Semi-continuous monomer

The presence of chain transfer agents during the second-stage polymerization will produce a decrease in the molar mass of the shell polymer, which will result in more chain mobility and fieedom to achieve the equilibrium morphology, even under conditions where kinetically controUed particle morphologies (i.e. semi-continuous monomer addition) would normally dominate [57,67]. 

There are three important processes for preparing PVAc latexes in the presence of PVA as a protective colloid batch, semi-continuous, and delayed addition of monomer [10]. In this Chapter, the effects of the addition of VAc and initiators on the properties of PVAc latexes are discussed using the three methods under the same charge of ingredients for polymerization as shown in Fig. 1 [1,11]. 

Compositional drift in continuous reactor trains can be altered by introducing feed streams of the more reactive monomer between reactors. This procedure is equivalent to programmed addition of the more reactive monomer in a semi-continuous system. 

The proceeding discussion of polymer composition was based on the assumption that essentially all polymer is formed in the organic phases of the reaction mixture. If a water-soluble monomer, such as some of the functional monomers, is used, the reactions taking place in the aqueous phase can contribute to variation in polymer composition. In fact, in extreme cases, water soluble polymer can be formed in the aqueous phase. This can happen in batch, semi-continuous or continuous reactors. The fate of functional monomers could be considerably different among the different reactor types, but detailed studies on this phenomenon have not been reported. 

Vinyl acetate-butyl acrylate copolymers (0-100% butyl acrylate) were prepared by both batch and starved semi-continuous polymerization using sodium lauryl sulfate emulsifier, potassium persulfate initiator, and sodium bicarbonate buffer. This copolymer system was selected, not only because of its industrial importance, but also because of its copolymerization reactivity ratios, which predict a critical dependence of copolymer compositional distribution on the technique of polymerization. The butyl acrylate is so much more reactive than the vinyl acetate that batch polymerization of any monomer ratio would be expected to give a butyl acrylate-rich copolymer until the butyl acrylate is exhausted and polyvinyl acetate thereafter. 

The results showed that all batch polymerizations gave a two-peaked copolymer compositional distribution, a butyl acrylate-rich fraction, which varied according to the monomer ratio, and polyvinyl acetate. All starved semi-continuous polymerizations gave a single-peaked copolymer compositional distribution which corresponded to the monomer ratio. The latex particle sizes and type and concentration of surface groups were correlated with the conditions of polymerization. The stability of the latex to added electrolyte showed that particles were stabilized by both electrostatic and steric stabilization with the steric stabilization groups provided by surface hydrolysis of vinyl acetate units in the polymer chain. The extent of this surface hydrolysis was greater for the starved semi-continuous sample than for the batch sample. 

Bassett and Hoy (7,8) investigated the influence of the method of monomer addition on the alkali-swelling behavior. In this case, carboxyl-containing monomers were fed in three different stages of the semi-continuous polymerization (i) in the... 

During the semi-continuous polymerization, 4-5 small samples were withdrawn from the polymerization for the determination of the comonomer and copolymer composition. A few drops of the sample latex were mixed with hydroquinone, cooled in ice, and subjected to GC analysis to determine the amounts of unreacted monomer. The rest of the sample (5-8 ml) was poured into mixed solvent of ispropanol/hexane (45/55) containing hydroquinone, and the precipitated polymer, after it was washed with hexane, was dried in a vacuum oven at 45°C for more than 5 hours. A certain amount of the dried polymer was dissolved in dimethyl formamide (DMF), and titrated for the carboxyl content with NaOH solution using phenolphthalein as the indicator. 

The instantaneous conversion of each monomer was calculated from the amount of unreacted monomers determined by GC, which was found to be higher than 90% during the course of semi-continuous polymerization and to increase slightly as the polymerization proceeded. The ratio of instantaneous conversion between the two... 

Although MAA monomer possesses a larger reactivity ratio than MMA monomer, more MAA was found to exist in the outer side of the particle in the batch latex, as shown in Figures 5 and 6. This behavior could be explained if one can accept the fact that the MAA-rich polymers, which are formed early on during the polymerization, can migrate to the surface of the particle due to their higher hydrophilicity and plasticization of the polymer with the monomer. In the semi-continuous process, it could be expected that copolymer with the same composition as the comonomer feed is formed, and the particle contains a uniform distribution of carboxyl groups. 

Preparation of latex Samples. Two-stage latex samples were prepared by emulsion polymerization of the second-stage monomer mix in the presence of the first-stage polymer latex. The first-stage latexes were either in-situ or separately made using an externally prepared polystyrene latex seed. The mode of polymerization was a semi-continuous process for both stages. 

For comparison, a few experiments were carried out using the semi-continuous process. In a typical experiment (N2) corresponding to run P2, a fourth of the monomer feed (AN 0.19 mole,... 

Another problem associated with the batch technique is poor reaction control (unsatisfactory stirring, temperature control, etc). To overcome the problems outlined above a semi-continuous polymerization technique has been introduced [27]. In this technique a mixed monomer/inifer feed is added at a sufficiently low constant rate to a well stirred, dilute BC13 charge. Due to stationary conditions maintained during the whole polymerization, well-defined telechelic products with symmetrical end groups and theoretical polydispersities could be obtained. The kinetics of the polymerization has been discussed and the DPn equation has been derived. In contrast to the batch technique, the DPn for the semi-continuous technique is simply given by the [monomer]/[inifer] ratio. Thus, very reactive or unreactive inifers, unsuitable for batch polymerization, can also be used in the semi-continuous process. 

Abstract This review describes how the unique nanostructures of water-in-oU (W/0), oil-in-water (0/W) and bicontinuous microemulsions have been used for the syntheses of some organic and inorganic nanomaterials. Polymer nanoparticles of diameter approximately 10-50 nm can easily be obtained, not only from the polymerization of monomers in all three types of microemulsions, but also from aWinsor l-like system. A Winsor 1-like system with a semi-continuous process can be used to produce microlatexes with high weight ratios of polymer to surfactant (up to 25). On the other hand, to form inorganic nanoparticles, it is best to carry out the appropriate chemical reactions in W/0- and bicontinuous microemulsions. 

A major drawback of conventional microemulsion polymerization is the high surfactant-to-monomer ratio usually needed to form the initial microemulsion. Surfactant can be used more efficiently in semi-continuous or fed polymerization processes. Several polymerization cycles can be run in a short period of time by stepwise addition of new monomer. After each cycle of monomer addition, most of the surfactant is still available to stabilize the growing hydro-phobic polymer particles, or to forms microemulsion again when a polar monomer is used. For instance, in the polymerization of vinyl acetate (VA) by a semi-continuous microemulsion process [21], latexes with a high polymer content of about 30 wt% were obtained at relatively low AOT concentrations of about 1 wt%. Moreover, their particle sizes and molecular weights were much smaller than those obtained by conventional emulsion polymerization. 

Though the continuous addition of monomer via hollow fibers into a Winsor I-Hke system is rather novel, it is not as convenient as the drop-wise addition of monomer under a semi-continuous process. Ming et al [67, 68]... 

The polymerization of styrene in Winsor I-like systems by semi-continuous feeding of monomer stabilized by either DTAB, TTAB or CTAB has been systematically investigated by Gan and coworkers [69a]. Rather monodisperse polystyrene microlatexes of less than 50 nm with molecular weights of over one million were obtained at a polymer/surfactant weight ratio of 14 1. The Winsor I-like (micro)emulsion polymerization of styrene stabilized by non-ionic surfactant and initiated by oil-soluble initiators has also been reported very recently [69b]. The sizes of the large monomer-swollen particles decreased with conversion and they merged with growing particles at about 40-50% conversion. 

High polymer/surfactant weight ratios (up to about 15 1) of polystyrene microlatexes [73] have been produced in microemulsions stabihzed by polymerizable nonionic surfactant by the semi-continuous process. The copolymerization of styrene with the surfactant ensures the long-term stabihty of the latexes. Nanosized PS microlatexes with polymer content (<25 wt%) were also obtained from an emulsifier-free process [74] by the polymerization of styrene with ionic monomer (sodium styrenesulfonate, NaSS), nonionic comonomer (2-hydroxyethylmethacryalte, HEM A), or both. The surfaces of the latex particles were significantly enriched in NaSS and HEMA, providing better stabilization. 

The reaction time is 16 hours for the batch procedure. In the semi-continuous procedure a seed latex is first prepared with 1/10 of the monomer amount during 30 minutes at 80 C. The remaining monomer is then added continuously during 2.5 hours.The polymerization is completed by heating the system for an additional 1 hour. 

Graft polyether polyols are synthesised by in situ radical polymerisation of vinylic monomers in liquid polyethers, by batch, semi-continuous or continuous processes. The solid fraction varies between 10-50%, more frequently being between 10-40% [1-10]. 

El-Aasser et al. [20] studied the difference between batch and semi-continuous polymerization of VAc and determined that batch polymerization produced a narrower molar mass distribution than the semi-continuous process. The semi-batch polymerization produced a high molar mass fraction which was attributed to CTP due to monomer-starved conditions. 

The need for continuous monitoring of monomer conversion in batch, semi-continuous and continuous emulsion polymerization is growing because the requested performance of polymer materials has caused higher demands on the reproducibility and fine tuning of the production processes. 

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