Latex grafts

The simplest technique is to dissolve the polymer in the appropriate solvent add the peroxide initiator, which abstracts a hydrogen radical and generates a radical on the polymer chain and then add fresh monomer for grafting onto this site. This technique has been employed in grafting methylacrylate onto natural rubber and synthetic polyisoprene. In this manner, several commercially useful products such as ABS resins have been prepared however, tire elastomers are not made in this manner because of the generation of micro and macro gel particles, which are detrimental to physical properties. In many cases when latex grafting has been used, the product has usually been targeted toward thermoplastic applications rather than rubber applications. 

Acrylonitrile—Butadiene—Styrene. ABS is an important commercial polymer, with numerous apphcations. In the late 1950s, ABS was produced by emulsion grafting of styrene-acrylonitrile copolymers onto polybutadiene latex particles. This method continues to be the basis for a considerable volume of ABS manufacture. More recently, ABS has also been produced by continuous mass and mass-suspension processes (237). The various products may be mechanically blended for optimizing properties and cost. Brittle SAN, toughened by SAN-grafted ethylene—propylene and acrylate mbbets, is used in outdoor apphcations. Flame retardancy of ABS is improved by chlorinated PE and other flame-retarding additives (237). 

Emulsion polymeriza tion of ABS (241) gives a mbber-phase particle morphology which is mostly deterrnined by the mbbet-seed latex. Since the mbber particle size, polydispersity, and cross-linking ate estabhshed before the preparation, the main variables relate to grafting, molecular weight... 

Porous membranes with selective permeabiUty to organic solvents have been prepared by the extraction of latex films prepared with moderate ratios of PVA—PVAc graft copolymer fractions. The extracted films are made up of a composite of spherical cells of PVA, PVAc microgel, and PVA—PVAc graft copolymers (113). 

To produce the Type 2 polymers, styrene and acrylonitrile are added to polybutadiene latex and the mixture warmed to about 50°C to allow absorption of the monomers. A water-soluble initiator such as potassium persulphate is then added to polymerise the styrene and acrylonitrile. The resultant materials will be a mixture of polybutadiene, polybutadiene grafted with acrylonitrile and styrene, and styrene-acrylonitrile copolymer. The presence of graft polymer is essential since straightforwsird mixtures of polybutadiene and styrene-acrylonitrile copolymers are weak. In addition to emulsion processes such as those described above, mass and mass/suspension processes are also of importance. 

We have found that in the system of presulfate initiator, the PVAc latexes are not dissolved transparently in the methanol-water mixture [8], and in the system of HPO initiator, the extraction of the polymer from the PVAc latex films with acetone greatly depends on the polymerization condition [9]. These results suggest that if a polymerization method can be found in which the grafting polymerization of VAc onto PVA is controlled to the minimum, a large portion of PVAc in the latex film will have a chance of extraction with solvents. In this Chapter, the preparations of the unique porous films from the PVAc latexes containing PVA as a protective colloid by an extraction of the PVAc particles with acetone and the characteristic properties of the porous films are summarized. 

This prediction is drawn according to the following model. Figure 5 illustrates that in the latex state the grafting PVA protects hydrophobic PVAc particles in water by concentrating on the surfaces of PVAc particles, but in the porous film after acetone extraction, the insoluble grafting PVAc conversely exists as an important component on the inner surface of spherical cells of PVA. 

There has been a conventional sense that the PVAc latexes prepared in the presence of PVA as a protective colloid contain the graft copolymer of PVA and PVAc, so that PVAc particles in the dried latex film are not extracted at a high ratio with solvents. In this Chapter, it has been defined without an influence by the usual sense that the porous PVA-PVAc composite can be prepared from the PVAc latex film with acetone extraction. The porous film consists of the spherical cells of PVA... 

Figure 9 The schematical representation of dispersion polymerization process, (a) initially homogeneous dispersion medium (b) particle formation and stabilizer adsorption onto the nucleated macroradicals (c) capturing of radicals generated in the continuous medium by the forming particles and monomer diffusion to the forming particles (d) polymerization within the monomer swollen latex particles, (e) latex particle stabilized by steric stabilizer and graft copolymer molecules (f) list of symbols.

Paine et al. [99] tried different stabilizers [i.e., hydroxy propylcellulose, poly(N-vinylpyrollidone), and poly(acrylic acid)] in the dispersion polymerization of styrene initiated with AIBN in the ethanol medium. The direct observation of the stained thin sections of the particles by transmission electron microscopy showed the existence of stabilizer layer in 10-20 nm thickness on the surface of the polystyrene particles. When the polystyrene latexes were dissolved in dioxane and precipitated with methanol, new latex particles with a similar surface stabilizer morphology were obtained. These results supported the grafting mechanism of stabilization during dispersion polymerization of styrene in polar solvents. 

As shown for the synthesis of PS [291], the monomer may be localized in the vicinity of the filler surface by previously grafting a polymer capable of swelling in the base monomer. Copolymeric latex of polychloroprenemethacrylic acid was added to the aqueous dispersion of chalk. The acid groups reacted with chalk and the latex particles became chemically grafted to chalk. When further portions of styrene were added they were completely absorbed by modified chalk. 

Serizawa and Akashi [95] analyzed the monolayer adsorption of polystyrene latex particles with cationic polyvinylamine grafted on their surface, while Serizawa et al. [96,97] used commercial anionic latex particles. Both types of particles were adsorbed on polyelectrolyte-coated substrates previously prepared by alternating adsorption of cationic and anionic polyelectrolytes such as polyallylamine hydrochloride (PAH) and polystyrene sulfonate sodium salt (PSS) according to the method described by Decher [164]. Using... 

Two different emulsion polymerization reactions were Investigated. One was the polymerization of acrylonitrile and methylacrylate (75/25 AN/MA) In the presence of an acrylonitrile elastomer (70/30 BD/AN) to produce a graft resin, llie second was the copolymerization oiE acrylonitrile and styrene (70/30 AN/S). Chromatographic analyses of latex solutions were conducted periodically during both types of polymerization reactions, using acetonitrile as latex solvent and chromatographic mobile phase. 

Latex solutions for chromatographic analysis were prepared by adding weighed amounts of latex to known amounts of acetonitrile. Latex solution concentrations were 0. 2 g/100 ml for AN/S copolymers and 1. 0 g/100 ml for the AN/MA graft resins. 

Overall goal of this work was to maximize the amount of information obtained from chromatographic analysis of latex solutions. More specific aims were (1) measure amounts of unreacted monomers, as one measure of conversion, (2) determine amount of polymer, as a second measure of conversion, (3) estimate chemical composition of the polymer formed, and (4) look for evidence of grafting (in the AN/M polymerization) as evidenced by detection of insoluble polymer formation. 

There are several reports on the stability of PEO-grafted latex particles synthesised using the macromonomer in highly concentrated electrolyte solutions [301,302], However, the stability of thermally responsive PEO-grafted... 

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