BROMINE CONTAINING COPOLYMER

Goobich, J., and Marom, G., Moisture Absorption by Tetraglycidyl 4,4/-Diaminodiphenyl Methane/4,4 Diamino-diphenyl Sulfone Epoxies Containing Brominated Epoxy Copolymers, Polymer Engineering and Science, vol. 22, 1982, p. 1052. 

The three possible approaches to flame-retardant polyester - additives to the polymer melt, flame-retardant copolymers and topical finishes - have all been used commercially to produce flame-retardant polyester textiles. All the methods employ phosphorous- or bromine-containing compounds as the active flame retardant. 

Homolytic bond cleavage, producing free radicals used in block copolymer formation, has also been reported. One of the first examples was the mastication of natural rubber swollen with methyl methacrylate (9). Photolytic degradation of polystyrene, capped with bromine containing groups (10) or copolymerized with carbon monoxide (11), has also been used in block copolymer preparation. Similarly ultrasonic degradation of homopolymers in the presence of a second monomer has been reported (12). 

Butyl rubber and other isobutylene polymers of technological importance iaclude various homopolymers and isobutylene copolymers containing unsaturation achieved by copolymerization with isoprene. Bromination or chlorination of the unsaturated site is practiced commercially, and other modifications are beiag iavestigated. 

Standard butyl rubber, which is a copolymer of isobutylene with about 2% of isoprene vulcanises in the same manner as natural rubber but, as it only contains a small proportion of polyisoprene, the cross-link percentage is much reduced. It is therefore not possible to make ebonite from a butyl rubber. The same vulcanisation chemistry, with some modifications, applies to ethylene-propylene terpolymers and brominated butyl rubber. 

The residual double bonds of poly(methyl acrylate) have been determined by bromination [9,27]. Bromination is accomplished through the addition of potassium bromide to potassium bromate in acidic medium [9]. Styrene-butadiene copolymers contain residual double bonds. The butadiene content of the copolymer has been determined by an iodine monochloride titration procedure [9],... 

Polystyrene and its divinylbenzene cross-linked copolymer have been most widely exploited as the polymer support for anchoring metal complexes. A large variety of ligands containing N, P or S have been anchored on the polystyrene-divinylbenzene matrix either by the bromination-lithiation pathway or by direct interaction of the ligand with C1-, Br- or CN-methylated polystyrene-divinyl-benzene network [14] (Fig. 7). 

T. Bhaskar, K. Murai, T. Matsui, M.A. Brebu, M.A. Uddin, A. Muto, Y. Sakata, and K. Murata, Studies on thermal degradation of acrylonitrile-butadiene-styrene copolymer (ABS-br) containing brominated flame retardant, J. Anal. Appl. Pyrolysis, 70(2) 369-381, December 2003. 

In all these reactions homopolymerization occurs simultaneously indeed the released bromine atoms induce polymerization of the added monomer, so that the final graft or block copolymer always contains homopolymer. Therefore the method based on the reaction of ceric ions (Ce-IV) with polyvinyl alcohol seems especially attractive ... 

Montenzin, F. Lopez-Cuesta, J. M. Crespy, A. Georlette, P. Flame retardant and mechanical properties of a copolymer PP/PE containing brominated compounds/antimony trioxide blends and magnesium hydroxide or talc, Fire and Materials, 1997, 21(6), 245-252. 

Brominated styrene grafted onto PET is capable of acting as a nonvolatile FR for PET fabrics [328]. Polyphosphate esters can be used as flame retardant plasticizers [204], phosphorus containing moieties act as color improvers and thermostabilizers in polyesters [198, 205]. Antistatic properties of copolymers containing moieties with sulfonic acids have been reported [107]. Some polymers, like poly(JV-vinylimidazole) impart anticorrosive and antirusting properties to protective coatings of metals [329]. 

The properties of such apparently soluble materials differed greatly from those containing stabilized polyacetylene crystallites. Attempts to dope the soluble copolymers yielded materials with low conductivities, and chemistry typical of solution chemistry (bromination) was observed rather than the formation of a stable bromine-doped polyacetylene phase. A poly(isoprene-fo-acetylene) copolymer oxidized with iodine gave conductivities as high as 1-10 S/cm, but the characterization of the copolymer was insufiScient to unambiguously identify it as a soluble copolymer. On the basis of previously reported work, this material is likely to correspond to a stabilized suspension rather than a solution. 

The photodegradable resin comprises a styrene-diene copolymer containing 0.1—10% by weight of butadiene or isoprene and >0.001% by weight of > 1 of the transition-metal salts together with a brominated aliphatic hydrocarbon... 

Butyl rubber consists mostly of isobutylene (95-98%) and about 2-5% isoprene units. 1 The isoprene unit is halogenated by either chlorine or bromine to obtain the corresponding halobutyl rubbers. Despite the superior elastomeric properties of halobutyl, the elastomer can easily undergo dehydrohalogenation leading to crosslinfang, and the isoprene unsaturation is subject to ozone cracking. To remedy these problems and to improve the halobutyl properties, a new class of elastomer poly(isobutylene-co-p-methylstyrene) [poly (IB-PMS)] was developed. Unlike butyl rubber, it contains no double bonds and therefore cannot be crosslinked unless otherwise functionalized. The chemical structures of butyl rubber and poly (IB-PMS) copolymers are shown below. 

Hence, the insensitivity to addition sequence for styrene and (AA) monomers makes it relatively easy to form (PS-fc-PAA), (PS-fc-PAA-fc-PS), and (PAA-Z -PS-Z -PAA) di- and tiiblock copolymers. However, when AN and MMA are involved, the poly(acrylonittile) block must be formed first, i.e., second monomer addition should be in the order shown in the preceding text. Unlike NMP methods, the use of ATRP presents no major problems when preparing block copolymers containing acrylates and methacrylates. Triblock (ABC) copolymers can be prepared by starting with a bromine-terminated polystyrene macroinitiator to polymerize Z-butyl acrylate, followed by methyl acrylate or methyl methacrylate using a CuBr/pentamethyl diethylene triamine catalyst. 

Kim YB, Lenz RW, Clinton Fuller R (1992) Poly(hydroxyalkanoate) copolymers containing brominated repeating units produced by Pseudomonas oleovorans. Macromolecules 25 1852-1857... 

---