Emulsion copolymerizations

Antiviriai. bactericide Modifiers in the emulsion copolymerization of butadiene... 

Nitrile Rubber. Nitrile mbbers are made by the emulsion copolymerization of acrylonitrile (9—50%) and butadiene (6) and designated NBR. The ratio of acrylonitrile (ACN) to butadiene has a direct effect on the properties on the nature of the polymers. As the ACN content increases, the oil resistance of the polymer increases (7). As the butadiene content increases, the low temperature properties of the polymer are improved (see Elastomers, SYNTHETIC-NITRILE RUBBER). 

Continuous emulsion copolymerization processes for vinyl acetate and vinyl acetate—ethylene copolymer have been reported (59—64). CycHc variations in the number of particles, conversion, and particle-size distribution have been studied. Control of these variations based on on-line measurements and the use of preformed latex seed particles has been discussed (61,62). 

Continuous polymerization systems offer the possibiUty of several advantages including better heat transfer and cooling capacity, reduction in downtime, more uniform products, and less raw material handling (59,60). In some continuous emulsion homopolymerization processes, materials are added continuously to a first ketde and partially polymerized, then passed into a second reactor where, with additional initiator, the reaction is concluded. Continuous emulsion copolymerizations of vinyl acetate with ethylene have been described (61—64). Recirculating loop reactors which have high heat-transfer rates have found use for the manufacture of latexes for paint appHcations (59). 

DSEP direct soapless emulsion polymerization, SSEC seeded soapless emulsion copolymerization, DDC direct dispersion copolymerization, TDSC two-stage dispersion copolymerization, ATES Allyl trietoxysilane, VTES vinyl trietoxysilane, DMAEM dimethylaminoethyl-methacrylate, CMS chloromethylstyrene, GA glutaraldehyde, AAc Acrylic acid Aam Acrylamide HEMA 2-hydroxyethylmethacrylate. 

The water solubilities of the functional comonomers are reasonably high since they are usually polar compounds. Therefore, the initiation in the water phase may be too rapid when the initiator or the comonomer concentration is high. In such a case, the particle growth stage cannot be suppressed by the diffusion capture mechanism and the solution or dispersion polymerization of the functional comonomer within water phase may accompany the emulsion copolymerization reaction. This leads to the formation of polymeric products in the form of particle, aggregate, or soluble polymer with different compositions and molecular weights. The yield for the incorporation of functional comonomer into the uniform polymeric particles may be low since some of the functional comonomer may polymerize by an undesired mechanism. 

Table 10 The Size of the Uniform Copolymer Latices Prepared by Direct Soapless Emulsion Copolymerization [113,114]...

Soapless seeded emulsion copolymerization has been proposed as an alternative method for the preparation of uniform copolymer microspheres in the submicron-size range [115-117]. In this process, a small part of the total monomer-comonomer mixture is added into the water phase to start the copolymerization with a lower monomer phase-water ratio relative to the conventional direct process to prevent the coagulation and monodispersity defects. The functional comonomer concentration in the monomer-comonomer mixture is also kept below 10% (by mole). The water phase including the initiator is kept at the polymerization temperature during and after the addition of initial monomer mixture. The nucleation takes place by the precipitation of copolymer macromolecules, and initially formed copolymer nuclei collide and form larger particles. After particle formation with the initial lower organic phase-water ratio, an oligomer initiated in the continuous phase is... 

The soapless seeded emulsion copolymerization method was used for producing uniform microspheres prepared by the copolymerization of styrene with polar, functional monomers [115-117]. In this series, polysty-rene-polymethacrylic acid (PS/PMAAc), poly sty rene-polymethylmethacrylate-polymethacrylic acid (PS/ PMMA/PMAAc), polystyrene-polyhydroxyethylmeth-acrylate (PS/PHEMA), and polystyrene-polyacrylic acid (PS/PAAc) uniform copolymer microspheres were synthesized by applying a multistage soapless emulsion polymerization process. The composition and the average size of the uniform copolymer latices prepared by multistage soapless emulsion copolymerization are given in Table 11. 

PS/PHEM A particles in micron-size range were also obtained by applying the single-stage soapless emulsion copolymerization method [124]. But, this method provided copolymer particles with an anomalous shape with an uneven surface. PS or PHEMA particles prepared by emulsifier-free emulsion polymerization were also used as seed particles with the respective comonomer to achieve uniform PS/PHEMA or PHEMA/PS composite particles. PS/PHEMA and PHEMA/PS particles in the form of excellent spheres were successfully produced 1 iLitm in size in the same study. 

To our knowledge, this is the first time that an emulsion copolymerization model has been developed based on a population balance approach. The resulting differential equations are more involved and complex than those of the homopolymer case. Lack of experimental literature data for the specific system VCM/VAc made it impossible to directly check the model s predictive powers, however, successful simulation of extreme cases and reasonable trends obtained in the model s predictions are convincing enough about the validity and usefulness of the mathematical model per se. 

Figure 5. VCM/VAc emulsion copolymerization (a) conversion vs. time in a batch reactor for extreme cases (b) instantaneous copolymer compostion (c) start-up procedures in an unseeded CSTR.

Poly(azophenylene-o-carborane) (see 6) has been prepared from diphenyl-o-carborane by means of nitration, reduction, and acylation to initially give 1,2-bis(/ -nitroso-acetylaminophenyl)-o-carborane (NAFC). Rapid decomposition in solution affords phenylene amino phenyl carborane (PAFC) by recombination of phenylene and azophenylene radicals.40 These radicals have also been utilized to form copolymers of carborane-containing copolymers from monomers polymerizable via radical mechanisms. Thus, copolymers of polystyrene and poly(azophenylene) can be readily formed by means of emulsion copolymerization of styrene with NAFC decomposition products. 

Microgels by Emulsion Copolymerization of Self-Emulsifying Unsaturated Polyesters and Comonomers... 

By emulsion copolymerization (ECP) of self-emulsifying unsaturated polyesters (EUP) and bifunctional monomers, such as styrene (S), microgels may be prepared which have a rather uniform diameter [109]. This uniformity of size is due to a special mechanism of particle formation involved in using EUP as comonomers. 

Emulsion copolymerization of EUP and comonomers may be initiated in the aqueous (persulfate) or in the non-aqueous phase (AIBN). On the decomposition of persulfates, sulfate and hydroxyl groups are introduced into macromolecules and microgels, thus influencing their surface properties [118,123-125]. By using AIBN as initiator a change of the chemical character of the surface and of the properties of the microgels is avoided. 

The parameters which influence the particle size of microgels have been studied during self-emulsifying, seeded emulsion copolymerization of an unsaturated polyester and butyl acrylate [134]. 

Fig. 56. Dependence of Mwof the microgels on the polymer yield in the anionic polymerization of EDMA in toluene by n-BuLi [254] (see Figure 53 caption for the reaction conditions). Reduced viscosity vs concentration of microgels a) Composition (mol %) N,N -methyl-enebisacrylamide (55%), methacrylamide (33%), methacrylic acid (2%), methacrylamido acetaldehyd-dimethylacetal (10%),measured at 20 °C in water, b) Composition (mol %) 1,4-DVB (35%), propenic acid amide-2-methyl-N-(4-methyl-2-butyl-l,3-dioxolane prepared by emulsion copolymerization and measured in dimethylformamide.

The use of a single-stage CSTR for HF alkylation of hydrocarbons in a special forced-circulation shell-and-tube arrangement (for heat transfer) is illustrated by Perry et al. (1984, p. 21-6). The emulsion copolymerization of styrene and butadiene to form the synthetic rubber SBR is carried out in a multistage CSTR. 

Continuous emulsion copolymerization processes, for vinyl acetate,... 

I, too, was caught up in the wave of enthusiasm for this new science which had the lofty goal of relating the properties of materials to their molecular structure, and, in the end, to "tailor-making molecules for specific properties. Since one of the big developments at that time was the newly-started synthetic rubber programs of the American and Canadian governments, I chose the topic of the emulsion copolymerization of butadiene-styrene as the subject of my doctoral dissertation. 

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