Emulsion vinyl chloride

Hayes established a list of some monomers in the order of decreasing activity towards grafting in emulsion vinyl chloride > vinyl acetate > styrene. Polymers can be listed in order of decreasing susceptibility to graft copolymerization, as follows polyvinyl chloride > polyacrylonitrile > polyvinyl acetate > polystyrene. 

Inovyl Polyvinyl chloride (emulsion) Vinyl chloride monomer High productivity, high quality grades, low residual VCM, effective condenser usage 2 1991... 

Vin Tec GmbH/Krupp Uhde Polyvinyl chloride (emulsion) Vinyl chloride monomer Batch process uses 2 or more reactors special coating/buildup suppressant allows many batch operations before cleaning NA NA... 

Emulsion Vinyl chloride 2-Ethyl hexyl acrylate Japan 13,927 1973 Shinetsu Chemical ... 

Cement emulsion Vinyl chloride 2-Ethylhexyl acrylate... 

Uses. The a2obisnitriles have been used for bulk, solution, emulsion, and suspension polymeri2ation of all of the common vinyl monomers, including ethylene, styrene vinyl chloride, vinyl acetate, acrylonitrile, and methyl methacrylate. The polymeri2ations of unsaturated polyesters and copolymeri2ations of vinyl compounds also have been initiated by these compounds. 

Wheieas the BPO—DMA ledox system works well for curing of unsaturated polyester blends, it is not a very effective system for initiating vinyl monomer polymerizations, and therefore it generally is not used in such appHcations (34). However, combinations of amines (eg, DMA) and acyl sulfonyl peroxides (eg, ACSP) are very effective initiator systems at 0°C for high conversion suspension polymerizations of vinyl chloride (35). BPO has also been used in combination with ferrous ammonium sulfate to initiate emulsion polymerizations of vinyl monomers via a redox reaction (36). 

MBS polymers are prepared by grafting methyl methacrylate and styrene onto a styrene—butadiene mbber in an emulsion process. The product is a two-phase polymer useful as an impact modifier for rigid poly(vinyl chloride). 

The principal use of the peroxodisulfate salts is as initiators (qv) for olefin polymerisation in aqueous systems, particularly for the manufacture of polyacrylonitrile and its copolymers (see Acrylonitrile polymers). These salts are used in the emulsion polymerisation of vinyl chloride, styrene—butadiene, vinyl acetate, neoprene, and acryhc esters (see Acrylic ester polymers Styrene Vinyl polymers). 

Hydroxyhydroquinone and pyrogaHol can be used for lining reactors for vinyl chloride suspension polymerization to prevent formation of polymer deposits on the reactor walls (98). Hydroxyhydroquinone and certain of its derivatives are useful as auxiUary developers for silver haUde emulsions in photographic material their action is based on the dye diffusion-transfer process. The transferred picture has good contrast and stain-free highlights (99). 5-Acylhydroxyhydroquinones are useful as stabilizer components for poly(alkylene oxide)s (100). 

Vinyhdene chloride copolymerizes randomly with methyl acrylate and nearly so with other acrylates. Very severe composition drift occurs, however, in copolymerizations with vinyl chloride or methacrylates. Several methods have been developed to produce homogeneous copolymers regardless of the reactivity ratio (43). These methods are appHcable mainly to emulsion and suspension processes where adequate stirring can be maintained. Copolymerization rates of VDC with small amounts of a second monomer are normally lower than its rate of homopolymerization. The kinetics of the copolymerization of VDC and VC have been studied (45—48). 

However, the kinetics of PVC emulsion does not foUow the above theory. The rate shows the same increasing behavior with conversion as mass polymerization (94,95). [N depends on [3], but the relationship varies with the emulsifier type (96,97). However, the rate is nearly independent of [N (95). The average number of radicals per particle is low, 0.0005 to 0.1 (95). The high solubiUty of vinyl chloride in water, 0.6 wt %, accounts for a strong deviation from tme emulsion behavior. Also, PVC s insolubiUty in its own monomer accounts for such behavior as a rate dependence on conversion. 

Solution Polymerization. In solution polymerization, a solvent for the monomer is often used to obtain very uniform copolymers. Polymerization rates ate normally slower than those for suspension or emulsion PVC. Eor example, vinyl chloride, vinyl acetate, and sometimes maleic acid are polymerized in a solvent where the resulting polymer is insoluble in the solvent. This makes a uniform copolymer, free of suspending agents, that is used in solution coatings (99). 

The largest volume commercial derivatives of 1-butanol are -butyl acrylate [141-32-2] and methacrylate [97-88-1] (10). These are used principally ia emulsion polymers for latex paints, ia textile appHcations and ia impact modifiers for rigid poly(vinyl chloride). The consumption of / -butanol ia the United States for acrylate and methacrylate esters is expected to rise to 182,000—186,000 t by 1993 (10). 

Random copolymers of vinyl chloride and other monomers are important commercially. Most of these materials are produced by suspension or emulsion polymerization using free-radical initiators. Important producers for vinyl chloride—vinyUdene chloride copolymers include Borden, Inc. and Dow. These copolymers are used in specialized coatings appHcations because of their enhanced solubiUty and as extender resins in plastisols where rapid fusion is required (72). Another important class of materials are the vinyl chloride—vinyl acetate copolymers. Principal producers include Borden Chemicals Plastics, B. F. Goodrich Chemical, and Union Carbide. The copolymerization of vinyl chloride with vinyl acetate yields a material with improved processabihty compared with vinyl chloride homopolymer. However, the physical and chemical properties of the copolymers are different from those of the homopolymer PVC. Generally, as the vinyl acetate content increases, the resin solubiUty in ketone and ester solvents and its susceptibiUty to chemical attack increase, the resin viscosity and heat distortion temperature decrease, and the tensile strength and flexibiUty increase slightly. 

Emulsions Emulsions have particles of 0.05 to 5.0 [Lm diameter. The product is a stable latex, rather than a filterable suspension. Some latexes are usable directly, as in paints, or they may be coagulated by various means to produce massive polymers. Figures 23-23d and 23-23 show bead and emulsion processes for vinyl chloride. Continuous emulsion polymerization of outadiene-styrene rubber is done in a CSTR battery with a residence time of 8 to 12 h. Batch treating of emulsions also is widely used. 

Poly(vinyl chloride) is commercially available in the form of aqueous colloidal dispersions (latices). They are the uncoagulated products of emulsion polymerisation process and are used to coat or impregnate textiles and paper. The individual particles are somewhat less than 1 p,m in diameter. The latex may be coagulated by concentrated acids, polyvalent cations and by dehydration with water-miscible liquids. 

Over 80% of the market is accounted for by suspension homopolymer, 13% by emulsion and paste-forming homopolymer, and the rest is mainly bulk homopolymer and vinyl chloride-vinyl acetate copolymer. In Western Europe about two-thirds of consumption is in the field of unplasticised PVC. 

The polymer may be prepared readily in bulk, emulsion and suspension, the latter technique apparently being preferred on an industrial scale. The monomer must be free from oxygen and metallic impurities. Peroxide such as benzoyl peroxide are used in suspension polymerisations which may be carried out at room temperature or at slightly elevated temperatures. Persulphate initiators and the conventional emulsifying soaps may be used in emulsion polymerisation. The polymerisation rate for vinylidene chloride-vinyl chloride copolymers is markedly less than for either monomer polymerised alone. 

The free radical initiators are more suitable for the monomers having electron-withdrawing substituents directed to the ethylene nucleus. The monomers having electron-supplying groups can be polymerized better with the ionic initiators. The water solubility of the monomer is another important consideration. Highly water-soluble (relatively polar) monomers are not suitable for the emulsion polymerization process since most of the monomer polymerizes within the continuous medium, The detailed emulsion polymerization procedures for various monomers, including styrene [59-64], butadiene [61,63,64], vinyl acetate [62,64], vinyl chloride [62,64,65], alkyl acrylates [61-63,65], alkyl methacrylates [62,64], chloroprene [63], and isoprene [61,63] are available in the literature. 

In the emulsion polymerization of vinyl chloride (VC) initiated with type II MAI composed of PDMS, block efficiency was as high as 95-97%, and solid particles with a narrow range of particle size, 0.1-50 microns, were obtained in high yield [15]. 

Chloride (poly) Vinyl Chloride invl Acetylene Emulsion 107 200 7.6 46 46 1... 

Cresylic acid is mainly used as degreasing agent and as a disinfectant of a stabilized emulsion in a soap solution. Cresols are used as flotation agents and as wire enamel solvents. Tricresyl phosphates are produced from a mixture of cresols and phosphorous oxychloride. The esters are plasticizers for vinyl chloride polymers. They are also gasoline additives for reducing carbon deposits in the combustion chamber. 

Emulsion polymerization is widely used to produce polymers in the form of emulsions, such as paints and floor polishes. It also used to polymerize many water insoluble vinyl monomers, such as styrene and vinyl chloride. In emulsion polymerization, an agent emulsifies the monomers. Emulsifying agents should have a finite solubility. They are either ionic, as in the case of alkylbenzene sulfonates, or nonionic, like polyvinyl alcohol. 

The most important industrial application of alkanesulfonates is the generation of the appropriate emulsions for polymerizing vinyl monomers, e.g., vinyl-chloride or styrene. Other uses are as textile and leather auxiliaries, formulating aids for plant protection agents, and fire-extinguishing foams. 

An example of an emulsifier for the polymerization of ethylenically unsaturated monomers is a 22 88 mixture of disodium a-sulfolaurate and sodium methyl a-sulfolaurate. The emulsion is stable for much longer than an emulsion with n-dodecylbenzenesulfonate as the emulsifier [92]. Ester sulfonates are also used as emulsifiers in the continuous manufacture of vinyl chloride polymers [93]. 

Vinyl chloride Free radical polymerization in bulk or emulsion rapid in presence of peroxides susceptible to photochemical polymerization —CH2—CH— 75 Largely amorphous, except when highly oriented by stretching. Hard. Soluble in ketones and esters... 

Polymerizations conducted in nonaqueous media in which the polymer is insoluble also display the characteristics of emulsion polymerization. When either vinyl acetate or methyl methacrylate is polymerized in a poor solvent for the polymer, for example, the rate accelerates as the polymerization progresses. This acceleration, which has been called the gel effect,probably is associated with the precipitation of minute droplets of polymer highly swollen with monomer. These droplets may provide polymerization loci in which a single chain radical may be isolated from all others. A similar heterophase polymerization is observed even in the polymerization of the pure monomer in those cases in which the polymer is insoluble in its own monomer. Vinyl chloride, vinylidene chloride, acrylonitrile, and methacryloni-trile polymerize with precipitation of the polymer in a finely divided dispersion as rapidly as it is formed. The reaction rate increases as these polymer particles are generated. In the case of vinyl chloride ... 

Capek, L Kinetics of the Free-Radical Emulsion Polymerization of Vinyl Chloride. Vol. 120, pp. 135-206. 

In the production of polyvinyl chloride by the emulsion process, the percentages of catalyst, wetting agent, initiator, and solvent all affect the properties of the resultant polymer. They must be carefully metered into the reaction vessel. The vinyl chloride used must also be very pure. Either the scope must specify that the purchased raw material shall meet certain specifications, or some purification equipment must be installed so that the required quality can be obtained. 

Polymerization of vinyl chloride occurs through a radical chain addition mechanism, which can be achieved through bulk, suspension, or emulsion polymerization processes. Radical initiators used in vinyl chloride polymerization fall into two classes water-soluble or monomer-soluble. The water-soluble initiators, such as hydrogen peroxide and alkali metal persulfates, are used in emulsion polymerization processes where polymerization begins in the aqueous phase. Monomer-soluble initiators include peroxides, such as dilauryl and benzoyl peroxide, and azo species, such as 1,1 -azobisisobutyrate, which are shown in Fig. 22.2. These initiators are used in emulsion and bulk polymerization processes. 

General. In this section, a mathematical dynamic model will be developed for emulsion homopolymerization processes. The model derivation will be general enough to easily apply to several Case I monomer systems (e.g. vinyl acetate, vinyl chloride), i.e. to emulsion systems characterized by significant radical desorption rates, and therefore an average number of radicals per particle much less than 1/2, and to a variety of different modes of reactor operation. 

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