STYRENE-BUTYL

During the early 1960s, various vinyl monomers (e.g. styrene, /-butyl styrene, chlorostyrene, vinyl chloride, vinyl acetate, acrylonitrile, acrylates, especially methyl methacrylate) were used to treat wood, and po-... 

As an illustration we refer to the data of Lackdavala and Salovey [160] who studied the flow of styrene/butyl methacrylate copolymer composites with ash of... 

A prime example of these features can be found in the synthesis of styrene/ (meth)acrylate random copolymers. By controlling the initiator/total monomer ratio, the molecular weight can be accurately controlled for both styrene/methyl methacrylate and styrene/butyl acrylate random copolymers. As can be seen in Figure 2.3 the polydispersity for both systems is essentially 1.10-1.25 over comonomer ratios ranging from 1/9 to 9/1. 

Buna-S Elastomeric copolymer of butadiene and styrene, butyl rubber Elastomeric copolymer of isobutylene and isoprene. 

Preparation of a Styrene/Butyl Acrylate/Methacrylic Acid Terpolymer Dispersion (Influence of Emulsifier)... 

The mechanical properties of these membranes were improved by including a crosslinker, methylene bisacrylamide, in the aqueous phase, and by using a styrene/butyl acrylate (BA) mixture as the continuous phase [185]. The styrene/BA mixture had to be prepolymerised to low conversion to allow HIPE formation. The permeation rate of the membrane was improved by including a porogen (hexane) in the organic phase, generating a permanent porous structure [186]. The pervaporation rate was indeed increased, however a drop in selectivity for water from water/ethanol mixtures was also observed. 

Handel and co-workers [11] have investigated the influence of the polymerization conditions on the molecular weight and chemical composition of styrene-butyl acrylate copolymers ... 

Figure 7.1.9 Contour plot obtained for a typical GPC-NMR on-line coupling analysis of a styrene-butyl acrylate copolymer...

Maleate Surfmers were found to outperform methacrylic and crotonic compounds in the copolymerization of styrene, butyl acrylate and acrylic acid in seeded and nonseeded semicontinuous processes [17]. The maleate Surfmer achieved high conversion without homopolymerization in the aqueous phase which can result in emulsion instability. The methacrylate Surfmer was too reactive as opposed to the crotonate which was not sufficiently reactive. The reported dependence of the maleate Surfmer conversion on the particle diameter is consistent with a reaction at the particle surface. 

The cationic Surfmers produced much smaller particle sizes in the emulsion polymerization of styrene and styrene/butyl acrylate than the amphoterics (20-50 nm versus 100-300 nm). Some of the latter, however, conferred to the copolymer lattices stability to electrolytes and freeze-thaw [24]. Similar, but nonreactive surfactants produced from succinic anhydride gave similar stability but had much inferior water resistance [25]. 

The maleic Surfmers were tested in core-shell emulsion polymerization of styrene/butyl acrylate in comparison with a standard nonreactive surfactant (nonyl phenol reacted with 30 mol of EO - NP30). While the methacrylic-derived Surfmer was completely incorporated during the polymerization (although about one-third of it was buried inside the particles) the NP30, the maleic Surfmer and the allylic and vinyl Surfmers were not incorporated and could be extracted with acetone (for the last two probably because of the formation of acetone-extractable oligomers due to a chain transfer behavior) [31]. 

Schoonbrood, H.A.S., Unzue, MJ., Beck, O. and Asua, J.M. (1997) Reactive surfactants in heterophase polymerization. 7. Emulsion copolymerization mechanism involving three anionic polymerizable surfactants (surfmers) with styrene-butyl acrylate acrylic acid. Macromolecules, 30, 6024-33. 

Sindt, O., Gauthier, C., Hamaide, T. and Guyot, AJ. (2000) Reactive surfactants in heterophase polymerization. XVI. Emulsion copolymerization of styrene-butyl acrylate-acrylic acid in the presence of simple maleate reactive surfactants. /. Appl. Polym. Sci, 77,2768-76. 

Abele, S., Gauthier, C., Graillat, C. and Guyot, A. (2000) Films from styrene-butyl acrylate lattices using maleic or succinic surfactants mechanical properties, water rebound and grafting of the surfactants. Polymer, 41, 1147-55. 

Watanabe62) studied systematically the copolymerization of ra-methacryloyl-polyoxyethylenes, with monomers such as acrylonitrile, styrene, butyl methacrylate, and methacrylic acid. It should be mentioned that the macromonomers that he prepared are very short so that no difficulties were encountered to isolate the graft copolymers formed. There are many applications for these graft copolymers, e.g. as additives in polyacrylonitrile films and fibers they cause improved antistatic properties. They have been tested as varnishes, coatings, and wood dimensional stabilization agents. 

Inaba et al. prepared a series of model styrene/butyl acrylate copolymer latexes with glass transition temperatures at room temperature. The functional monomer 2-(3-isopropenylphenyl)-2-methylethylisocyanate (TMI) was used as monomer/crosslinking agent for further film formation. A small amount of methacrylic acid was introduced in some formulations in order to enhance the crosslinking reaction. A redox initiation system was used to reduce premature crosslinking during the polymerization [82]. 

DiPaola-Baranyi, G., "Thermodynamic Miscibility of Various Solutes with Styrene-Butyl Methacrylate Polymers and Copolymers," Macromolecules, 14, 683 (1981). 

Data on Bonderite 37 treated steel are shown in Table IV. The samples are listed in order of reduci-bility. The difference in coating weights between reducible and non-reducible systems is clearly evident. The former deposit coating weights in the same range as for an amine-stabilized styrene/butyl acrylate latex. The latter was coated at pH 4 because of colloidal instability at a higher pH. 

Addition of the XIII as a macroinitiator to styrene polymerization resulted in the formation of S-MMA-S triblock copolymer. The same procedure was also used to make styrene-butyl acrylate block copolymers. 

Table 31.2 Contents of styrene, butylated hydroxytoluene (BHT) and styrene, dimer and trimers [8]. Reproduced by permission of the Food Hygiene Society of Japan... 

As a general statement, isomerizations occur much slower (around lOOtimes and more) in the film than in solution. It was already observed for azo compounds by Kamogawa et in the case of copolymers of 4-vinyl-4 -dimethylaminoazobenzene (I) with styrene and of 4-acryloylaminomethylaminoazobenzene (II) with styrene, butyl acrylate and methyl methacrylate. 

In the first detailed study of benzoin photoinitiated polymerization of vinyl monomers (styrene, butyl acrylate, methyl acrylate and methyl... 

Metal ion-imprinted microspheres were prepared as follows [14,15]. Seed emulsion was obtained by the polymerisation of styrene, butyl acrylate and methacrylic acid in water. Divinylbenzene, butyl acrylate and water were further added to the polymerisation mixture (seed emulsion) and the emulsion was left for a defined time so that the seed microspheres became swollen. The emulsion was combined with a metal ion solution to achieve complexation between the metal ion and the carboxyl group on the surface. Then the divinylbenzene-containing emulsion was polymerised by the use of y-rays at room temperature. The micro-spheres obtained by centrifugation were washed with a hydrochloric acid solution to remove the metal ion. The microspheres obtained were then dried under vacuum. Non-imprinted microspheres (as a reference) were synthesised similarly, but without a metal ion. 

Plots of the relationship between the styrene content and retention volume for copolymers of styrene-acrylate and styrene-methacrylate with the same ester group lay roughly on the same line. This result indicates that a pair of copolymers with the same ester group and the same styrene content could not be separated (24), For example, copolymers of styrene-methyl acrylate and styrene-MMA with the same styrene content cannot be separated by this technique. In copolymers with the same styrene content, styrene-butyl acrylate and styrene-butyl methacrylate copolymers eluted first from a column, the copolymers of ethyl esters were next, and those of methyl esters eluted last. 

Thermolysis of (19) in absence of a phosphine generates 1,2-thiaphosphole 2-sullides (21) which can be trapped with suitable dienophiles such as acrylonitrile, styrene, butyl vinyl ether, and norbornene. The [4-1-2] cycloadducts such as (22) are formed regiospecifically <85BCJ667>. The reaction with dimethyl ethynedicarboxylate or phenyl ethyne affords 1-phosphabarrelene 1-sulfides (23) (Scheme 3) <86Ba2047>. 

Paints and coatings are based on polymers that can form a film. The polymer is considered the binder or vehicle that carries the pigments and additives that are used to impart color or protect the surface of the substrates on which the paint or coating is applied. Some examples of polymers used as paint base are copolymers of styrene-butyl acrylate or of acrylic monomer-vinyl acetate. In the product, the polymer is either finely dispersed in water forming a latex or dissolved in a solvent (in oil-based paints). Latexes for paints are usually produced by emulsion polymerization (Chapter 14). 

MODEL STUDIES Early in this study it appeared that [2.2.1]bicyclic olefin resins added conventional crosslinking thiols in a rapid, exothermic, manner. These results appear to contradict earlier reports that internal olefins and cyclic olefins such as cyclohexene and cydopentene react only slowly with thiols. In reality, [2.2.1]bicydic olefins represent a separate dass of reactive olefins. These results are also consistent with reports (16-19) that bicyclic olefins such as norbomadiene are quite reactive to the addition of monofunctional thiols and thiyl radicals. In order to quantify the relative reactivity of norbornene resins with other "standard" ene components, a model study of the addition reaction was undertaken. A "typical" thiol (ethyl mercaptoacetate) was examined in a series of competitive reactions in which there was a defidency of olefin (Figure 4). Olefin substrates that were compared were norbornene, styrene, butyl vinyl ether, [2.2.2]bicydooctene and phenyl allyl ether. The results of that study are listed below in Table I. 

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