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     

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     

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。     

在无机分散剂存在下苯乙烯悬浮聚合宏观成粒的特征

以苯乙烯悬浮聚合为体系,考察羟基磷酸钙(HAP)或HAP与聚乙烯醇(PVA)复合为分散剂体系时,各种因素如分散剂浓度、油水比、搅拌速度等与瞬时液滴大小及分布之间的关系,并分析讨论瞬时液滴分散、合并的过程特征.结果表明,悬浮苯乙烯液滴聚合宏观成粒的特征与分散剂的分散机理无关,仅体现液滴分散、合并的过程特点.当采用分批加分散剂时,实验观察到瞬时液滴大小分布呈由单峰过渡到双峰,再发展成单峰分布的特征,从而找出了以分批加分散剂方式制备窄分布聚合物颗粒的理论依据.     

VAc聚合过程工艺条件对链支化的影响

研究了以甲醇为溶剂、偶氮二异丁腈(AIBN)为引发剂的VAc聚合过程,通过比较醇解前后PVAc和PVA聚合度的变化研究过程参数如溶剂、引发剂量和分段加入方式以及反应时间对PVAc链支化程度的影响。结果表明,在溶剂总量为20%(wt)、引发剂总量为0.00013%~0.0013%范围内,分段加入引发剂使PVAc链支化程度增加,醇解后PVA聚合度与PVAc聚合度相比有所下降;过低的引发剂浓度虽然可以获得比较高的PVAc聚合度,但醇解后的PVA聚合度相比PVAc下降可达27.0%。在引发剂总量为0.000 63%情况下分批加入溶剂,在合适的反应时间内可控制PVAc支链化程度,缩小PVAc和PVA聚合度的差异并获得相对较高PVA聚合度。无论是一次性加入溶剂或分段加入溶剂,过长的反应时间都使PVAc的支链化程度增加,醇解后PVA聚合度与PVAc聚合度相比差异增大。     

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     

Continuous Dosing of a Fast Initiator during Suspension Polymerization of Vinyl Chloride for Enhanced Productivity: Mathematical Modeling and Experimental Study

An adopted mathematical model was developed to reduce the batch time required for the suspension polymerization of vinyl chloride in order to improve the productivity by continuous dosage of a fast initiator during polymerization reaction. The model was accompanied by a particle swarm optimization (PSO) algorithm, so as to optimize the initiator dosage rate during the process for a certain conversion. A pilot scale reactor was employed to verify the mathematical model predictions. This showed that the model predictions are in very good agreement with the experimental data. A proper initiator dosage trajectory during the course of the reaction was obtained in such a way that the reaction rate over the course of polymerization was constant and corresponded to the maximum rate in the conventional case (non-continuous addition of a mild initiator). The maximum reduction in reaction time relative to conventional polymerization for the predefined conversion was 53%. Analyzing the molecular characteristics of the samples showed that the molecular characteristics of the final poly(vinyl chloride) (PVC) product remained relatively unchanged under an optimum initiator dosage trajectory compared with the conventional process.     

Dispersion polymerization of vinyl acetate in a mixture of ethanol and water

Dispersion polymerization of vinyl acetate (VAc) was studied in a mixed solvent of ethanol and water using poly(vinyl alcohol) (PVA) with a low degree of hydrolysis as a steric stabilizer. Six compositions were chosen from a homogeneous phase before the polymerization. In a composition with the highest solubility parameter, 450 nm particles with a size distribution close to monodispersity were obtained. With decreasing solubility parameters of the compositions, the particles became polydisperse. In the compositions with solubility parameter lower than 17.1, particles were not formed even at 100 % conversion. Degrees of polymerization obtained in this homogeneous phase were less than 100 and close to calculated values. With increasing solubility parameters of the system, degrees of polymerization increased but were still less than 200. Grafting of VAc onto PVA and grafted PVA were very small, indicating the presence of a competing reaction to the grafting. Copyright © 2004 Society of Chemical Industry     

Study on preparation of monodispersed poly(styrene‐co‐N‐dimethylaminoethyl methacrylate) composite microspheres by SPG (Shirasu Porous Glass) emulsification technique

Monodispersed poly(styrene‐co‐N‐dimethylaminoethyl methacrylate) [P(St‐DMAEMA)] composite microspheres were prepared by employing a Shirasu Porous Glass (SPG) emulsification technique. A mixture of monomer, hexadecane (HD), and initiator N,N′‐azobis(2,4‐dimethylvaleronitrile) (ADVN) was used as a dispersed phase and an aqueous phase containing stabilizer [poly(vinyl pyrrolidone) (PVP) or poly(vinyl alcohol) (PVA)], sodium lauryl sulfate (SLS), and water‐soluble inhibitor [hydroquinone (HQ), diaminophenylene (DAP), or sodium nitrite (NaNO₂)], was used as a continuous phase. The dispersed phase was permeated through the uniform pores of SPG membrane into the continuous phase by a gas pressure to form the uniform droplets. Then, the droplets were polymerized at 70°C. The effects of inhibitor, stabilizer, ADVN, and DMAEMA on the secondary nucleation, DMAEMA fraction in the polymer, conversion, and morphologies of the particles were investigated. It was found that the secondary nucleation was prevented effectively in the presence of HQ or DAP when PVP was used as the stabilizer. The secondary particle was observed when ADVN amount was raised to 0.3 g (/18 g monomer); however, no secondary nucleation occurred even by increasing DMAEMA fraction to 10 wt %. This result implied that the diffusion of ADVN into the aqueous phase was a main factor responsible to the secondary nucleation more than that of DMAEMA. The hollow particles were obtained when NaNO₂ was used, while one‐hole particles formed in the other cases. By adding crosslinking agent, the hole disappeared and the monomer conversion was improved. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2408–2424, 2001     

RADICAL DESORPTION IN EMULSION POLYMERIZATION OF VINYL ACETATE

In the present paper a model equation for calculating the radical desorption rate constant,k_0,in the emulsion polymerization of vinyl acetate was suggested and the various parameters forevaluating k_0 were determined.Effects of reaction temperature,emulsifier concentration,initiator con-centration,monomer conversion and phase ratio on k_0 were studied.It indicates that the desorptionof radicals from latex particles to aqueous phase must be taken into account in the modelling ofemulsion polymerization for the monomers with higher hydrophilicity such as vinyl acetate.     

Evolution of vinyl chloride conversion below critical micelle concentration: A response surface analysis

Utilizing response surface methodology, the conversion of vinyl chloride monomer (VCM) was monitored when the polymerization temperature, the type of surfactant, and the weight ratio of water‐to‐monomer (W/M) were taken as the emulsion polymerization variables. Because the homogeneous nucleation was found to be the dominant mechanism in VCM emulsion polymerization, irrespective of the surfactant concentration, the whole experiments have been carried out below critical micelle concentration of the used surfactants. Among all the studied variables, the polymerization temperature appeared as the most effective parameter; moreover, its interactive effect with W/M caused different trends in the alteration of final conversion being observed. Also, depending on the reaction temperature, the VCM conversion would be affected by the type of the surfactant used. Contrarily, simultaneous change in the type of surfactant and W/M revealed an insignificant effect on the evolution of VCM conversion. The optimization of final conversion of VCM was also accessible through contour plots of response surface methodology. It is worth noting that, taking a conventional approach into consideration, the alteration of VCM conversion seemed to be a monotonic function of temperature. J. VINYL ADDIT. TECHNOL., 21:157–165, 2015. © 2014 Society of Plastics Engineers     

Preparation of high molecular weight poly(vinyl alcohol) with high yield using low‐temperature solution polymerization of vinyl acetate

Vinyl acetate (VAc) was solution‐polymerized in tertiary butyl alcohol (TBA) and in dimethyl sulfoxide (DMSO) having low chain transfer constant at 30, 40, and 50°C, 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 acetate) (PVAc) and corresponding poly(vinyl alcohol) (PVA) obtained by saponification with sodium hydroxide. The polymerization rates of VAc in TBA and in DMSO were proportional to the 0.49 and 0.72 powers of ADMVN concentration, respectively. For the same polymerization conditions, TBA was absolutely superior to DMSO in increasing the molecular weight of PVA. In contrast, TBA was inferior to DMSO in causing conversion to polymer, indicating that the initiation rate of VAc in TBA was lower than that in DMSO. These effects could be explained by a kinetic order of ADMVN concentration calculated using initial rate method and by an activation energy difference of polymerization obtained from the Arrhenius plot. Low‐temperature solution polymerization of VAc in TBA or DMSO by adopting ADMVN proved successful in obtaining PVA of high molecular weight (number–average degree of polymerization (P_n): 4100–6100) and of high yield (ultimate conversion of VAc into PVAc: 55–80%) with diminishing heat generated during polymerization. In the case of bulk polymerization of VAc at the same conditions, maximum P_n and conversion of 5200–6200 and 20–30% was obtained, respectively. The P_n and lightness were higher, and the degree of branching was lower with PVA prepared from PVAc polymerized at lower temperatures in TBA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1003–1012, 2001     

碳纤维原丝用聚丙烯腈的聚合反应条件

采用水相沉淀聚合法,以过硫酸铵为引发剂,制备了丙烯腈-丙烯酸甲酯-甲叉丁二酸三元共聚物,研究了聚合温度、单体浓度、引发剂浓度对聚丙烯腈共聚物相对分子质量和单体转化率的影响。结果表明:当反应温度为58℃,反应时间为2.5 h,单体质量分数为25%,引发剂质量分数为1.5%时,聚合物的黏均分子质量达3.8×105,单体转化率为79%。     

PVAc Microspheres via Semicontinuous Emulsion Polymerization: Synthesis,Characterization, Kinetic,and Surface Morphology Studies

Poly (vinyl acetate) (PVAc) latexes are economically important products with many desirable features. They are used as adhesives for porous materials in various processing stages of industries. Synthesis parameters have an important role on the physico-chemical properties of PVAc latexes such as: viscosity, average molecular weight, degree of polymerization, and surface morphology. In this work, PVAc was prepared via semicontinous emulsion polymerization (delayed monomer and initiator addition process) in the presence of ammonium persulfate (APS) as conventional anionic initiator, poly (vinyl alcohol) (PVA) as stabilizer, and sodium lauryl sulfate (SLS) as anionic emulsifier. The surface morphology of PVAc microspheres was, examined using a scanning electron microscope (SEM) and atomic force microscope (AFM). It is evident from the SEM photographs that all the particles became microspheres and are uniform in shape. The use of AFM for imaging of polyvinyl acetate confirms a typical sphere polymer. The effect of changes in the different parameters such as concentration of emulsifier, initiator concentration, and presence or absence of buffer on the vinyl acetate (VAc) conversion, the steady state polymerization rate, the viscosity-average molecular weight, and the final latex viscosity of synthesized PVAc were investigated. The effects of anionic emulsifier on the synthesized PVAc are also compared with those obtained by the nonionic emulsifier. The comparison indicated that the VAc monomer conversion and the final latex viscosity of the anionic system were higher than for the nonionic system but the viscosity-average polymer molecular weight of the anionic system was lower than that of the nonionic system. The adhesive strength of the synthesized PVAc latex was examined and the load and deflection data were reported.     

丙烯腈与丙烯酸混合介质悬浮聚合工艺研究

以偶氮二异丁腈(AIBN)为引发剂,聚乙烯酸(PVA)为分散剂,研究了丙烯腈与丙烯酸在水和二甲基甲酰胺混合介质中的自由基悬浮共聚合反应.考察了单体浓度、引发剂浓度、分散剂浓度、反应温度和时间等对共聚反应的影响.分别用称重法和乌氏粘度计测定了反应的转化率和产物的相对分子质量.用IR、DSC和TG对产物的结构和性能进行了表征.研究表明,最佳的反应条件是:总单体浓度30%,AIBN占总单体浓度1%,PVA占0.1%,反应温度为60℃,时间为2h.     

Effect of PVA in dispersion polymerization of MMA

Monodisperse poly(methylmethacrylate) microspheres having a diameter of 2.6 μm and a molecular weight of 102,277 g/mol with 5.3% of the C_v (the coefficient of variation) were synthesized by the dispersion polymerization using hydrophilic polyvinylalcohol (PVA) in methanol/water mixture media. Then, the structural verification of the synthesized materials is confirmed by using ¹H NMR and FT-IR spectroscopy. The effects of PVA and the polymerization parameters such as the initiator, monomer and stabilizer concentrations, and the reaction time on the characteristics of the final particles were studied. Thus, the role of PVA in the dispersion polymerization of MMA is not only a steric stabilizer by physically adsorbed in methanol phase, but also a colloid protective to give relatively monodisperse polymer particles in water phase, simultaneously.     

2‐Hydroxypropylmethacrylate based mono‐ and bifunctional gel beads prepared by suspension polymerization

Spherical and swellable gel beads in the size range 35–200 µm were prepared by suspension polymerization of 2‐hydroxypropylmethacrylate (HPMA). In the proposed method, a mixture of cyclohexanol and octanol was used as a diluent phase dispersed in an aqueous medium including poly(vinyl pyrrolidone) (PVP) as the stabilizer. The polymerization was initiated within the organic phase including the monomer and the crosslinker (ethylene glycol dimethacrylate) by an oil soluble initiator benzoyl peroxide. Spherical and swellable gel beads carrying both hydroxyl and carboxyl functional groups were also prepared by suspension copolymerization of HPMA and a water soluble comonomer (methacrylic acid). For this purpose, the suspension polymerization method proposed for HPMA was modified by using poly(vinyl alcohol) as a stabilizer instead of PVP. The effect of initiator concentration, polymerization temperature, monomer/diluent ratio, crosslinker concentration, stirring rate on yield, average size, size distribution, and carboxyl content of the HPMA based gel beads, were investigated. The swelling characteristics of the gel beads were defined. © 2000 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     

Synthesis of syndiotacticity‐rich high molecular weight poly(vinyl alcohol) by suspension polymerization of vinyl pivalate and saponification

Vinyl pivalate (VPi) was suspension‐polymerized to synthesize high molecular weight (HMW) poly(vinyl pivalate) (PVPi) with a high conversion above 95% for a precursor of syndiotacticity‐rich HMW poly(vinyl alcohol) (PVA). Also, the effects of the polymerization conditions on the conversion, molecular weight, and degree of branching (DB) of PVPi and PVA prepared by the saponification of PVPi were investigated. Bulk polymerization was slightly superior to suspension polymerization in increasing the molecular weight of PVA. On the other hand, the latter was absolutely superior to the former in increasing the conversion of the polymer, indicating that the suspension polymerization rate of VPi was faster than that of the bulk one. These effects could be explained by a kinetic order of a 2,2′‐azobis(2,4‐dimethylvaleronitrile) concentration calculated by the initial rate method. Suspension polymerization of VPi at 55°C by controlling various polymerization factors proved to be successful in preparing PVA of HMW [number‐average degree of polymerization (P_n): 8200–10,500], high syndiotactic diad content (58%), and very high yield (ultimate conversion of VPi into PVPi: 94–98%). In the case of the bulk polymerization of VPi at the same conditions, the maximum P_n and conversion of 10,700–11,800 and 32–43% were obtained, respectively. The DB was lower and the P_n was higher with PVA prepared from PVPi polymerized at lower initiator concentrations. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 832–839, 2003     

Synthesis and characterization of polyurethaneurea–vinyl polymer (PUU–VP) uniform hybrid microspheres by SPG emulsification technique and subsequent suspension polymerization

Uniform polyurethaneurea–vinyl polymer (PUU–VP) hybrid microspheres of about 20 μm were prepared by a Shirasu porous glass (SPG) membrane emulsification technique and a subsequent radical suspension polymerization process, that is, a mixture of a 40 wt % urethane prepolymer (UP) solution of xylene and a vinyl monomer (VP) containing an initiator was permeated through the uniform pores of the SPG membrane into a continuous phase containing a stabilizer to form uniform droplets. Then, the droplets were allowed to stand for chain extension at room temperature with di‐ or triamines for 2 h in the absence or presence of ethyl acetate (EA), followed by suspension polymerization at 70°C for 24 h. The effect of the type and the amount of the monomer composition, crosslinker, and chain extender on the monomer conversion, particle morphology, and stability of the dispersion was investigated. A strong relationship was found between the compatibility of PUU with VP and the stability of the dispersion. The monomer conversion increased and the stability of the dispersion was improved as the amount of the crosslinker was increased. Solid and spherical PUU–VA hybrid particles with a smooth surface and a higher destructive strength were obtained when a trifunctional crosslinker and a chain extender were used together. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 163–178, 2003