Chloromethylstyrene

Polymer-type antioxidants have been prepared by Eriedel-Crafts reaction of -cresol andp- and/or y -chloromethylstyrene in the presence of boron trifluoride-etherate (198). The oligomeric product resulting from the alkylation of phenyl-a-naphthylamine using C12—15 propylene oligomer in the presence of AlCl or activated white clays is used as an antioxidant additive for lubricating oils (199). 

ACPA azobis(4-cyanopentanoic acid) AIBN azobis isobutyronitrile) BPO benzoyl peroxide DVB divinyl benzene, EGA 2-ethylcyano-acrylate HPC hydroxypropyl cellulose MMA methyl methacrylate PAAc polyacrylic acid PEI polyethyleneimine, PEO/PPO polyethylene oxide/polypyropylene oxide copolymer PVME polyvinylmethylether PVP polyvinylpyrrolidone K-30 DMSO dimethylsulfoxide PGA polyglutaraldehyde CMS chloromethylstyrene PMMA-g-OSA polymethylmethacrylate grafted oligostearic acid. 

DSEP direct soapless emulsion polymerization, SSEC seeded soapless emulsion copolymerization, DDC direct dispersion copolymerization, TDSC two-stage dispersion copolymerization, ATES Allyl trietoxysilane, VTES vinyl trietoxysilane, DMAEM dimethylaminoethyl-methacrylate, CMS chloromethylstyrene, GA glutaraldehyde, AAc Acrylic acid Aam Acrylamide HEMA 2-hydroxyethylmethacrylate. 

Various substituted styrenes have been also polymerized by NMP. These include 1 03-1 07, p-chloromethylstyrene (108), p-halostyrenes, and p-aceloxystyrene. Vinyl pyridines (e.g. 109) are amenable to NMP21 and may be quaternized post-polymerization to provide water-soluble polymers. 

A combination of TEMPO living free radical (LFRP) and anionic polymerization was used for the synthesis of block-graft, block-brush, and graft-block-graft copolymers of styrene and isoprene [201]. The block-graft copolymers were synthesized by preparing a PS-fo-poly(styrene-co-p-chloromethylstyrene) by LFRP [Scheme 110 (1)], and the subsequent re-... 

The living radical polymerization of some derivatives of St was carried out. The polymerizations of 4-bromostyrene [254], 4-chloromethylstyrene [255, 256], and other derivatives [257] proceed by a living radical polymerization mechanism to give polymers with well-controlled structures and block copolymers with poly(St). The random copolymerization of St with other vinyl... 

Liquid phase graft copolymerization with chloromethylstyrene and styrene... 

Authors thank Seimi Chemical Co. Ltd. for a gift of chloromethylstyrene and Mitsubishi Chemical Co. Ltd. for a gift of Diaion CRP200. We also acknowledge Ms. Ayumi Meakawa for her help in measurement, and Dr. Shoji Aoki, Mr. Mitsuhiro Nakao for their help in graft polymerization. 

POLY (TRIM ETHYLS ILYLMETHYL METHACRYLATE-CO-CHLOROMETHYLSTYRENE)... 

Grafting of these preformed monoliths with dormant radicals is achieved by filling the pores with a monomer solution and heating to the desired temperature to activate the capped radicals. For example, a functionalization of poly(styrene-divinylbenzene) monolith with chloromethylstyrene and vinyl-pyridine to obtain material with up to 3.6 mmol/g of functionalities has been demonstrated [88]. 

Method C. (tri-phase catalysis) NaCN (0.6 g) in H20 (1 ml) and the haloalkane (0.6 mmol) in PhMe (1 ml) are shaken for 2 min with the quaternary ammonium resin (74 mg), obtained by reaction of Me2BuN with poly-4-chloromethylstyrene. The mixture is kept at 110°C for ca. 5.5 h and it is then filtered and extracted with CH2C12 (3 x 10 ml). The dried (MgS04) extracts are evaporated to yield the nitrile. 

Materials. A series of a,to-bis(hydroxyphenyl)PSU oligomers with different molecular weights were synthesized and characterized as was previously reported (12). Two samples of PPO (one from Aldrich and one from General Electric Co.) were both purified by precipitation from chloroform solution into methanol. A commercial sample (Dow Chemical) of an isomeric mixture of chloromethylstyrenes (C1MS, 40% para, 60% meta) was used as received. 1-Chloromethoxy-4-chlorobu-tane (CMCB) was prepared according to a procedure developed by Olah et al. (14) and modified by Daly et al. (15), i.e., from paraformaldehyde, tetrahydrofuran and anhydrous HC1. 

Figure 35. The normalized change in thickness remaining after development vs storage time after exposure for COP resist and poly (chloromethylstyrene). The styrene analog shows little or no ""dark-...

Figure 36. Effect of change in molecular weight at constant dispersity on the e-beam sensitivity of poly (chloromethylstyrene), PCMS. (Reproduced with permission from Ref 47 J...

Finally, the lithiation of a soluble chloromethylated polystyrene 16 (prepared by AIBN-indnced copolymerization of styrene and 4-chloromethylstyrene in a 3 1 molar ratio) with lithinm and a catalytic amonnt of DTBB (10%) in THF at —78 °C gave the expected... 

Kenawy 64) immobilized ammonium and phosphonium peripheral functionalized dendritic branches on a montmorillonite supported chloromethylstyrene/methyl methacrylate copolymer (74-75). These polymer/montmorillonite-supported dendrimers were used as phase transfer catalysts (PTC) for the nucleophilic substitution reaction between -butyl bromide and thiocyanate, cyanide, and nitrite anions in a toluene or a benzene/water system. These PT catalysts could be recycled by filtration of the functionalized montmorillonite from the reaction mixture. Generally,... 

When the polymeric initiator contains many halogens, there will be many grafted side chains, and the product is called a comb or brush polymer. A variety of polymers can be used as the polymeric initiator, including polymers containing vinyl chloride and 4-chloromethylstyrene units, and halogenated natural and butyl rubbers. Graft copolymers are discussed further in Chaps. 5, 6, and 9. 

Various halogenated polymers are used as the polymeric initiator for ATRP, for example, vinyl chloride-vinyl chloroacetate and styrene-p-chloromethylstyrene copolymers, bromi-nated butyl rubber, and chlorosulfonated polyethylene [Bomer and Matyjaszewski, 2002 Coskun and Temuz, 2003], (The vinyl chloride units have much lower reactivity for ATRP compared to the vinyl chloroacetate units because of steric reasons.) The density of grafting is adjusted by varying the copolymer composition. 

Using the grafting-from method with NMP requires the synthesis and (co)polymerization of monomers that contain the nitroxide group [Hawker et al., 2001]. A halogen-containing monomer such as vinyl chloroacetate or p-chloromethylstyrene is reacted with an HO-containing alkoxyamine to yield a vinyl alkoxyamine, which is used as a NMP initiator to... 

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