Emulsion Polymerization of Styrene and Vinyl Acetate with Cationic Surfactant

Summary: In this study, the emulsion homopolymerization system containing vinyl acetate and styrene, potassium persulfate, and a new cationic surfactant was studied in the classical glass emulsion polymerization reactor. The effects of new polymeric emulsifier on the physicochemical properties of obtained vinyl acetate and styrene latex properties were investigated depending on surfactant percentage in homopolymerizations.     

Glass transition and film formation of VeoVa/vinyl acetate latices; role of water and co-solvents

The physical forces causing deformation of latex particles during the film formation process have been witley studied. However, the forces resisting particle deformation are still poorly characterized. It is clear that the extent of particle deformation is dependent on the viscoelastic nature of the polymer. In an emulsion, the latex particles will normally contain water, surfactants and “free” monomers which lead to plasticization of the polymer. Although this effect has been recognized, so far it has been studied only on films that had been dried and then partially or completely swollen by water. In this work, plasticization of the emulsion polymers by water and co-solvent has been quantified via differential scanning calorimetry investigation directly on the aqueous latex dispersions. More specifically, the plasticizing effect of water on VeoVa/vinyl acetate copolymer latices and its influence on minimum film-forming temperature (MFFT) has been studied. A linear correlation has been found between T_g and MFFT for the wet latices. This new direct method should help to improve our understanding of the forces resisting latex film formation. Additionally, the homogeneous distribution of the hydrophobic and hydrophilic monomers (VeoVa and vinyl acetate respectively) in the latex particles was verified via a ¹³C-NMR (nuclear magnetic resonance) study performed directly on the latices. This study confirmed that no significant core/shell type of morphology had influenced latex film formation.     

醋酸乙烯酯的辐射乳液聚合

本文研究了各种因素对醋酸乙烯酯(VAc)辐射乳液聚合反应速度、胶乳粒子数、分子量、分子量分布及支化度的影响,在Friis导出的VAc化学引发乳液聚合的动力学和分子量公式的基础上,修改了K′_α等参数表达式,对VAc辐射乳液聚合曲线、分子量等随转化率变化的曲线作了理论计算,与实验结果较吻合。     

Different types of water in the film formation process of latex dispersions as detected by solid-state nuclear magnetic resonance spectroscopy

 The properties of polymer films prepared from latex dispersions are influenced by the drying or film formation process. In order to investigate this process, various systems of aqueous latex dispersions were dried until a specific solid content was reached. The samples investigated were based on vinyl acetate, vinyl acetate/ethylene and pure acrylics employing different surfactants and polyelectrolytes as stabilisers of the dispersions. The role of water in these partially dried films was investigated using ¹H and ²H solid-state NMR spectroscopy. Different types of water could be distinguished in the spectra. The drying latex films were found to contain interfacial external water, water at ionic and nonionic groups at surfactants in the polymer/water interface and also water inside the swollen polymer. These different types of water were examined separately using various NMR techniques. Received: 22 October 1999/Accepted in revised form: 19 November 1999     

Emulsion polymerization of styrene and methyl methacrylate using a hydrophobically modified inulin and comparison with other surfactants

The use of a new class of graft polymer surfactants, based on inulin, in emulsion polymerization of poly(methyl methacrylate) (PMMA) and polystyrene (PS) particles is described. PS and PMMA were synthesized by emulsion polymerization, and stable particles with a high monomer content (50 wt %) were obtained with a very small amount of polymeric surfactant ([surfactant]/[monomer] = 0.0033). The latex dispersions were characterized by dynamic light scattering and by transmission electron microscopy to obtain the average particle size and the polydispersity index, and the stability was determined by turbidimetry measurements and expressed in terms of critical coagulation concentration. The last section gives a comparison of PMMA particles prepared by emulsion polymerization using classical surfactants from different types as emulsifiers with that obtained using the copolymer surfactant. It shows the superiority of INUTEC SP1 as it is the only one that allows stable particles at 20 wt % monomer content, with a smaller ratio [surfactant]/[monomer] = 0.002.     

Polymer particle formation in suspension polymerization of vinyl chloride and vinyl acetate

Equipment has been designed and assembled in such a way that direct microscopic observation of polymer particle formation in suspension polymerization of vinyl chloride and vinyl acetate is possible. The apparent mode of transformation from monomer droplets into polymer particles has thus been studied under two sets of conditions: (1) with agitation and (2) without agitation. In both cases, as the initial vinyl acetate/vinyl chloride ratio was raised, the apparent change in the shape and transparency of particles occurring during the course of polymerization became less evident. In vinyl chloride homopolymerization and vinyl acetate–vinyl chloride copolymerization with relatively high vinyl chloride concentrations, the polymer particles burst during the course of polymerization. Some factors which affect the change in the size of particles are also discussed.     

Miniemulsion copolymerization of vinyl acetate and butyl acrylate. I. Differences between the miniemulsion copolymerization and the emulsion copolymerization processes

Differences between the emulsion copolymerization and miniemulsion copolymerization processes, in terms of emulsifier adsorption, emulsion stability, polymerization kinetics, copolymer composition and dynamic mechanical properties were studied for the comonomer mixture of 50:50 molar ratio vinyl acetate (VA+)—butyl acrylate (BuA), using sodium hexadecyl sulfate (SHS) as a surfactant and hexadecane (HD) as a co-surfactant. The use of hexadecane with the appropriate SHS initial concentration led to a higher adsorption of surfactant, smaller droplet size, higher stability of the emulsions, lower polymerization rates, and larger latex particle size. The copolymer composition during the initial 70% conversion was found to be less rich in Vac monomer units for the miniemulsion process. The dynamic mechanical properties of the copolymer films showed less mixing between the BuA-rich core and the VAc-rich shell in the miniemulsion latexes compared to the conventional latex films.     

Surfactant‐free synthesis of amphiphilic diblock copolymer in aqueous phase by a self‐stability process

Amphiphilic polymeric particles with hydrophobic cores and hydrophilic shells were prepared via living radical emulsion polymerization of styrene using a water‐soluble poly(acrylamide)‐based macro‐RAFT agent in aqueous solution in the absence of any surfactants. Firstly, the homopolymerization of acrylamide (AM) was carried out in aqueous phase by reversible addition‐fragmentation chain transfer radical polymerization (RAFT) using a trithiocarbonate as a chain transfer agent. Then the PAM‐based macro‐RAFT agent has been used as a water‐soluble macromolecular chain transfer agent in the batch emulsion polymerization of Styrene (St) free of surfactants. The RAFT controlled growth of hydrophobic block led to the formation of well‐defined poly(acrylamide)‐copolystyrene amphiphilic copolymer, which was able to work as a polymeric stabilizer (self‐stability). Finally, very stable latex was prepared, having no visible phase separation for several months. FTIR and ¹H‐NMR measurements showed that the product was the block copolymer PAM‐co‐PS in the form of stable latex. Atomic force microscope (AFM), transmission electron microscope (TEM), and dynamic light scattering (DLS) studies indicated that the nanoparticles have a narrow particle size distribution and the average particle hydrodynamic radius was kept in the diameter of 58 nm. Core‐shell structure of the copolymer was also recorded by TEM. The mechanism of the self‐stability of polymer particles during the polymerization in the absence of surfactants was studied. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3098–3107, 2008     

Particle nucleation in high solids batch miniemulsion polymerization stabilized with a polymeric surfactant

The nucleation of polymer particles in the miniemulsion polymerization of vinyl acetate/VeoVa10 (VAc/VeoVa10) stabilized with PVOH was studied. The effect of costabilizer type, PVOH concentration, and type (thermal water‐soluble and oil‐soluble; and redox water‐soluble) and concentration of initiator on the extent of droplet nucleation were studied. Droplet nucleation was maximized by improving miniemulsion stability and using efficient initiators. These high solids dispersions could not be obtained by using a conventional batch emulsion polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6407–6415, 2008     

Synthesis,characterization, and emulsion polymerization of polymerizable coumarin derivatives

We describe the synthesis of a new polymerizable coumarin derivative, [6‐(β‐acryloxyethoxy)‐7‐isopropoxy‐4‐methyl coumarin ( 3 )], whose UV absorption spectrum significantly overlaps the emission spectrum of 9‐alkyl phenanthrene chromophore. This dye can serve several purposes in latex films. It can be a tracer for fluorescence microscopy experiments, or it can act as a donor or acceptor dye in nonradiative energy transfer experiments. Here we emphasize its role as an energy transfer acceptor in experiments with phenanthrene as the corresponding donor. Coumarin‐labeled poly(butyl methacrylate) latex dispersions could be synthesized by conventional batch emulsion polymerization with complete monomer conversion, complete dye incorporation, and uniform dye distribution. Attempts to extend this reaction to poly(vinyl acetate) copolymers failed because the dye inhibited monomer conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3479–3489, 2004     

Preparation and characterization of polysiloxane-poly(butyl acrylate-styrene) composite latices and their film properties

Gamma ray induced seeded emulsion co-polymerization of styrene and butyl acrylate was carried out in the presence of polymerizable polysiloxane seed latex which was obtained by the ring opening co-polymerization of octamethyl cyclotetrasiloxane (D₄) and tetramethyl tetravinyl cyclotetrasiloxane (VD₄) catalyzed by dodecylbenzene sulphonic acid (DBSA). A series of polysiloxane seed latices with different molecular weight, vinyl content, and particle size were used. The conversion-time curve showed that the polymerization rate was accelerated much by the seed latex. The obtained composite latices also showed good storage stability, mechanical stability and high electrolyte resistance ability. The morphology of the composite latex particles was found to be a quite uniform fine structure by transmission electron microscope (TEM). The graft polymerization between polymerizable polysiloxane and butyl acrylate or styrene was confirmed by the Fourier transform infrared spectroscopy (FT-IR) and the graft efficiency was also studied. The influence of seed content, molecular weight, vinyl content of the polysiloxane and seed latex particles size to the mechanical performance, water absorption ratio, surface properties, transparency and UV resistance of the latex films, was also investigated.     

Cosolvent gel-like materials from partially hydrolyzed poly(vinyl acetate)s and borax

A gel-like, high-viscosity polymeric dispersion (HVPD) based on cross-linked borate, partially hydrolyzed poly(vinyl acetate) (xPVAc, where x is the percent hydrolysis) is described. Unlike hydro-HVPDs prepared from poly(vinyl alcohol) (PVA) and borate, the liquid portion of these materials can be composed of up to 75% of an organic cosolvent because of the influence of residual acetate groups on the polymer backbone. The effects of the degree of hydrolysis, molecular weight, polymer and cross-linker concentrations, and type and amount of organic cosolvent on the rheological and structural properties of the materials are investigated. The stability of the systems is explored through rheological and melting-range studies. (11)B NMR and small-angle neutron scattering (SANS) are used to probe the structure of the dispersions. The addition of an organic liquid to the xPVAc-borate HVPDs results in a drastic increase in the number of cross-linked borate species as well as the agglomeration of the polymer into bundles. These effects result in an increase in the relaxation time and thermal stability of the networks. The ability to make xPVAc-borate HVPDs with very large amounts of and rather different organic liquids, with very different rheological properties that can be controlled easily, opens new possibilities for applications of PVAc-based dispersions.     

Heterogeneous polymer systems. IV. Mechanism of rubber particle formation in rubber-modified vinyl polymers

A mechanism for the formation of rubber particles in the polymerization of solutions of rubber in vinyl monomers is presented. A polymeric oil-in-oil emulsion is formed in the first phase of the polymerization. This polymeric oil-in-oil emulsion is transtormed into a solid dispersion of rubber in vinyl polymer in the second phase of the polymerization. A phase inversion takes place in the emulsion in the first phase of the polymerization. Rubber solution droplets are formed at the phase inversion point. These droplets harden as the polymerization proceeds and are gradually transformed into the solid, crosslinked rubber particles of the final polymer.     

Characterization of poly(vinyl alcohol) during the emulsion polymerization of vinyl acetate using poly(vinyl alcohol) as emulsifier

During the emulsion polymerization of vinyl acetate (VAc) using poly(vinyl alcohol) (PVA) as stabilizer and potassium persulfate as initiator, the VAc reacts with PVA forming PVA-graft-PVAc. When the grafted polymer reaches a critical size it becomes water-insoluble and precipitates from the aqueous phase contributing to the formation of polymer particles. Since particle formation and therefore the properties of the final latex will depend on the degree of grafting, it is important to quantify and to characterize the grafted PVA. In this work, the quantitative separation and characterization of the grafted water-insoluble PVA was carried out by a two-step selective solubilization of the PVAc latex, first with acetonitrile to separate PVAc homopolymer, followed by water to separate the water-soluble PVA from the remaining acetonitrile-insoluble material. After the separation, the water-soluble and water-insoluble PVA were characterized by Fourier Transform Infrared (FTIR) spectroscopy and ¹H and ¹³C nuclear magnetic resonance (NMR) analyses, from which the details of the PVA-graft-PVAc structure were obtained. © 1996 John Wiley & Sons, Inc.     

Evidence for and against concentration gradients in polymerizing latex particles

A single-charge emulsion polymerization involving a monomer which is a good solvent for its polymer is considered. It is shown to be unlikely that within the polymerizing latex particles there are concentration gradients large enough measurably to affect the kinetics of the reaction. The average displacement of monomers due to Brownian motion within the latex particles and in the absence of concentration gradients is calculated. This diffusive mean free path, corresponding to an interval involving less than 1% change in conversion, is shown to be much longer than the radius of the latex particle. Consequently, loci where monomer concentration is perturbed by conversion to polymer are immediately swamped by unreacted monomer. Also, direct experimental evidence exists showing that the monomer concentration in latex particles is about the same when nonpolymerizing latex particles are saturated or during polymerization in the presence of monomer excess. The thermodynamics of saturation swelling preclude the possibility of the existence of large concentration gradients. The arguments that have been advocated in the literature for core–skin separation within polymerizing latex particles were based on conversion data which were thought to be linear with time, while a reexamination indicates that they were not. The observed core–skin separation obtained when butadiene or tritiated styrene were copolymerized with styrene in the presence of a polystyrene homopolymer seed latex has questionable relevance to single-charge homopolymerization. There are reasons to doubt that the distribution of co-monomers within latex particles can be frozen by their conversion to polymers in a two-stage emulsion polymerization.     

Preparation of a xanthate‐terminated dextran by click chemistry: Application to the synthesis of polysaccharide‐coated nanoparticles via surfactant‐free ab initio emulsion polymerization of vinyl acetate

Stable monodisperse poly(vinyl acetate) (PVAc) submicronic latex particles were synthesized by ab initio batch emulsion polymerization using a dextran derivative from renewable resource as an efficient steric stabilizer. The dextranend‐functionalized by a xanthate moiety was synthesized by Huisgen's 1,3‐dipolar cycloaddition (click chemistry). It was applied as a macromolecular RAFT (reversible addition fragmentation chain transfer) agent in surfactant‐free emulsion polymerization of vinyl acetate to form in situ an amphiphilic block copolymer able to efficiently stabilize the latex particles. The method afforded the preparation of high solids content (27%) latices coated by dextran. Both the kinetic study and the molar mass analyses confirmed the involvement of the dithiocarbonate group in the emulsion polymerization process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2845–2857, 2008     

Emulsion Polymerization of Vinyl Monomers in Presence of Chitosan with Peroxide Groups

Peroxychitosans with ditertiary peroxide fragments were synthesized via radical reactions of chitosan and 5-tert-butylperoxy-5-methyl-l-hexen-3-in. They can be used as macroinitiators and coemulsifiers for emulsion polymerization of vinyl monomers. It is shown that peroxychitosans are grafted to the surface of latex particles and impart antibacterial properties to emulsion polymer.     

The emulsion polymerization of vinyl acetate. Factors controlling particle surface area and rate of polymerization

An emulsion polymerization system with uniform continuous addition of vinyl acetate monomer, Pluronic F68 surfactant, and persulfate initiator has been examined with variation of the surfactant concentration over a tenfold range. The particle surface area per unit weight of emulsion was found to vary directly as the surfactant/monomer ratio, as also did the emulsion viscosity. At constant polymer/emulsion weight the number of particles per unit emulsion weight varied directly as the cube of the surfactant concentration. It is shown that these relationships apply also to other monomers, such as styrene and methacrylate esters. The solubility of vinyl acetate in a range of Pluronic F68 aqueous solutions was determined, and it was shown that the rate of polymerization is dependent on the solubility of the monomer in the surfactant solution. It is concluded that when a water-soluble initiator is used, polymerization proceeds in the aqueous phase. The principal factors controlling the rate of polymerization in the emulsion polymerization of vinyl acetate are, consequently, the initiating system and the concentration of monomer in the aqueous phase. Solubilization characteristics indicate that the surfactant concentration will have a much greater effect on the less water-soluble monomers, such as styrene, than on the more soluble ones, such as vinyl acetate.     

Emulsion polymerization and copolymerization of vinyl benzoate

Emulsion polymerization of vinyl benzoate and its copolymerization with vinyl acetate or styrene are described. The effect of the potassium persulfate initiator, and the sodium lauryl sulfate emulsifier concentration on the rate of vinyl benzote homopolymerization and the molecular weight of the polymers was determined. In copolymerization with vinyl benzoate, both comonomers, vinyl acetate and styrene, decrease the initial polymerization rate. With increasing amounts of styrene in the comonomer mixture the polymerization rate increases but with vinyl acetate an opposite effect is observed. Reactivity ratios of copolymerizations were determined. For the vinyl benzoate [M₁]-styrene [M₂] comonomer system a r₁ = 0.03 and a r₂ = 29.58 and for vinyl benzoate [M₁]-vinyl acetate [M₂], a r₁ = 1.93 and a r₂ = 0.20 was obtained. From the vinyl benzoate-styrene reactivity ratios the Qe parameters were calculated.     

Acetal‐functionalized polymer particles useful for immunoassays. II. Surface and colloidal characterization

Monodisperse polymer colloids with dimethyl and diethyl acetal functionalities were synthesized by a two‐step emulsion polymerization process. The first step consisted of a batch emulsion homopolymerization of styrene (St). The dimethyl and diethyl acetal functionalities were obtained by batch emulsion terpolymerization of St, methacrylic acid (MAA), and methacrylamidoacetaldehyde dimethyl acetal (MAAMA) or methacrylamidoacetaldehyde diethyl acetal (MAADA) in the second step, onto the previously formed polystyrene latex particles. The latexes were characterized by TEM and conductimetric titration, in order to obtain the particle size distribution and the amount of carboxyl and acetal groups on the surface, respectively. The chemical stability of the functionalized surface groups during the storage time was analyzed. The hydrophilic character of the surface of the polymer particles was determined by means of nonionic emulsifier titration. The colloidal stability of the synthesized latexes was studied by measuring the critical coagulation concentration (CCC) against KBr electrolyte, and the existence of a hairy layer on the surface of the latex particles was analyzed by measuring the hydrodynamic particle diameter at several electrolyte concentrations. The surface functionalized groups remained stable for 2 years. The relative hydrophilic character and the colloidal stability were affected by the pH of the medium. On the other hand, the higher the surface charge, the larger the thickness of the hairy layer. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 501–511, 1999