Bromine styrene polymerization

Brominated Styrene. Dibromostyrene [31780-26 ] is used commercially as a flame retardant in ABS (57). Tribromostyrene [61368-34-1] (TBS) has been proposed as a reactive flame retardant for incorporation either during polymerization or during compounding. In the latter case, the TBS could graft onto the host polymer or homopolymerize to form poly(tribromostyrene) in situ (58). 

A combination of metallocene-catalyzed syndiospe-cific styrene polymerization and the metal-catalyzed radical polymerization affords various graft copolymers consisting of syndiotactic polystyrene main chains (G-8).433 The reactive C—Br bonds (7—22% content) were generated by bromination of the polystyrene main chain with AZ-bromos uccimid e in the presence of AIBN. 

Figure 3. Effect of brominated additives on styrene polymerization...

Copolymerizations are powerful ways to produce polymers with speeifie properties with well defined strueture. However, they involve the costly modification of existing production facilities of polystyrenes. To satisfy small market niches, modified polystyrenes ean be obtained through grafting reactions by chemical reactions on a polymer melt in an extruder (reactive extrusion) to achieve functionalities on the polymeric chains. Thus, grafting reactions are the preferred methods to achieve functionality commercially because they are low cost alternatives to the eopolymerization processes despite low grafting efficieney. For example, polystyrenes have been grafted with brominated styrene to enhanee the flame resistance of polystyrenes, as shown in Reaction 13. 

Around 8% bromine content in the final PBT compound is sufficient to achieve the V-0 test rating for all types of brominated flame retardants, but some affect the physical and mechanical properties of the resultant materials more than others. Polymeric brominated styrene additives would be preferred in glass-filled compounds. Brominated polystyrene, such as Saytex HP-7010 from Albemarle Corp. and poly(dibromostyrene) are such materials. They retain excellent properties after heat ageing. High impact strengfti and excellent electrical properties are especially noted for HP-7010 due to the additive s high purity and low aliphatic halogen content. 

The selection of appropriate polymeric bromine reagent according to the polymeric structure (step of crosslinking, porosity, step of dilution with styrene, granulation, type of heterocyclic ring incorporated, numbers of N) is very important. From production point of view the use of polymeric reagents reduces the costs for solvents and working hours. 

The same heterobifunctional initiator, 2-phenyl-2-[(2,2,6,6-tetramethy-piperidino)oxy] ethyl 2-bromo-2-methyl propanoate, was employed for the synthesis of PMMA-fo-PfBuA-fo-PS triblock terpolymers via the combination of ATRP and NMP [136]. Styrene was initially polymerized through the alkoxyamine function in bulk at 125 °C, leading to PS chains with bromine end groups. Subsequent addition of fBuA in the presence of CuBr/PMDETA provided the PS-fr-PfBuA diblock. Further addition of CuCl, to achieve halogen exchange and MMA yielded the desired triblock copolymer with... 

Troth (32) has studied the polymerization of vinyl acetate in the presence of triphenylmethane and observed the effects discussed above. In practice, there are complications resulting from reactions involving the initiator radicals and the transfer agent. These complications were found also when carbon tetrabromide was used as a transfer agent in the polymerization of styrene in this case, the bromine contents of the polymers were determined by neutron activation analysis (17). 

Photolysis of this polymer gives radicals on which side chains can be formed, giving graft polymerization 122, 123, 153). Similarly the polymerization of styrene (152) or vinyl acetate (157) in the presence of bromotrichloromethane gives telomers carrying terminal bromine atoms and trichloromethyl groups. By ultraviolet irradiation (3500 A) in the presence of methyl methacrylate the carbon-bromine links are broken and block copolymers are formed. The telomerization of acrylonitrile and acrylic acid with bromoform is based on the same technique the end groups of both polyacrylonitrile and polyacrylic acid were photolyzed in the presence of acrylamide and afforded polyacrylamide blocks linked to polyacrylonitrile or polyacrylic acid blocks (164, 165). 

Polymerizable surfactants capable of working as transfer agents include thiosulfonates, thioalkoxylates and methyl methacrylate dimer/trimer surfactants. Thioalkoxylates with 17-90 ethylene oxide units were produced from ethoxylated 11 bromo-undecanol by replacing the bromine with a thiol group via the thiazonium salt route [8]. In the presence of water-soluble azo initiator the thio ended Transurfs (used at a concentration above the CMC) gave monodispersed latex particles in emulsion polymerization of styrene. However, the incorporation of the Transurf remained low, irrespective of the process used for the polymerization (batch, semibatch, seeded). The stability of the lattices when the surfactant and the transfer function were incorporated in the same molecule was better than when they were decoupled. 

The accelaration of styrene photopolymerization by oxygen is also explained by excitation of the DA complex of these two substances [82], A copolymer is produced which decomposes upon illumination [83]. Polymerization of methyl methacrylate is initiated by the photoexcited complex of the monomer with triethylaluminium [84]. Methyl methacrylate, acrylonitrile and acrylates in general readily produce unstable DA complexes which decompose to products quite different from the initial components. Methyl methacrylate, for example, polymerizes in the presence of quinoline and bromine. With the monomer, these pairs yield a DA complex which is unstable upon illumination [85a]... 

The most recent work on styrene [102] has been carried out in benzene solution with initiation by boron trifluoride etherate, BF3 0(C2H5)2. An accurate estimate of the number of active centres, [P ], was achieved by a method similar to that used in Saegusa et al. [45] in ring opening polymerizations (see Section 7.1). Reactions were prematurely terminated by addition of 2-bromothiophene, and the bromine content of the polymers produced estimated by radio activation analysis. Application of the simple relationship (which assumes rapid initiation)... 

A similar well-defined graft copolymer consisting of polystyrene main chain and branches (G-7) can be prepared simply via repetition of copper-catalyzed living radical polymerizations.209 Thus, the synthesis starts with the copolymerization of styrene and />(acetoxymethy 1)styrene or />(methoxymethyl)sty-rene, followed by bromination of the substituent into the benzyl bromide moiety, which then initiates the copper-catalyzed radical polymerization of styrene to give graft polymers with 8—14 branches. 

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