Phenyl polymerizability

Vinylphenyl-terminated PBE dendrons were prepared as polymerizable den-drons from 4-vinylbenzyl chloride [37]. The vinylphenyl-terminated PBE dendrons are useful to make the lanthanide-cored dendrimer complexes polymerizable. The Ist-generation Tb +-cored dendrimer complex bearing the vinyl-phenyl terminal on the dendron subunits (Fig. 5) was copolymerized with N-iso-propylacrylamide in the presence of methylene bis-acrylamide (as crosslinker) in DMSO to give a green-luminescence transparent gel. The DMSO gel was con-... 

Poly(azophenylene-o-carborane) (see 6) has been prepared from diphenyl-o-carborane by means of nitration, reduction, and acylation to initially give 1,2-bis(/ -nitroso-acetylaminophenyl)-o-carborane (NAFC). Rapid decomposition in solution affords phenylene amino phenyl carborane (PAFC) by recombination of phenylene and azophenylene radicals.40 These radicals have also been utilized to form copolymers of carborane-containing copolymers from monomers polymerizable via radical mechanisms. Thus, copolymers of polystyrene and poly(azophenylene) can be readily formed by means of emulsion copolymerization of styrene with NAFC decomposition products. 

Synthetic utilization of non-(homo)polymerizable diolefins has been first shown for the coupling reaction of living PIB [69, 70]. Using 2,2-bis[4-(l-phenylethenyl)phenyl]propane (BDPEP) or 2,2-bis[4-(l-tolylethenyl)phe-nyl]propane (BDTEP) as a coupling agent (Scheme 6), a rapid and quantita-... 

Cationic polymerizations induced by thermally and photochemically latent N-benzyl and IV-alkoxy pyridinium salts, respectively, are reviewed. IV-Benzyl pyridinium salts with a wide range of substituents of phenyl, benzylic carbon and pyridine moiety act as thermally latent catalysts to initiate the cationic polymerization of various monomers. Their initiation activities were evaluated with the emphasis on the structure-activity relationship. The mechanisms of photoinitiation by direct and indirect sensitization of IV-alkoxy pyridinium salts are presented. The indirect action can be based on electron transfer reactions between pyridinium salt and (a) photochemically generated free radicals, (b) photoexcited sensitizer, and (c) electron rich compounds in the photoexcited charge transfer complexes. IV-Alkoxy pyridinium salts also participate in ascorbate assisted redox reactions to generate reactive species capable of initiating cationic polymerization. The application of pyridinium salts to the synthesis of block copolymers of monomers polymerizable with different mechanisms are described. 

With a view to preparing polymerizable complexes, thiophene-substituted nickel-dithiolene complexes [Ni(L)(L )] have been synthesized and used to prepare films by electrochemical polymerization. The features of the complexes and of the polymers depend on the number of thiophene substituents. In particular, the complex with four thiophene substituents (L = L = thpdt, 12) shows a narrower HOMO-LUMO gap as compared to complexes with two thiophene and two phenyl groups or four phenyl groups [Xmax, nm (e, M- cm- ) 976 (38800) L = L = 12 931 (37700) L = 12, L = 9, R = Ph 866 (30900) L = L = 9, R = Ph] and gave a polymer whose electrochemical features are similar to those of poly[l,2-di(2,5-thienylene)ethane], suggesting that similar extended chains are formed"". 

Some other interesting copolymers having properties of PVC thermal stabUizers, like poly[Af-(a-benzothiazolonylmethyl)methacrylate-co-methyl methacrylate] [45], of flame retardants like a terpolymer of styrene, acrylonitrile and a polymerizable perbrominated phenol [76] or poly[4-methacryloyloxy-2,3,5,6-tetrabromobenzyldi-phenyl phosphonate-co-methyl methacrylate] [104] (93), bioddes, mostly copolymers of monomers containing tris(n-butyl tin) or triphenyl tin moieties and alkyl acrylates, methacrylates, vinyl acetate, acrylonitrile, styrene or A-vinylpyrrolidone [105], e.g. a terpolymer of styrene, MMA and tri(n-butyl tin) itaconate [106] (94),... 

Alkenyl- and alkynyl-triazoles have received little attention. By analogy with the behaviour of other azoles they are expected to polymerize but to be less reactive in addition reactions than alkenes or alkynes. Although the most promising polymers derived from triazoles are obtained by different methods (see Section 4.12.5.2.3), some information is available on potentially polymerizable vinyltriazole (63MI4120i). The styryltriazole (134) could be oxidized to 3-methyl-l-phenyl-l,2,4-triazole, i.e. without affecting either the triazole or iV-phenyl ring, but hydroxylation of the alkene chain failed (s4JCS4256). 

Fu, S. Gupta, A. Albertsson, A.C. Vogl, O. New polymerizable 2(2-hydroxyphenyl)2H-benzotria-zole ultraviolet absorbers 2[2,4-dihydroxy-5-vinyl (isopropenyl)phenyl]2,3-2H-dibenzotriazole. In Ne w Trends in the Photochemistry of Polymers, Allen, N.S., Rabek, J.F., Eds. Elsevier Applied Science London, 1985 247-264. 

Monomers Not Polymerizable by Plasma Initiation. When styrene and a-methy1styrene were subjected to plasma treatment, the monomers became yellowish and only trace amounts of insoluble films were formed. The discoloration was intensified and extensive formation of dark films were observed if carbon tetrachloride was added as the solvent. No post-polymerization was detectable for these monomers. Generally styrene and a-methylstyrene readily undergo thermal polymerization. However, no thermal polymerization was possible for these monomers after having been subjected to plasma treatment for one minute or less. It has been demonstrated from the emission spectra of glow discharge plasma of benzene (6) and its derivatives (7 ) that most of the reaction intermediates are phenyl or benzyl radicals which subsequently form a variety of compounds such as acetylene, methylacetylene, allene, fulvene, biphenyl, poly(p-phenylenes) and so forth. It is possible that styrene and a-methylstyrene also behave similarly, so that species from the monomer plasma are poor initiators for polymerization. 

Polymerizable Ultraviolet Stabilizers — Miscellaneous Types. In our research on polymerizable ultraviolet stabilizers, we have decided to prepare styrene-type monomers in which the vinyl (or isopropenyl) group is directly attached to the phenyl group of the stabilizer, which might be polymerized similarly to styrene. These monomers can indeed be polymerized and copolymerized successfully with styrene, acrylic and methacrylic acid derivatives with azobisisobutyronitrile (AIBN) as the radical initiator (12-Ut-). 

ETHER, ETHYL PHENYL (103-73-1) CgHjoO CgHsOCiHs Combustible polymerizable liquid (flash point 145°F/63°C). Able to form unstable and explosive peroxides strong acids or other initiators may cause exothermic polymerization. Violent reaction with strong acids, strong oxidizers, ammonium persulfate, bromine dioxide, acyl halides, permanganates, peroxides. On small fires, use dry chemical powder (such as Putple-K-Powder), alcohol-resistant foam, or CO2 extinguishers. 

ETHYL PHENYL ETHER (103-73-1) CjHjoO CjHsOCjHs Combustible polymerizable liquid (flash point 145°F/63°C). Able to form unstable and... 

METHYL-l-PHENYL-ETHYLENE (98-83-9) C9H10 Flammable liquid. Forms explosive mixture with air [explosion limits in air (vol %) 0.9 to 6.1 flash point 129°F/54°C autoignition temp 1066°F/574°C Fire Rating 2], Easily polymerizable. Unless inhibited, forms unstable peroxides. Reacts with heat and/or lack of appropriate inhibitor concentration. Reacts with catalysts for vinyl or ionic polymerization, such as aluminum, iron chloride or 2,5-dimethyl-2,5-di(ieri-butylperoxy)hexane. Violent reaction with strong oxidizers, butyl lithium, oleum, xenon tetrafluoride. Incon atible with acids. The uninhibited monomer vapor may block vents and confined spaces by, forming a solid polymer material. Attacks aluminum and copper. On small fires, use dry chemical powder (such as Purple-K-Powder), foam, or CO2 extinguishers. 

Instead of acryloyl chloride or methacryloyl chloride, the glycidyl esters are used for functionalization with polymerizable compounds. Such a compound is 2-[2-hydroxy-4-alkoxy-(2-oxypropyl methacrylate)phenyl]-2H-4-methoxybenzotriazoIe, as shown in Figure 9.9. It is prepared by the reaction of 4-(5-methoxy-2H-benzotriazole-2-yl)resorcinol with glycidyl methacrylate. Tetrabutylammonium bromide is used as a catalyst and hy-droquinone is used as a polymerization inhibitor. 

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