Styrene metals

Precatalyst ligand abbreviations Bn = benzyl acac = acetylacetonato bipy = 2,2-bipyridine Cp Styrene/metal molar ratio. 

Typical Use General purpose - high performance. Typical Use Construction. PVC, ABS, Acrylics, GRP, Styrene, metals. ... 

Ketone Peroxides. These materials are mixtures of compounds with hydroperoxy groups and are composed primarily of the two stmctures shown in Table 2. Ketone peroxides are marketed as solutions in inert solvents such as dimethyl phthalate. They are primarily employed in room-temperature-initiated curing of unsaturated polyester resin compositions (usually containing styrene monomer) using transition-metal promoters such as cobalt naphthenate. Ketone peroxides contain the hydroperoxy (—OOH) group and thus are susceptible to the same ha2ards as hydroperoxides. 

The mechanism of the anionic polymerization of styrenes and 1,3-dienes initiated by alkaU metals has been described in detail (3,20) as shown in equations 3—5 where Mt represents an alkaU metal and M is a monomer molecule. Initiation is a heterogeneous process occurring on the metal surface. The... 

Anionic polymerization of vinyl monomers can be effected with a variety of organometaUic compounds alkyllithium compounds are the most useful class (1,33—35). A variety of simple alkyllithium compounds are available commercially. Most simple alkyllithium compounds are soluble in hydrocarbon solvents such as hexane and cyclohexane and they can be prepared by reaction of the corresponding alkyl chlorides with lithium metal. Methyllithium [917-54-4] and phenyllithium [591-51-5] are available in diethyl ether and cyclohexane—ether solutions, respectively, because they are not soluble in hydrocarbon solvents vinyllithium [917-57-7] and allyllithium [3052-45-7] are also insoluble in hydrocarbon solutions and can only be prepared in ether solutions (38,39). Hydrocarbon-soluble alkyllithium initiators are used directiy to initiate polymerization of styrene and diene monomers quantitatively one unique aspect of hthium-based initiators in hydrocarbon solution is that elastomeric polydienes with high 1,4-microstmcture are obtained (1,24,33—37). Certain alkyllithium compounds can be purified by recrystallization (ethyllithium), sublimation (ethyllithium, /-butyUithium [594-19-4] isopropyllithium [2417-93-8] or distillation (j -butyUithium) (40,41). Unfortunately, / -butyUithium is noncrystaUine and too high boiling to be purified by distiUation (38). Since methyllithium and phenyllithium are crystalline soUds which are insoluble in hydrocarbon solution, they can be precipitated into these solutions and then redissolved in appropriate polar solvents (42,43). OrganometaUic compounds of other alkaU metals are insoluble in hydrocarbon solution and possess negligible vapor pressures as expected for salt-like compounds. 

GopolymeriZation Initiators. The copolymerization of styrene and dienes in hydrocarbon solution with alkyUithium initiators produces a tapered block copolymer stmcture because of the large differences in monomer reactivity ratios for styrene (r < 0.1) and dienes (r > 10) (1,33,34). In order to obtain random copolymers of styrene and dienes, it is necessary to either add small amounts of a Lewis base such as tetrahydrofuran or an alkaU metal alkoxide (MtOR, where Mt = Na, K, Rb, or Cs). In contrast to Lewis bases which promote formation of undesirable vinyl microstmcture in diene polymerizations (57), the addition of small amounts of an alkaU metal alkoxide such as potassium amyloxide ([ROK]/[Li] = 0.08) is sufficient to promote random copolymerization of styrene and diene without producing significant increases in the amount of vinyl microstmcture (58,59). 

The reactions of alkyl hydroperoxides with ferrous ion (eq. 11) generate alkoxy radicals. These free-radical initiator systems are used industrially for the emulsion polymerization and copolymerization of vinyl monomers, eg, butadiene—styrene. The use of hydroperoxides in the presence of transition-metal ions to synthesize a large variety of products has been reviewed (48,51). 

The reaction rate of fumarate polyester polymers with styrene is 20 times that of similar maleate polymers. Commercial phthaHc and isophthaHc resins usually have fumarate levels in excess of 95% and demonstrate full hardness and property development when catalyzed and cured. The addition polymerization reaction between the fumarate polyester polymer and styrene monomer is initiated by free-radical catalysts, commercially usually benzoyl peroxide (BPO) and methyl ethyl ketone peroxide (MEKP), which can be dissociated by heat or redox metal activators into peroxy and hydroperoxy free radicals. 

Catalyst Selection. The low resin viscosity and ambient temperature cure systems developed from peroxides have faciUtated the expansion of polyester resins on a commercial scale, using relatively simple fabrication techniques in open molds at ambient temperatures. The dominant catalyst systems used for ambient fabrication processes are based on metal (redox) promoters used in combination with hydroperoxides and peroxides commonly found in commercial MEKP and related perketones (13). Promoters such as styrene-soluble cobalt octoate undergo controlled reduction—oxidation (redox) reactions with MEKP that generate peroxy free radicals to initiate a controlled cross-linking reaction. 

Rubber. The mbber industry consumes finely ground metallic selenium and Selenac (selenium diethyl dithiocarbamate, R. T. Vanderbilt). Both are used with natural mbber and styrene—butadiene mbber (SBR) to increase the rate of vulcanization and improve the aging and mechanical properties of sulfudess and low sulfur stocks. Selenac is also used as an accelerator in butyl mbber and as an activator for other types of accelerators, eg, thiazoles (see Rubber chemicals). Selenium compounds are useflil as antioxidants (qv), uv stabilizers, (qv), bonding agents, carbon black activators, and polymerization additives. Selenac improves the adhesion of polyester fibers to mbber. 

Copolymers with acrylonitrile, butadiene, isoprene, acrylates, piperjiene, styrene, and polyethylene have been studied. The high cost of sorbic acid as a monomer has prevented large-scale uses. The abiUty of sorbic acid to polymerize, particularly on metallic surfaces, has been used to explain its corrosion inhibition for steel, iron, and nickel (14). 

Other miscellaneous compounds that have been used as inhibitors are sulfur and certain sulfur compounds (qv), picryUiydrazyl derivatives, carbon black, and a number of soluble transition-metal salts (151). Both inhibition and acceleration have been reported for styrene polymerized in the presence of oxygen. The complexity of this system has been clearly demonstrated (152). The key reaction is the alternating copolymerization of styrene with oxygen to produce a polyperoxide, which at above 100°C decomposes to initiating alkoxy radicals. Therefore, depending on the temperature, oxygen can inhibit or accelerate the rate of polymerization. 

Polymers. In combination with various metal salts, sorbitol is used as a stabilizer against heat and light in poly(vinyl chloride) (qv) resins and, with a phenohc antioxidant, as a stabilizer in uncured styrene—butadiene mbber (qv) compositions and in polyolefins (see Heat stabilizers Olefin POLYMERS Rubbercompounding). Heat-sealable films are prepared from a dispersion of sorbitol and starch in water (255). Incorporation of sorbitol in coUagen films gready restricts their permeabiUty to carbon dioxide (256). 

Ring Additions Catalyzed by Alkali Metals. The addition of tributyltin chloride and olefins such as styrene, isoprene, or butadiene to sulfolane is cataly2ed by alkah metals, including sodium and lithium, and by sodium amide (10—13). The addition of tributyltin chloride to sulfolane in the... 

Oiganometallic usage is shown in the piepaiation of titanium- oi vanadium-containing catalysts foi the polymerisation of styrene or butadiene by the reaction of dimethyl sulfate with the metal chloride (145). Free-radical activity is proposed for the quaternary product from dimethylaruline and dimethyl sulfate and for the product from l,l,4,4-tetramethyl-2-tetra2ene and dimethyl sulfate (146,147). 

Titanium—Vanadium Mixed Metal Alkoxides. Titanium—vanadium mixed metal alkoxides, VO(OTi(OR)2)2, are prepared by reaction of titanates, eg, TYZOR TBT, with vanadium acetate ia a high boiling hydrocarbon solvent. The by-product butyl acetate is distilled off to yield a product useful as a catalyst for polymeri2iag olefins, dienes, styrenics, vinyl chloride, acrylate esters, and epoxides (159,160). 

Wilkinson Hyd.rogena.tion, One of the best understood catalytic cycles is that for olefin hydrogenation in the presence of phosphine complexes of rhodium, the Wilkinson hydrogenation (14,15). The reactions of a number of olefins, eg, cyclohexene and styrene, are rapid, taking place even at room temperature and atmospheric pressure but the reaction of ethylene is extremely slow. Complexes of a number of transition metals in addition to rhodium are active for the reaction. 

The performance of many metal-ion catalysts can be enhanced by doping with cesium compounds. This is a result both of the low ionization potential of cesium and its abiUty to stabilize high oxidation states of transition-metal oxo anions (50). Catalyst doping is one of the principal commercial uses of cesium. Cesium is a more powerflil oxidant than potassium, which it can replace. The amount of replacement is often a matter of economic benefit. Cesium-doped catalysts are used for the production of styrene monomer from ethyl benzene at metal oxide contacts or from toluene and methanol as Cs-exchanged zeofltes ethylene oxide ammonoxidation, acrolein (methacrolein) acryflc acid (methacrylic acid) methyl methacrylate monomer methanol phthahc anhydride anthraquinone various olefins chlorinations in low pressure ammonia synthesis and in the conversion of SO2 to SO in sulfuric acid production. 

Between the 1920s when the initial commercial development of mbbery elastomers based on 1,3-dienes began (5—7), and 1955 when transition metal catalysts were fkst used to prepare synthetic polyisoprene, researchers in the U.S. and Europe developed emulsion polybutadiene and styrene—butadiene copolymers as substitutes for natural mbber. However, the tire properties of these polymers were inferior to natural mbber compounds. In seeking to improve the synthetic material properties, research was conducted in many laboratories worldwide, especially in the U.S. under the Rubber Reserve Program. 

ABS plastic, a polymer consisting of polybutadiene spheroids is dispersed in a continuous phase of poly(styrene—acrylonitrile). The chromic acid attacks the polybutadiene at a much higher rate than the continuous phase. This gives an excellent microroughened surface with superior metal-to-plastic bond strength. A typical recommended formulation consists of 20 vol % sulfuric acid, 420 g/L chromic acid, and 0.1—1.0% of a fluorocarbon wetting agent. The plastic is treated with this formulation for 6—10 min at 60—65°C. 

Efficiency and pressure drop data for Siilzer BX metal gauze structured packing and for three test mixtures are shown in Fig. 14-7.5. For the ethyl benzene/styrene test mixture, the effect of operating pressure is shown. The high viscosity mixture, propylene glycoL/ethylene... 

Polymerization of olefins such as styrene is promoted by acid or base or sodium catalysts, and polyethylene is made with homogeneous peroxides. Condensation polymerization is catalyzed by acid-type catalysts such as metal oxides and sulfonic acids. Addition polymerization is used mainly for olefins, diolefins, and some carbonyl compounds. For these processes, initiators are coordination compounds such as Ziegler-type catalysts, of which halides of transition metals Ti, V, Mo, and W are important examples. 

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