Halogenated polymethacrylates

Table II. Photoelectric Mass Absorption Coefficients of the Halogenated Polymethacrylates and of PMMA...

Polymers with saturated carbon chain backbone include polyolefins, polystyrenes, halogenated polyolefins, halogenated polystyrenes, polyvinyls substituted with various groups such as -OH, -OR, -0(0)C-R, -C(0)0-R, -C(0)-R, -C5H4N, etc. In this class also are included polyacrylates, polymethacrylates, polymers with ketone groups in the backbone, as well as other polymers with saturated carbon chain backbone. The polymers with a saturated carbon chain backbone form the most important and common class of polymers. 

It had been known that PMMA was compatible with PVC under some conditions, but contrary to earlier reports it has recently been found that a wide range of polyacrylates and polymethacrylates show compatibility with PVC. Such polymers are believed to be compatible due to a specific interaction between the carbonyl group in the ester and the hydrogen or halogen in the PVC. Similarly, it was known that poly(vinylidene fluoride) was compatible with PMMA and poly(ethyl methacrylate), it has now also been shown to be compatible with poly(vlnyl acetate), poly(vinyl methyl ketone), and polyacrylates. This work has also been extended to show the effect of tacticity on the compatibility of poly(ethyl methacrylate) where ail isomers are compatible but the isotactic form phase separates on heating."... 

Of particular relevance to ATRP are alkyl halides that structurally resemble the halogen-terminated polymer chains, i.e., the dormant species. Some of these alkyl halides (see Figure 8.5) include 1-phenylethyl halides (1-PhEtX), 2-halopropionate esters (R-XP, where R = alkyl or aryl), 2-halopropionitriles (XPN), and 2-haloisobutyrate esters (R-XiB, R = alkyl or aryl) that mimic the chain ends of halogen-capped polystyrenes, polyacrylates, polyacrylonitrile, and polymethacrylates, respectively (in all cases, X = C1, Br). Some other important initiators include methacrylate-type dimers ((R-MA)2X, which are better models of X-capped polymethacrylates than R-XiB), arenesulfonyl halides (ArS02X, e.g., 4-methylbenzenesulfonyl (tosyl) chloride, which is often used in the polymerization of methacrylates and acrylonitrile ), 2-halophenylacetate esters (R-XPA), and 2-halo-2-methylmalonate esters (RR XMM, suitable in the polymerization of methacrylates under low-catalyst-concentration conditions ). 

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