Suspended emulsion,a new process for vinyl chloride polymerization: Morphology control through surface active additives

Suspended emulsion is a new polymerization process in which a water phase containing the initiator is suspended in an organic phase containing the monomer; the polymer formed is insoluble in both the organic and water phase. The final morphology of the polymer is a powder of grains (around 100–300 microns) formed with agglomerates of primary particles (around 1 micron). This article describes the effects of small amounts of either suspending agents (water-soluble polymers) or surfactants. These effects concern mainly the morphology (grain and particle size), but also the polymerization kinetics. A rather homogeneous distribution of grains and particles inside the grain may be obtained by using a cellulosic polymer as the suspending agent and an anionic surfactant such as sodium dodecyl sulfate. © 1994 John Wiley & Sons, Inc.     

Measurements of particle-size distribution during suspension polymerization

The particle-size distribution is one of the main characteristics of polymers produced by suspension polymerization which determines the final properties of the product. Since the on-line measurement of particle-size distribution during the course of polymerization is not a straightforward task, a technique has been developed to accomplish such a measurement for a predefined polymerization process. In this paper the experimental procedure is described in detail and the experimental data are shown for the batch suspension polymerization of methyl methacrylate using benzoyl peroxide as initiator, water as suspending phase and agarose as suspending agent. The particle-size distributions have been measured both for a base case and also when varying some operating conditions including stirring speed, water-to-monomer weight ratio, and suspending agent concentration. Average values and variances of the surface distribution and of the volume distribution are also computed and shown for comparison. © 1999 Society of Chemical Industry     

Antielectrostatic agent addition in low-dielectric-constant polymerization media

In the coordinative polymerization of α-olefin by a slurry process, a low-dielectric-constant suspending agent, such as hexane or heptane, must be used. As a result of solvent movement and its friction between system components, electrostatic charges are generated. Because of low electrical conduction of these solvents, the generated charges accumulate in the polymerization medium. Consequently, a repulsive force between same charges effects the growth of the polymer particles and causes them to form fine particles. In this article, we present research results on the effects of antielectrostatic agents on the increase of the electrical conduction of the polymerization medium, particle size distribution, and also the quantity of fine particles in the final polymer. Techniques gained from the fuel industry were applied to modify the subjected polymerization medium. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

PVC树脂中杂质粒子的来源及消除方法

系统地分析了PVC树脂中杂质粒子的来源和产生原因，提出了解决的方法。杂质粒子与所用原材料、设备、工艺、聚合配方组分及氯乙烯单体中的铁化合物有关。在配方中全用聚乙烯醇做悬浮剂时由于反应前后浓度变化大而容易产生自聚物和粘釜物而增加杂质粒子，加入少量纤雏素可稳定悬浮剂浓度。单体含酸含水所产生的铁锈与氯化铁形成有色胶状物是杂质粒子的重要来源，采用在合成工段滴加碱溶液的方法消除酸和氯化铁，避免胶状物的产生。     

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.     

BA悬浮溶胀接枝聚合PVC的制备与性能研究

采用水相悬浮溶胀聚合的方法在PVC颗粒内部原位接枝丙烯酸丁酯(BA),考察了反应温度、分散剂用量对接枝反应和颗粒形态的影响,结果表明:接枝率随反应温度的升高而增大,分散剂用量为1.0份时,产物的颗粒形态规则,与PVC共混物的力学性能较好.PVC-g-BA/PVC共混体系动态力学性能分析(DMA)的结果表明:两相呈微观相态分离的结构特点;转矩流变性能测试结果表明:交联剂用量为3份时,PVC-g-BA/PVC共混体系的塑化性能较好.     

金属注射成型专用粘结剂主体聚合物合成研究

对金属注射成型专用粘结剂的主体聚合物进行了研究 ,结果表明 ,用甲基丙烯酸甲酯与乙酸乙烯酯共聚 ,用偶氮二异丁腈作自由基引发剂 ,用硫醇作分子量调节剂可以获得较理想的粘结剂主体聚合物 ;并考察了各因素对聚合物产率和熔点的影响     

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     

氧化还原体系引发苯乙烯乳液聚合

以不同的过氧化物引发剂分别与硫酸亚铁组成氧化还原引发体系,引发苯乙烯的乳液聚合,研究反应温度和还原剂用量等对聚合的影响.采用气相色谱、三检测体积排除色谱、动态光散射对单体转化率、聚苯乙烯的相对分子质量及其分布和乳胶粒径进行了分析.结果表明:升高温度或增加还原剂用量均会使聚合物的相对分子质量增大,聚合反应速率加快,与常规...     

Effect of molecular weight on the surface morphology of crosslinked polymer particles in the RITP-dispersion polymerization

The RITP (reverse iodine transfer polymerization)-dispersion polymerization of methyl methacrylate (MMA) was conducted and the molecular weight and SEM images of them were investigated to propose the mechanism of the formation of surface morphology in crosslinked polymers. The morphology of the crosslinked particles varied depending on the sorts and contents of the crosslinking agents and iodine. As the iodine content increased under the same content of the crosslinking agent, the average molecular weight of the polymers [uncrosslinked portion of the polymers] decreased and the surface roughness simultaneously reduced. On the other hand, as the contents of the crosslinking agent increased, the molecular weight of polymers reduced and the surface morphology changed from smooth to rough in the absence of iodine. On the other hand, was the molecular weight was barely changed and the solubility increased upon iodine. Thus the mechanism of the formation of crosslinked polymers in the RITP-dispersion polymerization was proposed as the following; when crosslinking agent and iodine were simultaneously involved, the low molecular weight of polymers were first formed due to the effect of iodine and then the crosslinking was taking place, resulting in that iodine was a critical factor in controlling the molecular weight, particle size, solubility and the surface morphology in the crosslinked polymer particles.     

Magnetite‐coated polystyrene hybrid microspheres prepared by miniemulsion polymerization

Hybrid microspheres with a polystyrene core coated with magnetite nanoparticles were prepared by miniemulsion polymerization. Acrylic acid was used as a comonomer to promote the anchoring of the magnetite nanoparticles onto the polymeric surface. The addition of a hydrophobic agent prevents effectively the monomer from diffusing into the aqueous phase. Magnetite was treated with a silane coupling agent in order to introduce some interactions with the polymers. The morphology and the structure of the hybrid microspheres were characterized using X‐ray diffraction, infrared spectroscopy, transmission electron microscopy and thermogravimetric analysis. The results show that the morphology of the hybrid microspheres was influenced by the concentrations of acrylic acid, hydrophobic agent and surfactant, and that the degree of coating can be tuned by changing these parameters. The miniemulsion polymerization technique is adaptable to the synthesis of magnetite‐coated polymer particles, and the synthesis can be scaled up. Copyright © 2008 Society of Chemical Industry     

Grafting of hyperbranched aromatic polyamide onto silica nanoparticles

Hyperbranched aromatic polyamide grafted nano-silica particles were successfully prepared via “one-pot” melt polycondensation. The particles were firstly treated with a silane coupling agent to introduce amine groups as the growth points, and then grafting of the hyperbranched polymers started from the modified surface. The percentage grafting can be as high as 32.8%. The key reaction conditions, including feeding ratio, reaction temperature and time, were carefully investigated to determine a set of optimal grafting parameters. It was found that the significant steric hindrance between the hyperbranched polymers during graft polymerization played a key role in controlling molecular structure of the grafted polymers, while adsorption of grafting monomer onto SiO₂ particles prior to the reaction facilitated higher degree of branching and apparent molecular weight of ungrafted polymers.     

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。     

纳米Al_2O_3表面接枝聚合改性的研究

为改善纳米Al2O3粒子在聚合物中的分散状况,本工作先在粒子表面引入双键,然后通过溶液自由基引发接枝单体丙烯酰胺和苯乙烯在Al2O3粒子表面的聚合,使接枝物与纳米粒子之间形成化学键合。系统研究了投料方式、引发剂浓度、单体浓度、反应时间等对接枝效果的影响,为调控纳米粒子表面的化学性质提供依据。     

Photopolymerization studies: I. Polymers from new photoredox catalyst system

A new photoredox catalyst is described wherein a phenothiazine dye in its excited state oxidizes a catalyst to a free radical. This free radical efficiently initiates the polymerization of metal acrylates giving rise to polymers which are insoluble in the monomer-containing medium. The polymers precipitate as insoluble colloidal particles. Optical transmission measurements are used to follow the polymerization and to calculate the number and size of the polymer particles. The effect of various factors such as the nature of the catalyst and the photooxidant, the pH and the temperature of the medium on photopolymerization are described. It is indicated that this new system may be useful for rapid photographic imaging and display applications.     

The influence of poly(vinyl alcohol) suspending agents on suspension poly(vinyl chloride) morphology

The requirements for PVC suspension resin have changed considerably in the last few years, so much so that few companies have products on their ranges that are more than 4 or 5 years old. The suspending agent has a crucial influence on the morphology of the resin, so the changes in resin characteristics have largely been achieved by changes in the suspending agent systems. After a brief review of the mechanism of PVC suspension polymerisation, the properties of polymers made using PVOH suspending agents are related to changes in the latter. The effect of variations in PVAc degree of hydrolysis and viscosity are related to changes in surface tension. Methods of achieving higher porosity by using low hydrolysis co-suspending agents are described. It is shown that higher bulk densities can be achieved by delayed addition of the PVOH. Levels of conjugated unsaturation and copolymer distributions are also shown to have important influences.     

含功能基的核—壳型聚丙烯酸酯乳液的合成与性能

本文以种子乳液聚合法制备了PBA/MMA-MAA核-壳型聚合物,考察了壳层单体MMA和MAA的含量不同时对聚合反应及聚合物其它性能的影响,并用TEM观察了粒子的形态。     

Preparation of poly(methyl methacrylate)/titanium oxide composite particles via in‐situ emulsion polymerization

Poly(methyl methacrylate) (PMMA)/Titanium oxide (TiO₂) composite particles were prepared via in‐situ emulsion polymerization of MMA in the presence of TiO₂ particles. Before polymerization, the TiO₂ particles was modified by the silane coupling agent, which is crucial to ensure that PMMA reacts with TiO₂ via covalent bond bindings. The structure of the obtained PMMA/TiO₂ composite particles was characterized using Fourier transform infrared spectra (FTIR) and thermogravimetric analysis (TGA). The results indicate that there are covalent bond bindings between PMMA macromolecules and TiO₂ particles. Based on these facts, several factors affecting the resulting PMMA/TiO₂ composite system, such as the type of coupling agents, the mass ratio of the MMA to the modified TiO₂, the emulsifier concentration, and the initiator concentration, etc., were examined by the measurement of conversion of monomers, the gel content of polymers, the percentage of grafting, and the grafting efficiency, using gravity method or TGA method. As a result, the optimized recipe was achieved, and the percentage of grafting and the grafting efficiency could reach 216.86 and 96.64%, respectively. In addition, the obtained PMMA/TiO₂ composite particles were found to a stable colloidal dispersion in good solvent for PMMA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4056–4063, 2006     

两种制备疏松PVC树脂的新型聚合方法

介绍了制备疏松PVC树脂的两种新聚合方法——以正丁烷为反应介质分散聚合和悬浮态乳液聚合，并对树脂颗粒的特性进行了简述。结果表明：以正丁烷为反应介质的非均相VC分散聚合所得树脂的粒径和颗粒形态与聚合体系VC／But比例和转化率等有关，由于存在向But的链转移，PVC分子质量小于相同聚合温度下生产的悬浮PVC树脂。悬浮态乳液聚合所得树脂粒径分布和颗粒形态与水油比、转化率和添加剂品种有关。     

Acrylamide‐based anionic polyelectrolytes and their applications: A survey

Water‐soluble polymers are found in a very broad range of industrial applications. An important class of these is acrylamide‐based polymers which bear negative charges along the polymer chain and are called anionic polyelectrolytes. These negatively charged polymers are widely used as flocculants, rheology control agents, and adhesives. They are employed especially in oil field operations as viscosity control agents for enhanced oil recovery and to a lesser degree in engineering fluids used for lubrication, for effluent reclaiming, and for opening oil passage channels in oil‐bearing rock. Paper manufacture, mining, and water treatment processes also benefit from the use of acrylamide‐based polymers to flocculate solids in aqueous dispersions. The acrylamide‐based polymers are made by the free‐radical polymerization of acrylamide and its derivatives via bulk, solution, precipitation, suspension, emulsion, and copolymerization techniques. Among these, solution polymerization is a preferred technique because of difficulty with temperature and agitation control in bulk polymerization and the cost of surfactants and solvents for suspension, emulsion, and precipitation polymerization. The anionic polymers may interact with particles in aqueous dispersions in several ways that result in the stability or instability of the dispersions. The particles in solid‐liquid phases can be destabilized through three main mechanisms which promote flocculation and cause destabilization. These mechanisms are polymer bridging, charge neutralization, and polymer adsorption. The particles in solid‐liquid phases can be stabilized by the anionic polymers through both electrostatic and steric repulsive forces. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers