Polymers halogenation reactions

Chemical reactions are used to modify existing polymers, often for specialty applications. Although of considerable importance for plastics, very few polymer reactions (aside from crosslinking) are important for elastomers. Chlorination and bromination of Butyl rubber to the extent of about one halogen atom per isoprene unit yields elastomers which are more easily crosslinked than Butyl rubber. Substitution occurs with rearrangement to yield an allylic halide structure... 

Reactions of benzylic phosphonium salts were carried out at 20 °C using 10 mL of methylene chloride, 1.5 mmol of the polymeric phosphonium salt, and 3 mL of 50% NaOH (aq). The linear polystyrene had a MW of 150,000 with 2.7 mmol of -PPh2/g of polymer. The cross-linked polystyrene contained 3.0-3.5 mmol of -PPh2/g of polymer. The halogenated phosphonium ion was prepared from phos-phinated polystyrene having 0.4 mequiv of -PPh2/g of polymer and was allowed to react with para-tolualdehyde at 50 C for 16 h. 

C, and the other comprises the reaction of dihydroxy(phthalocyaninato)germane with triphenylsi-lylthiol in refluxing chlorobenzene. The conductivity of polymer 84 is determined to be 2x10 in the undoped state. Exposure of the polymer to halogen vapor resulted in the decomposition of the Ge-S... 

For most vinyl polymers, head-to-tail addition is the dominant mode of addition. Variations from this generalization become more common for polymerizations which are carried out at higher temperatures. Head-to-head addition is also somewhat more abundant in the case of halogenated monomers such as vinyl chloride. The preponderance of head-to-tail additions is understood to arise from a combination of resonance and steric effects. In many cases the ionic or free-radical reaction center occurs at the substituted carbon due to the possibility of resonance stabilization or electron delocalization through the substituent group. Head-to-tail attachment is also sterically favored, since the substituent groups on successive repeat units are separated by a methylene... 

Either mechanism can be used to describe how antimony—halogen systems operate in both the condensed and vapor phases. In the condensed phase a chat that is formed during the reaction of the polymer, antimony trioxide, and the halogen reduces the rate of decomposition of the polymer therefore, less fuel is available for the flame (16). 

Multifunctional Hydroxy, Mercapto, and Amino Compounds. These are used to cross-link halogenated polymers. Depending on the labihty of the halogen, the cross-linking agents can be capped to reduce reactivity or used in combination with accelerators to increase the rate of reaction. Benzoyl capping is common with hydroxy and mercapto compounds forming the carbamate by reaction with one equivalent of carbon dioxide is used with diamines. 

Butyl and Halobutyl Rubber. Butyl mbber is made by the polymerization of isobutylene a small amount of isoprene is added to provide sites for curing. It is designated HR because of these monomers. Halogenation of butyl mbber with bromine or chlorine increases the reaction rate for vulcanization and laminates or blends of halobutyl are feasible for production of mbber goods. It is estimated that of the - 100 million kg of butyl (UR) and halobutyl (HIIR) mbber in North America, over 90% is used in tire apphcations. The halogenated polymer is used in the innerliner of tubeless tires. Butyl mbber is used to make innertubes and curing bladders. The two major suppHers of butyl and halobutyl polymers in North America are Exxon and Bayer (see ELASTOLffiRS,SYNTHETIC-BUTYLrubber). 

Meta.1 Oxides. Halogen-containing elastomers such as polychloropreae and chlorosulfonated polyethylene are cross-linked by their reaction with metal oxides, typically ziac oxide. The metal oxide reacts with halogen groups ia the polymer to produce an active iatermediate which then reacts further to produce carbon—carbon cross-links. Ziac chloride is Hberated as a by-product and it serves as an autocatalyst for this reaction. Magnesium oxide is typically used with ZnCl to control the cure rate and minimize premature cross-linking (scorch). 

At temperatures near the critical temperature, many organic degradation reactions are rapid. Halogenated hydrocarbons loose the halogen in minutes at 375°C (38). At temperatures typical of nuclear steam generators (271°C (520°F)), the decomposition of amines to alcohols and acids is well known (39). The pressure limits for the treatment of boiler waters using organic polymers reflect the rate of decomposition. 

Caprolactam is an amide and, therefore, undergoes the reactions of this class of compounds. It can be hydrolyzed, Ai-alkylated, O-alkylated, nitrosated, halogenated, and subjected to many other reactions (3). Caprolactam is readily converted to high molecular weight, linear nylon-6 polymers. Through a complex series of reactions, caprolactam can be converted to the biologically and nutritionally essential amino acid L-lysine (10) (see Amino acids). 

Fiber-Reactive Dyes. These dyes can enter iato chemical reaction with the fiber and form a covalent bond to become an iategral part of the fiber polymer. They therefore have exceptional wetfastness. Thein main use is on ceUulosic fibers where they are appHed neutral and then chemical reaction is initiated by the addition of alkaH. Reaction with the ceUulose can be by either nucleophilic substitution, using, for example, dyes containing activated halogen substituents, or by addition to the double bond in, for example, vinyl sulfone, —S02CH=CH2, groups. 

Cross-linking reactions for the polyisobutylene-type polymers depend on adding a reactive site, usually an aHyUc hydrogen or halogen. These reactive sites allow vulcanization with sulfur and accelerators or metal oxides (76,77). 

Vulcanization oi cuting is accomplished via chemical cioss-linking reactions involving allyhc hydrogen or halogen sites along the polymer backbone to... 

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