring opening polymerization of ε‐caprolactone in bulk was investigated, and a series of poly(vinyl alcohol)‐graft‐poly(ε‐caprolactone) (PVA‐g‐PCL) copolymers were prepared, with the degree of polymerization (DP) of PCL side chains and the degree of substitution (DS) of PVA by PCL being in the range of 3–24 and 0.35–0.89, respectively. The resultant comb‐like PVA‐g‐PCL copolymers were confirmed by means of FTIR, ¹H NMR, and viscometry measurement. The introduction of hydrophilic backbone resulted in the decrease in both melting point and crystallization property of the PVA‐g‐PCL copolymers comparing with linear PCL. With higher microwave power, the DP of PCL side chains and DS of PVA backbone were higher, and the polymerization reaction proceeded more rapidly. Both the DP and monomer conversion increased with irradiation time, while the DS increased first and then remained constant. With initiator in low concentration, the DP and DS were higher, while the monomer was converted more slowly. Microwaves dramatically improved the polymerization reaction in comparison of conventional heating method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 3973–3979, 2007     

Suspension stabilizers for PVC production II: Drop size distribution

The drop size distribution of vinyl chloride in water emulsions has been studied using a photographic technique. A large difference in coalescence stability was observed between emulsions stabilized by a poly(vinyl alcohol), Rhodoviol 5/270, and those stabilized by a cellulose ether, Methocel MF50. Experiments simulating the transport of a monomer soluble initiator to the monomer phase of a coalescence stable vinyl chloride in water emulsion showed that the manner of introducing the initiator may have large consequences on the polymerization process.     

Influences of diallyl phthalate as chain extender on the properties of high molecular weight poly(vinyl chloride) resin

A higher porosity with better thermostability is desirable for poly(vinyl chloride) (PVC) resin. In this study, high molecular weight PVC resins are prepared by vinyl chloride monomer (VCM)‐diallyl phthalate (DAP) suspension copolymerization in a 20‐L reactor at 50 °C using DAP as chain extender. SEM, BET, and analyses of plasticizer absorption results show the high molecular weight poly(vinyl chloride) (HPVC) by DAP‐VCM copolymerization is loose and porous. With increasing DAP content when the mass ratio of DAP/VCM (ω) is below the gel point, the porosity and the degree of polymerization increase. Nevertheless, the bulk density and particle size decrease. When more than the gel point, these relationships are reversed. Thermogravimetric analysis revealed that the HPVC had better thermostability than that of commercial PVC, and its thermostability increases with increasing ω before it reaches the gel point. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45093.     

Synthesis of spherical core‐shell poly(vinyl acetate)/poly(vinyl alcohol) particles for use in vascular embolization: Study of morphological and molecular modifications during shell formation

Transarterial vascular embolization and chemoembolization has become common medical procedures, where partially hydrolyzed poly(vinyl alcohol) (PVA) beads remains as one of the most used embolic agent materials. Although synthetic, PVA cannot be synthesized by direct polymerization and must be obtained by chemical modification of another polymer, usually poly(vinyl acetate) (PVAc). The aim of the present work is to synthesize spherical core‐shell PVAc/PVA particles and study the morphological and molecular modifications during shell formation. The polymer particles where produced in two stages, where first the PVAc core was obtained by suspension polymerization of vinyl acetate (VAc) and then the PVA shell synthesized through hydrolysis. Spherical PVAc particles were successfully produced and isolated using an optimized suspension polymerization process. During the shell formation, it was shown that none of the conditions used affected the overall morphology of the particles although changes in the final size distribution could be observed. However, it was possible to identify the process variables and reaction condition that affect the molecular weight averages and polydispersities of the final copolymer. POLYM. ENG. SCI., 55:2237–2244, 2015. © 2015 Society of Plastics Engineers     

Synthesis of poly(vinyl alcohol) core-polystyrene shell-type flower microgels

Four types of poly(vinyl alcohol-b-styrene-b-vinyl alcohol) (P(VA-b-S-b-VA)) triblock copolymers were synthesized by hydrolysis of poly(vinyl acetate-b-styrene-b-vinyl acetate) triblock copolymers prepared by radical living polymerization. The polyvinyl alcohol (PVA) core-polystyrene corona-type flower micelles were formed with ASA-4 in benzene at 25°C. The PVA core part of the micelle was crosslinked with hexamethylene diisocyanate in solution. The monodispersed spherical products (microspheres) were synthesized by crosslinking. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 849–854, 1997     

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     

Synthesis of high-molecular weight poly(vinyl alcohol) by low-temperature emulsifier-free emulsion polymerization of vinyl acetate and saponification

High-molecular weight (HMW) poly(vinyl alcohol) (PVA) was prepared via an emulsifier-free emulsion polymerization of vinyl acetate (VAc) using a redox initiation system in low temperatures, and the subsequent saponification with potassium hydroxide in methanol. The effect of the polymerization conditions on the conversion, molecular weight, and branching degree was investigated. PVA with maximum viscosity-average degree of polymerization (DP) of 8270 could be prepared by saponification of poly(vinyl acetate) (PVAc), with DP of 10,660 obtained at temperature of 10°C, monomer concentration of 30%, potassium persulfate molar ratio to monomer of 1/2000, agitation speed of 160 rpm. The conversion was above 90%. From the emulsifier-free emulsion polymerization of VAc in low temperature, PVAc with HMW and high linearity was effectively prepared, which might be useful for the preparation of high-strength and high-modulus PVA fiber. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influences of some polymerization conditions on particle properties of suspension poly(vinyl chloride) resin

Effects of polymerization temperature, conversions, and nonionic surfactant on the particle properties of suspension poly(vinyl chloride) (PVC) resins were investigated. It was shown that polymerization temperature has no significant influences on the mean particle size of PVC resin, and that the cold plasticiser absorption (CPA) of resin decreases linearly with the increase of polymerization temperature. Agglomeration of VCM droplets finishes before 20% conversion, and the mean particle size keeps almost constant at later stages of the polymerization process, but the CPA continues decreasing with the increase of conversion. Scanning Electron Microscopy (SEM) micrographs show that the degree of agglomeration of primary particles increases with polymerization temperature and conversion. Addition of nonionic surfactant to the VCM suspension system, as a secondary suspending agent, has a great influence on the particle properties of PVC resin. The particle size and CPA increase as the concentration of nonionic surfactant increases. The nonionic surfactant with a greater HLB value is more effective in raising the mean particle size, but is less effective in raising the CPA. It is considered that the added nonionic surfactant would be absorbed faster on the VCM/water interface than the poly(vinyl alcohol) (PVA), which was used as the primary suspending agent. Because the colloid protection ability of the nonionic surfactant is less than that of PVA, droplets become less resistant to coalescence, and the mean particle size of the final PVC resin increases consequently. The increase of porosity is caused by the combined effects of increased coalescence of VCM droplets and the nonionic surfactant's steric effect inside the droplets. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1544–1552, 2002     

Synthesis,characterization, and properties of poly(vinyl acetate)‐ and poly(vinyl alcohol)‐grafted chitosan

Graft copolymers of chitosan and vinyl acetate were synthesized by free radical technique using cerium (IV) as the initiator. Under controlled conditions, as much as 92% grafting with a grafting yield of 30–40% could be achieved. Chitosan‐g‐poly(vinyl alcohol) copolymers were derived by the alkaline hydrolysis of the chitosan‐g‐poly(vinyl acetate) precursor. Thermogravimetric, FTIR, and X‐ray diffraction analyses of chitosan and the copolymers confirmed the grafting reaction between chitosan and vinyl acetate and also the subsequent hydrolysis. Both the copolymers possessed very good film‐forming properties. Grafting resulted in a significant increase in mechanical strength of both the copolymers in the dry condition. Chitosan‐g‐poly(vinyl acetate) (CH‐PVAc) proved more hydrophobic than did pure chitosan, whereas chitosan‐g‐poly(vinyl alcohol) (CH‐PVOH) exhibited enhanced hydrophilicity as evident from their swelling characteristics and contact angle measurements. The enhanced swelling of CH‐PVOH was ascribed to the presence of the pendant poly(vinyl alcohol) group. At pH 1.98, the CH‐PVAc copolymer films showed greater stability than do pure chitosan films, which is highly beneficial for specific biomedical applications. Both the copolymers showed lower glass transition temperature than do pure chitosan. Grafting did not affect the overall thermal stability, and the differential thermogram substantiated the grafting. The investigations indicate that the synthetic–natural hybrid copolymers having desirable mechanical properties and tailored hydrophilic/hydrophobic characteristics are realizable. These polymers could be exploited for varied biomedical applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1852–1859, 2007     

Dispersion copolymerization of acrylonitrile‐vinyl acetate in supercritical carbon dioxide

Dispersion copolymerization of acrylonitrile‐vinyl acetate (AN‐VAc) had been successfully performed in supercritical carbon dioxide (ScCO₂) with 2,2‐azobisisobutyronitrile (AIBN) as a initiator and a series of lipophilic/CO₂‐philic diblock copolymers, such as poly(styrene‐r‐acrylonitrile)‐b‐poly(1,1,2,2‐tetrahydroperfluorooctyl methacrylate) (PSAN‐b‐PFOMA), as steric stabilizers. In dispersion copolymerization, poly(acrylonitrile‐r‐vinyl acetate) (PAVAc) was emulsified in ScCO₂ effectively using PSAN‐b‐PFOMA as a stabilizer. Compared with the precipitation polymerization (absence of stabilizer), the products prepared by dispersion polymerization possessed of higher yield and higher molecular weight. In addition, the particle morphology of precipitation polymerization was irregular, but the particle morphology of dispersion polymerization was uniform spherical particles. In this study, the effects of the initial concentrations of monomer and the stabilizer and the initiator, and the reaction pressure on the yield and the molecular weight and the resulting size and particle morphology of the colloidal particles were investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5640–5648, 2006     

Influences of individual and composed poly(vinyl alcohol) suspending agents on particle morphology of suspension poly(vinyl chloride) resin

Effects of individual and composed poly(vinyl alcohol) (PVA) suspending agents on the particle morphology of poly(vinyl chloride) (PVC) resins were investigated and discussed in the view of PVA absorption at the oil/water interface and interfacial behavior. It was shown that the percentage and surface coverage of PVA at the oil/water interface decreased with the increase of the degree of hydrolysis (DH) of PVA in the DH range of 70–98 mol %, while the interfacial tension of VC/PVA aqueous solution increased linearly with the increase of DH of PVA. PVC resin with more regular particle shape, increased agglomeration and fusion of primary particles, lower porosity and higher bulk density, was prepared by using PVA with a higher DH as a suspending agent. This was caused by the occurrence of drop coalescence at the very early stage of VC polymerization, the increase of particle shrinkage, and the lower colloidal protection to primary particles. It was also shown that the interfacial tension of VC/water in the presence of composed PVA suspending agents varied linearly with the weight composition of the composed PVA suspending agents. The particle properties of PVC resin prepared by using the composed PVC suspending agents were usually situated in between the properties of PVC resins prepared by using the corresponding individual PVA suspending agent. The particle morphology and properties of PVC resin could be controlled by the suitable choice of the composed PVA suspending agents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3848–3855, 2003     

Graft polymerization of vinyl acetate onto starch. Saponification to starch–g–poly(vinyl alcohol)

Graft polymerizations of vinyl acetate onto granular corn starch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinylacetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. However, over half of the polymer was present as ungrafted poly-(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficiency. However, grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate-methyl methacrylate was carried out near 0°C, although conversion of monomers to polymer was low and grafted polymer contained 40-50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch–g–poly(vinyl acetate) to starch–g–poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch–g–poly(vinyl alcohol) in hot water was less than 50%; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized starch for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch–g–poly(vinyl acetate) with about 35% add-on, and a grafting efficiency of about 40% was obtained. A film cast from a starch–g–poly(vinyl alcohol) copolymer in which homopolymer was not removed exhibited a higher ultimate tensile strength than a comparable physical mixture of starch and poly(vinyl alcohol).     

Role of molecular weight of atactic poly(vinyl alcohol) (PVA) in the structure and properties of PVA nanofabric prepared by electrospinning

Atactic poly(vinyl alcohols) (a‐PVAs) having number‐average degrees of polymerization [(P_n)s] of 1700 and 4000 were prepared by the solution polymerization of vinyl acetate, which was followed by the saponification of poly(vinyl acetate) to investigate the effects of molecular weights of a‐PVA on the characteristics of electrospun a‐PVA nanofabrics. A‐PVA nanofabrics were prepared by electrospinning with controlling the process parameters including the electrical field, conductivity, tip‐to‐collector distance, and solution concentration. Through a series of characterization experiments, we identified that the molecular weight of a‐PVA had a marked influence on the structure and properties of nanofabrics produced. That is, the higher the molecular weight of PVA, the superior the physical properties of PVA nanofabric. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1638–1646, 2004     

Synthesis and characterization of conducting copolymers of poly(vinyl alcohol) with thiophene side‐groups and pyrrole

Graft copolymers of poly(vinyl alcohol) with thiophene side‐groups and pyrrole were synthesized by electrochemical polymerization methods. Poly(vinyl alcohol) with thiophene side‐groups (PVATh) was obtained from the reaction between poly(vinyl alcohol) (PVA) and thiophene‐3‐acetic acid. The syntheses of copolymers of PVATh and pyrrole were achieved electrochemically by using three different supporting electrolytes, p‐toluene sulfonic acid (PTSA), sodium dodecyl sulfate (SDS) and tetrabutylammonium tetrafluoroborate (TBAFB). Characterization of PVATh and graft copolymers was performed by a combination of techniques including cyclic voltammetry, scanning electron microscopy, thermal gravimetry, differential scanning calorimetry, size‐exclusion chromatography, ¹H NMR and FT‐IR. The conductivities were measured by the four‐probe technique. Copyright © 2004 Society of Chemical Industry     

Preparation of high‐molecular‐weight poly(vinyl alcohol) with high yield by solution polymerization of vinyl acetate in methanol using 4,4′‐azobis(4‐cyanovaleric acid)

Vinyl acetate (VAc) was solution‐polymerized at 40°C and 50°C using 4,4′‐azobis(4‐cyanovaleric acid) (ACVA) as an initiator and methanol as a solvent, and effects of polymerization temperature and initiator concentration were investigated in terms of conversion of VAc into poly (vinyl acetate) (PVAc), degree of branching (DB) for acetyl group of PVAc, and molecular weights of PVAc and resulting poly(vinyl alcohol) (PVA) obtained by saponifying with sodium hydroxide. Slower polymerization rate by adopting ACVA and lower viscosity by methanol proved to be efficient in obtaining linear high‐molecular‐weight (HMW) PVAc with high conversion and HMW PVA. PVA having maximum number–average degree of polymerization (P_n) of 4300 could be prepared by the saponification of PVAc having maximum P_n of 7900 polymerized using ACVA concentration of 2 × 10^?5 mol/mol of VAc at 40°C. Moreover, low DB of below 1 could be obtained in ACVA system, nevertheless of general polymerization temperatures of 40°C and 50°C. This suggests an easy way for producing HMW PVA with high yield by conventional solution polymerization without using special methods such as low‐temperature cooling or irradiation. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 4831–4834, 2006     

氯乙烯SET-DT悬浮聚合动力学和成粒过程的相互关系

以碘仿为引发剂、连二亚硫酸钠/碳酸氢钠为催化体系、聚乙烯醇(PVA)和/或纤维素衍生物(MC)为分散体系,进行氯乙烯单电子转移-蜕化链转移(SET-DT)活性自由基悬浮聚合,采用在线示踪气相色谱法和激光粒度分析系统研究分散剂种类和浓度、搅拌转速等对聚合动力学和单体液滴/聚合物颗粒粒径分布的影响。发现在相同搅拌转速下,以MC为分散剂的氯乙烯聚合速率最大,以PVA为分散剂时反应速率最小;分散剂种类固定时,聚合速率随分散剂浓度增大而增大。SET-DT悬浮聚合过程中,水相连二亚硫酸钠分解产生的自由基向单体液滴的扩散速率与液滴粒径分布和皮膜结构有关,因此聚合成粒过程影响聚合动力学。尽管不同条件下的聚合均经历液-液分散、液滴黏并、树脂颗粒稳定(转化率>30%)等成粒阶段,但各阶段的液滴/颗粒平均尺寸随分散体系和搅拌转速的变化而变化,引起聚合速率变化;采用MC为分散剂得到的PVC树脂皮膜少,有利于水相产生的自由基向单体相的扩散,聚合速率大。