Polymerization, initiation

Poly (methyl Acrylate). The monomer used for preparing poly(methyl acrylate) is produced by the oxidation of propylene. The resin is made by free-radical polymerization initiated by peroxide or azo catalysts and has the following formula ... 

CINNAMICACID,CINNAMALDEHYDEANDCINNAMYLALCOHOL] (Vol6) -as polymerization initiator [INITIATORS - CATIONIC INITIATORS] (Vol 14)... 

Tetrahydrofurfuryl alcohol is used in elastomer production. As a solvent for the polymerization initiator, it finds appHcation in the manufacture of chlorohydrin mbber. Additionally, tetrahydrofurfuryl alcohol is used as a catalyst solvent-activator and reactive diluent in epoxy formulations for a variety of apphcations. Where exceptional moisture resistance is needed, as for outdoor appHcations, furfuryl alcohol is used jointly with tetrahydrofurfuryl alcohol in epoxy adhesive formulations. 

Compounds with active hydrogen add to the carbonyl group of acetone, often followed by the condensation of another molecule of the addend or loss of water. Hydrogen sulfide forms hexamethyl-l,3,5-trithiane probably through the transitory intermediate thioacetone which readily trimerizes. Hydrogen cyanide forms acetone cyanohydrin [75-86-5] (CH2)2C(OH)CN, which is further processed to methacrylates. Ammonia and hydrogen cyanide give (CH2)2C(NH2)CN [19355-69-2] ix.orn. 6<55i the widely used polymerization initiator, azobisisobutyronitrile [78-67-1] is made (4). 

In addition to the monomers, the polymerization ingredients include an emulsifier, a polymerization initiator, and usually a chain-transfer agent for molecular weight control. 

If a linear mbber is used as a feedstock for the mass process (85), the mbber becomes insoluble in the mixture of monomers and SAN polymer which is formed in the reactors, and discrete mbber particles are formed. This is referred to as phase inversion since the continuous phase shifts from mbber to SAN. Grafting of some of the SAN onto the mbber particles occurs as in the emulsion process. Typically, the mass-produced mbber particles are larger (0.5 to 5 llm) than those of emulsion-based ABS (0.1 to 1 llm) and contain much larger internal occlusions of SAN polymer. The reaction recipe can include polymerization initiators, chain-transfer agents, and other additives. Diluents are sometimes used to reduce the viscosity of the monomer and polymer mixture to faciUtate processing at high conversion. The product from the reactor system is devolatilized to remove the unreacted monomers and is then pelletized. Equipment used for devolatilization includes single- and twin-screw extmders, and flash and thin film evaporators. Unreacted monomers are recovered for recycle to the reactors to improve the process yield. 

Acryhc stmctural adhesives have been modified by elastomers in order to obtain a phase-separated, toughened system. A significant contribution in this technology has been made in which acryhc adhesives were modified by the addition of chlorosulfonated polyethylene to obtain a phase-separated stmctural adhesive (11). Such adhesives also contain methyl methacrylate, glacial methacrylic acid, and cross-linkers such as ethylene glycol dimethacrylate [97-90-5]. The polymerization initiation system, which includes cumene hydroperoxide, N,1S7-dimethyl- -toluidine, and saccharin, can be apphed to the adherend surface as a primer, or it can be formulated as the second part of a two-part adhesive. Modification of cyanoacrylates using elastomers has also been attempted copolymers of acrylonitrile, butadiene, and styrene ethylene copolymers with methylacrylate or copolymers of methacrylates with butadiene and styrene have been used. However, because of the extreme reactivity of the monomer, modification of cyanoacrylate adhesives is very difficult and material purity is essential in order to be able to modify the cyanoacrylate without causing premature reaction. 

Other Plastics Uses. The plasticizer range alcohols have a number of other uses in plastics hexanol and 2-ethylhexanol are used as part of the catalyst system in the polymerization of acrylates, ethylene, and propylene (55) the peroxydicarbonate of 2-ethylhexanol is utilized as a polymerization initiator for vinyl chloride various trialkyl phosphites find usage as heat and light stabHizers for plastics organotin derivatives are used as heat stabHizers for PVC octanol improves the compatibHity of calcium carbonate filler in various plastics 2-ethylhexanol is used to make expanded polystyrene beads (56) and acrylate esters serve as pressure sensitive adhesives. 

The Kleber-Colombes rigid PVC foam (253,254) is produced by compression mol ding vinyl plastisol to react and gel the compound, followed by steam expansion. The process involves mixing, mol ding, and expansion. The formulation consists of PVC, isocyanate, vinyl monomers such as styrene, anhydrides such as maleic anhydride, polymerization initiators, FC-11, and nucleators. The ingredients are mixed in a Wemer-Pfleiderer or a Baker Perkins... 

Peioxydicaibonates are efficient polymerization initiators for most vinyl monomer polymerizations, especially for monomers such as acrylates, ethylene, and vinyl chloride. They are particularly good initiators for less reactive monomers such as those containing aHyl groups. They are also effective for curing of unsaturated polyester mol ding resins. 

Others. Oxahc acid is used for the production of cobalt, as a raw material of various agrochemicals and pharmaceuticals, for the manufacture of electronic materials (76—83), for the extraction of tungsten from ore (84), for the production of metal catalysts (85,86), as a polymerization initiator (87—89), and for the manufacture of zirconium (90) and beryhium oxide (91). 

Nylon-6 is the polyamide formed by the ring-opening polymerization of S-caprolactam. The polymerization of S-caprolactam can be initiated by acids, bases, or water. Hydrolytic polymerization initiated by water is often used in industry. The polymerization is carried out commercially in both batch and continuous processes by heating the monomer in the presence of 5—10% water to temperatures of 250—280°C for periods of 12 to more than 24 h. The chemistry of the polymerization is shown by the following reaction sequence. 

These spectral properties give rise to the wide range of appHcations of PMDs as silver haHde sensitizers (11), laser media components (12,13), polymerization initiators (14), etc. 

Fig. 3. Polymerization initiation and propagation by radiation-generated free radicals. A is the initiating radical produced by irradiating the Hquid coating. (1) represents the Hquid monomer—unsaturated polymer reactive coating system. R is functional. (2) is the growing polymer chain (free radical). The cured...

The basic constituents of all commercial emulsion polymerization recipes are monomers, emulsifiers, and polymerization initiators. Other common components are modifiers, inorganic salts and free alkaH, and shortstops. The function of these different components and the mechanism of emulsion polymerization have been described (43,44). 

A mixture of they -menthadienes can be hydrogenated to produce a mixture of i7j -y-menthane [6069-98-3] and /ra/ j -p-menthane [1678-82-6]. Oxidation to a mixture ofy)-menthane hydroperoxides gives a usehil polymerization initiator used in the mbber industry. 

Butadiene is also known to form mbbery polymers caused by polymerization initiators like free radicals or oxygen. Addition of antioxidants like TBC and the use of lower storage temperatures can substantially reduce fouling caused by these polymers. Butadiene and other olefins, such as isoprene, styrene, and chloroprene, also form so-called popcorn polymers (250). These popcorn polymers are hard, opaque, and porous. They have been reported to... 

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