Organic Peroxide Initiators

Approximately 100 different organic peroxide initiators, in well over 300 formulations, are commercially produced throughout the wodd, primarily for the polymer and resin industries (22—27). A multiclient study covets the commercial producers and users of organic peroxides as well as other initiators, and their commercial markets and appHcations (28). 

Bulk polymerization has been studied at relatively low temperatures and in toluene and carbon tetrachloride solutions carried to low conversions (12). The effects of temperature and different organic peroxide initiators have been observed. The molecular weight of soluble polymer after 3% conversion is ca — 19,000 and is somewhat dependent on initiator concentration or temperature between 35 and 65 °C. With di-2-methylpentanoyl... 

A polymerization process involving a monomer, an organic peroxide initiator and an organic solvent underwent an energetic runaway reaction. All the contents in the polymerization reactor were lost. The emergency relief system prevented major damage to the equipment. 

Qiu et al. [11] reported that the aromatic tertiary amine with an electron-rich group on the N atom would favor nucleophilic displacement and thus increase the rate of decomposition of diacyl peroxide with the result of increasing the rate of polymerization (Table 1). They also pointed out that in the MMA polymerization using organic peroxide initiator alone the order of the rate of polymerization Rp is as follows ... 

VL Antonovskii. Organic Peroxide Initiators. Moscow Khimiya, 1972 [in Russian]. 

POSTech A process for making copolymers of styrene with polyols. A special stabilizer is used, as well as an organic peroxide initiator. 

In the presence of an organic peroxide Initiator, the alkenes and their derivatives undergo addition polymerisation or chain growth polymerisation through a free radical mechanism. Polythene, teflon, orlon, etc. are formed by addition polymerisation of an appropriate alkene or Its derivative. Condensation poiymerisation reactions are... 

Approximately 100 different organic peroxide initiators, in well over 300 formulations, are commercially produced throughout the world, primarily for the polymer and resin industries. 

Thus the induced H202 dissociation and auto-induced decomposition of organic peroxides (initiators) are accompanied by a change of, at least, one of three reaction parameters (a) stoichiometric equation of the reaction (decomposition products remain typical of the current substance) (b) reaction type and (c) reaction pathway (mechanism) with decomposition overall stoichiometric equation preserved. 

In GPPS systems, these peroxides mainly supplemented the free radicals generated by thermal initiation, whereas in the HIPS process, it was found that they could enhance the grafting of styrene to unsaturated rubbers, such as polybutadiene. Additional benefits of organic peroxide initiators were increased production per unit reactor volume, reduction of styrene oligomers and lower reactor temperatures. The instantaneous removal of peroxide feed to a runaway reactor also provides a safety mechanism. Peroxide-initiated systems have higher reaction rates owing to shorter reactor residence times, so the ability to remove one source of radical initiation quickly is important. 

Chapter 1 is used to review the history of polyethylene, to survey quintessential features and nomenclatures for this versatile polymer and to introduce transition metal catalysts (the most important catalysts for industrial polyethylene). Free radical polymerization of ethylene and organic peroxide initiators are discussed in Chapter 2. Also in Chapter 2, hazards of organic peroxides and high pressure processes are briefly addressed. Transition metal catalysts are essential to production of nearly three quarters of all polyethylene manufactured and are described in Chapters 3, 5 and 6. Metal alkyl cocatalysts used with transition metal catalysts and their potentially hazardous reactivity with air and water are reviewed in Chapter 4. Chapter 7 gives an overview of processes used in manufacture of polyethylene and contrasts the wide range of operating conditions characteristic of each process. Chapter 8 surveys downstream aspects of polyethylene (additives, rheology, environmental issues, etc.). However, topics in Chapter 8 are complex and extensive subjects unto themselves and detailed discussions are beyond the scope of an introductory text. 

This plastic is a partially fluorinated straight-chain polymer with a very high molecular weight. It is produced by free-radical polymerization mechanism in a solvent or a hybrid (a solvent/aqueous mixture) media, using an organic peroxide initiator. Copolymerization of tetrafluoroethylene and ethylene (CH2=CH2, molecular weight 28, CAS number 74-85-1) proceeds by an addition mechanism. 

Maximilian Dom (1994) Organic Peroxides (Initiators for the Polymer Industry). Verlag Modeme Industrie, UK, p 70... 

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