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     

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     

可逆加成-断裂链转移聚合制备聚氯乙烯-b-聚乙二醇-b-聚氯乙烯共聚物

合成了含黄原酸酯端基的聚乙二醇（X-PEG-X）大分子链转移剂,并以其为可逆加成-断裂链转移试剂调控氯乙烯（VC）溶液和悬浮聚合,合成聚氯乙烯-b-聚乙二醇-b-聚氯乙烯（PVC-b-PEG-b-PVC）三嵌段共聚物。X-PEG-X调控VC溶液聚合得到的共聚物的分子量随聚合时间增加而增大,分子量分布指数小于1.65。X-PEG-X具有水/油两相分配和可显著降低水/油界面张力的特性,以X-PEG-X为链转移剂和分散剂,通过自稳定悬浮聚合也可合成PVC-b-PEG-b-PVC共聚物,共聚物颗粒无皮膜结构,分子量随聚合时间增加而增大;由于VC悬浮聚合具有聚合物富相和单体富相两相聚合特性,共聚物分子量分布指数略大于溶液聚合共聚物。通过乙酸乙烯酯（VAc）扩链反应进一步证实了PVC-b-PEG-b-PVC的“活性”,并合成PVAc-b-PVC-b-PEG-b-PVC-b-PVAc共聚物。水接触角测试表明PVC-b-PEG-b-PVC的亲水性优于PVC。     

Facile fabrication of poly(vinyl alcohol) gels and derivative aerogels

A facile preparation of poly(vinyl alcohol) (PVOH) hydrogels and their derivative PVOH/montmorillonite clay aerogels is reported, using water as solvent and divinylsulfone as crosslinking agent, making use of an environmentally friendly freeze drying process. The materials exhibit significantly increased mechanical properties after crosslinking. The compressive modulus of an aerogel prepared from an aqueous suspension containing 2 wt% PVOH/8 wt% clay increased 29-fold upon crosslinking, for example. Crosslinking of the polymer/clay aerogels decreased the onset decomposition temperature as measured by thermogravimetric analysis, and generated a more continuous structure at higher clay contents. Such polymer/clay aerogels are promising materials for low flammability applications.     

Nonaqueous polymerization of vinyl chloride: An environmentally friendly process

Poly(vinyl chloride) (PVC) is produced via a nonaqueous polymerization process in which hexane is used as a diluent. This nonaqueous process can lead to significant energy savings, significant reductions in carbon dioxide emissions, and the elimination of wastewater. Various suspending agents have been used to evaluate their effects on the shape and morphology of PVC grains. The nonaqueous process leads to the formation of PVC grains with higher porosity than that of typical suspension PVC. The bulk density is slightly lower than that of suspension PVC, but the thermal stability seems to be similar. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Starch–poly(vinyl alcohol) foamed articles prepared by a baking process

Composite foam plates were prepared by baking a mixture of granular starch and aqueous poly(vinyl alcohol) (PVOH) solution inside a hot mold. Foam strength, flexibility, and water resistance were markedly improved by addition of 10–30% PVOH to starch batters. The improvement in strength at low humidity was greater for partially (88%) hydrolyzed PVOH while strength at higher humidities improved most with fully (98%) hydrolyzed PVOH. Foam flexibility increased with higher PVOH molecular weight. Scanning electron micrographs of the surface of the foams revealed a phase-separated morphology in which swollen starch granules were embedded in a matrix of PVOH. The starch component was gelatinized (melted) during baking while the PVOH component crystallized to a high degree during baking. Crosslinking agents such as Ca and Zr salts were added to starch batters to give further increases in water resistance. Respirometry studies in soil showed that the starch component of starch–PVOH foams biodegraded relatively rapidly (weeks) while the PVOH component degraded more slowly (months). Baked foams prepared from starch and PVOH have mechanical properties that are adequate for use as packaging containers over a wide range of humidity. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 2129–2140, 1998     

Thermal and structural characterization of nanofibers of poly(vinyl alcohol) produced by electrospinning

Poly(vinyl alcohol) (PVOH) was obtained from the alkaline hydrolysis of poly(vinyl acetate) (PVAc). Nonwoven membranes (mats) of PVOH nanofibers were produced by electrospinning of solutions of PVOH in water with and without aluminum chloride. The concentration of the PVOH/water solution was 12.4% w/v. The morphology of the mats was analyzed by scanning electron microscopy (SEM). The thermal properties and the degree of crystallinity of the nanofibers were measured by differential scanning calorimetry (DSC); the crystal structure of the mats was evaluated by wide‐angle X‐ray diffraction. The best nanofibers were obtained by electrospinning the PVOH/water solution with aluminum chloride (45% w/v) in which an electrical field of 3.0 kV/cm was applied. It was observed that the addition of the aluminum chloride and the increase in the applied electrical field decreased the number‐average nanofibers diameters. The mats without aluminum chloride had higher melting temperatures and higher degrees of crystallinity than the mats with the salt. The crystal structure of the mats was found to be monoclinic; however, the mats were neither highly oriented nor have a high degree of crystallinity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of poly(vinyl acetate) suspending agents on suspension polymerisation of vinyl chloride monomer

Abstract

When partially hydrolysed poly(vinyl acetate) (PVAc) is used as a suspending agent in the suspension polymerisation of vinyl chloride monomer, it has significant effects on the morphology of the resulting poly(vinyl chloride) (PVC) particles. At the initial step of polymerisation, PVC molecules are grafted onto the molecules of the suspending agent forming a PVC–PVAc membrane. The properties of this membrane depend on the type of suspending agent, the polymerisation temperature, the mixing efficiency, and other factors. The morphology of the growing PVC particles and the properties of the PVC resin obtained depend in turn on the characteristics of the membrane. A model has been developed relating to the connection between the polymerisation conditions and the characteristics of the suspending agent on one hand, and on the PVC properties on the other hand. The model is based on an analysis of the characteristics of the PVC–PVAc membrane and their effect on PVC properties.     

Study on characterization of pyrolysis and hydrolysis products of poly(vinyl chloride) waste

Poly(vinyl chloride) PVC pyrolysis and hydrolysis are conducted in a fixed bed reactor and in an autoclave, respectively, under different operating conditions such as the temperature and time. The product distribution is studied. For the PVC pyrolysis process, the main gas product is HCl (55% at 340°C), there is 9% hydrocarbon gas (C₁–C₅), the liquid product fraction is about 5% (at 340°C), and the solid residue fraction is about 31% (at 340°C). For the hydrolysis process, the main gas product is HCl (55.8% at 240°C) and the solid residue is about 49.6% (at 240°C). The pyrolysis liquid product is analyzed by using gas chromatography with magic‐angle spinning. Aromatic hydrocarbons are the main class (90%), of which the major part is benzene (33%). The residue produced through pyrolysis and hydrolysis is investigated by high‐resolution solid‐state ¹³C‐NMR. These details revealed by the high‐field NMR spectra provide importmant information about the chemical changes in the PVC pyrolysis and hydrolysis process. The mechanism of PVC hydrolysis dechlorination is also discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3252–3259, 2003     

Gellan/poly(vinyl alcohol) hydrogels: characterization and evaluation as delivery systems

Bioartificial polymeric materials in the form of hydrogels were prepared starting from blends of poly(vinyl alcohol) (PVOH) with gellan, using a procedure based on freeze–thawing cycles. The effect exerted by gellan on the properties of these materials was investigated. The materials were loaded with human growth hormone (GH) and the release of the drug was evaluated. The results obtained indicated that gellan favours the crystallization process of PVOH allowing the formation of a material with a more homogeneous and stable structure than that of pure PVOH hydrogels. Both the PVOH melting enthalpy and the elastic modulus increased with increasing gellan content in the hydrogels; in addition, the higher the gellan content in the samples, the lower was the amount of PVOH released. Gellan/PVOH hydrogels were able to release GH and the release was affected by the content of the biological component. The amount of GH released was within a physiological range. © 2001 Society of Chemical Industry     

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.     

聚氯乙烯/纳米氧化铝复合材料的制备与性能

利用硅烷偶联剂（KH 550）对纳米氧化铝进行有机化处理,并通过熔融共混制备了聚氯乙烯/纳米氧化铝复合材料。通过红外分析对纳米氧化铝进行了表征,采用扫描电子显微镜观察了纳米氧化铝在聚氯乙烯树脂中的分散状况,并对复合材料的热性能和力学性能进行了研究。结果表明,经过表面改性的纳米氧化铝粒子在PVC基体中分布均匀;加入纳米氧化铝改善了复合材料的热性能和力学性能;当纳米氧化铝含量为3.0 %（质量分数,下同）时,复合材料的拉伸强度和冲击强度相对于纯聚氯乙烯材料分别提高了16.25 %和20.27 %。     

Average mixing torque,tensile and impact properties,and thermal stability of poly(vinyl chloride)/sawdust composites with different silane coupling agents

Unique explanations are given to describe changes in the mixing torque and tensile and impact properties of poly(vinyl chloride) (PVC)/wood sawdust composites affected by various types and concentrations of silane coupling agents. Concentrations of 0.5–1.0 and 1.5 wt % coupling agent are recommended for the optimization of the tensile and impact properties of the composites, respectively. Changes in the tensile and impact properties of the composites with a low sawdust content were more sensitive to the addition of silane coupling agents than those with a high sawdust content. KBM603 was suitable for improving the tensile properties, whereas KBE603 is recommended for high impact resistance of the composites. The differences in the mechanical and thermal properties of the PVC/sawdust composites were dependent on the characteristics of the functional groups in the silane coupling agents used, such as hydrophilic level, number of functional groups, self‐condensation reaction, and effectiveness of the hydrolysis reaction. Silane coupling agents above 1.0 wt % resulted in an increase in polyene sequences in the PVC structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 213–221, 2005     

Absorption of trioctyl trimellitate into mass‐polymerization and suspension‐polymerization poly(vinyl chloride)

Poly(vinyl chloride) (PVC) slush powder has been widely used; we prepared it by dry blending. We found that the absorption of plasticizer by the PVC resins was the most important factor in the dry‐blending process and, further, that different types of PVC resin had different absorption rates. This results of this study provide new information about the relationship of absorption to PVC and other parameters. Haake rheomix testing and the quantity of plasticizers absorbed by the PVC resins were used to characterize the absorption process. Suspension‐polymerization poly(vinyl chloride) (SPVC) and mass‐polymerization poly(vinyl chloride) (MPVC) in different sizes were used for the test. The results showed that the MPVC absorbed the plasticizer more quickly than SPVC, especially at a higher temperature. However, for the same PVC resin type, the absorbing speeds were nearly independent of particle size. The studies that used a scanning electric microscope and specific surface area revealed that the morphology of the two types of particles was different. The surfaces of the individual particles of SPVC were smoother than those of MPVC. There was a “skin” covering the SPVC particles, whereas with the MPVC particles, the primary polymer was exposed directly on the surface. This difference in morphology was shown to be a significant factor in the different rates of absorption of the plasticizers for the different PVC resins. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2369–2374, 2004     

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。     

Water dilutable secondary stabilisers in suspension polymerisation of vinyl chloride monomer

Abstract

One of the continuing trends in the development of superior quality suspension poly(vinyl chloride) (sPVC) resin has been the need to impart higher grain porosity, facilitating improved vinyl chloride monomer removal and faster, more uniform, plasticiser uptake. To achieve this, PVC producers have adopted the use of specific secondary suspending agents, traditionally in the form of low hydrolysis, low molecular weight poly(vinyl acetate) (PVAc).

It is well known that low hydrolysis PVAc is insoluble in water, and as such must be supplied as alcohol or alcohol rich solutions, typically in methanol. The use of methanol presents safety and environmental hazards relating to its particular toxicity and flammability. These concerns led to the development, during the 1980s, of water based secondary suspending agents, with a low methanol content, typically at 55% hydrolysis. These partially hydrolysed PVAcs remained for a long time the optimum hydrolysis at which a stable, aqueous product could be supplied, while imparting good PVC grain porosity. Nevertheless, in certain sPVC formulations, aqueous based 55% hydrolysed secondary suspending agents were failing to achieve the same high porosity levels as the solvent based systems, which typically had hydrolysis levels below 50%.

The recent development of a lower hydrolysis, water soluble, fully dilutable grade, named Alcotex WD30, has provided an ideal solution, giving all the advantages of both secondary systems. This has been achieved by the ionic modification of the polymer, imparting superior water solubility, and allowing the production of a stable, aqueous partially hydrolysed PVAc at less than 50% hydrolysis. It has been demonstrated, using experimental design software, that such a water based, modified secondary, of 45–50%hydrolysis, is anoptimum product for producing high porosity PVC, with an acceptable grain size, in conjunction with a 72·5% hydrolysed PVAc as the primary suspending agent. The actual molecular weight of the polymer, or the degree of ionic modification required to aid the solubility of the polymer in water, has a negligible effect on the PVC properties.     

Influences of initiator addition methods in suspension polymerization of vinyl chloride on poly(vinyl chloride) particles properties

Vinyl chloride suspension polymerization was carried out in a pilot‐scale reactor to study the effects of different methods of initiator addition on poly(vinyl chloride) (PVC) resin properties. The experiments used different arrangements for adding the initiator to the reactor, whereas other reaction conditions were the same: (i) initiator was added to the continuous aqueous phase and then monomer was dispersed in it (conventional method); (ii) initiator was predissolved in monomer before dispersing in the continuous aqueous phase; and (iii) suspending agents along with initiator were added to the monomer before polymerization. The PVC resin prepared by method of (i) had a higher monomer conversion and a higher Sauter mean diameter of grains with a narrow particle size distribution comparable to that of PVC resins by other methods. Scanning electron microscopy showed more uniform particles and fused primary particles in the grains, which confirms lower porosity and lower cold plasticizer absorption (CPA) for PVC grains produced by procedure of (ii). The results showed that when the suspending agents were also predispersed in monomer along with initiator (iii), CPA increases dramatically due to internal porosity of the grains. Simultaneously, a marked decrease in Sauter mean diameter was apparent. Scanning electron microscopy micrographs show that primary particles in the interior of PVC grains prepared by the latter method are looser, and there is more free volume between primary particles resulting the high internal porosity and consequently higher CPA. Mercury porosimetry analysis also confirms these results. K value as a molecular weight characteristic for all methods was the same . J. VINYL ADDIT. TECHNOL., 24:116–123, 2018. © 2016 Society of Plastics Engineers     

Improving the antifouling property of poly(vinyl chloride) membranes by poly(vinyl chloride)‐g‐poly(methacrylic acid) as the additive

To improve the antifouling property of poly(vinyl chloride) (PVC) membranes, a series of poly(methacrylic acid) grafted PVC copolymers (PVC‐g‐PMAA) with different grafting degree were synthesized via one‐step atom transfer radical polymerization process utilizing the labile chlorines on PVC backbones followed by one‐step hydrolysis reaction. PVC/PVC‐g‐PMAA blend membranes with different grafting degree and copolymer content were prepared by nonsolvent induced phase separation method. The surface chemical composition, surface charge, membrane structures, wettability, permeability, separation performances and the fouling resistance of blend membranes were carefully investigated. The results indicated that the PMAA chains were segregated towards the surface and the membranes were endowed with negative charge. The hydrophilicity and permeability of the blend membranes were obviously improved. Furthermore, the antifouling ability especially at neutral or alkaline environments was also significantly increased. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42745.     

Effect of poly(vinyl chloride) resin type in the preparation process of slush powder

During the preparation of the poly(vinyl chloride) (PVC) slush powder, we found that PVC resins obtained by different polymerization methods affected many properties of slush powder and its products. Two types of commercial PVC resins were used for slush powder preparation: mass poly(vinyl chloride) (M‐PVC) and suspension poly(vinyl chloride) (S‐PVC). We used the Haake rheomix test to characterize the absorption of plasticizers into PVC resins, and the results showed that M‐PVC absorbed the plasticizers more quickly than S‐PVC. The fusion behavior of the two slush powders was studied by the thermal plate test and Haake rheomix test, and the results showed that the slush powder of M‐PVC was easier to fuse than that of S‐PVC. The different properties of the two resins and slush powder could be explained by the morphology, average size, and size distribution. Due to the “skin” of the particles' surfaces, the wider size distribution, and the large size of particles, S‐PVC absorbed the plasticizers more slowly and was more difficult to fuse. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3331–3335, 2002     

Improving mechanical properties of poly(vinyl chloride) by doping with organically functionalized reactive nanosilica

Nanosilica particles are functionalized by in situ surface‐modification with trimethyl silane and vinyl silane. Resultant reactive nanosilica (coded as RNS) contains double bonds and possesses good compatibility with vinyl chloride (VC) and polyvinyl chloride (PVC). This makes it feasible for RNS to copolymerize with VC generating RNS/PVC composites via in situ suspension polymerization. As‐prepared RNS/PVC composite resins are analyzed by means of FTIR. The tensile strength and impact strength of compression‐molded RNS/PVC composites are measured and compared with that of compression‐molded PVC composites doped with dispersible nano‐SiO₂ particles (abridged as DNS) surface‐modified with trimethyl silane alone. Moreover, the thermal stability of compression‐molded RNS/PVC and DNS/PVC composites is evaluated by thermogravimetric analysis. It has been found that RNS/PVC composites possess greatly increased impact strength and tensile strength than PVC matrix, while DNS/PVC composites possess higher impact strength than PVC matrix but almost the same tensile strength as the PVC matrix. This implies that DNS is less effective than RNS in improving the mechanical strength of PVC matrix. Particularly, RNS/PVC composites prepared by in situ suspension polymerization have much higher mechanical strength than RNS/PVC composites prepared by melt‐blending, even when their nanosilica content is only 1/10 of that of the melt‐blended ones. Besides, in situ polymerized RNS/PVC and DNS/PVC composites have better thermal stability than melt‐blended nanosilica/PVC composites. Hopefully, this strategy, may be extended to fabricating various novel high‐performance polymer‐matrix composites doped with organically functionalized nanoparticles like RNS. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013