Functionalized vinyl monomers

Solvent Evaporation from Solutions of Thermoplastic Polymers. A solution of a copolymer of vinyl chloride (chloroethene) [75-01-4] C2H2CI, vinyl acetate (acetic acid ethenyl ester) [108-05-4] and a hydroxy-functional vinyl monomer having a number average molecular... 

The polymerization of AB -functional vinyl monomers is fundamentally different from the step-growth polymerization of AB2-monomers. Condensation of AB2-monomers results immediately in the formation of hyperbranched polymers since the reactivity of the end-groups are the same, regardless of what type of repeat unit (linear or dendritic) that is formed. 

Johnson LK, Mecking S, Brookhart M, Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium(II) Catalysts, J Am Chem Soc, 118, 267-268 (1996)... 

The Inifer process developed by Kennedy can be used to functionalize vinyl monomers via a cationic route by initiating a polymerization with an alkyl halide-boron trichloride mixture R BCl. The termination by transfer to an alkyl halide leaves a halide-terminated polymer. This can be transformed to a hydroxyl terminal unit via the sequence (1) dehydrohalogenation, (2) hydroboration, and (3) oxidation and hydrolysis (Equation 5.24). These co-functional blocks may be coupled to form diblock copolymers using standard reaction techniques, e.g., diisocyanate will couple cohydroxy and co-amine blocks together. Direct reactions can also occur, and co-acid chlorides combine readily with co-hydroxy units. 

Several studies further utilizing UPy quadmple hydrogen-bonding units have been published by various authors, all utilizing UPy functional monomers copolymerized in various quantities into polymeric backbones. Coates and co-workers developed a UPy functional vinyl monomer that cotrld be copolymerized with 1-hexene by Ni-catalyzed polymerization and were observed to form elastomeric materials whose material properties can be controlled through dissolution in chloroform or toluene or through addition of monovalent UPy units. Long and co-workers described UPy pendant methacrylate monomers that could be... 

Berber H (2012) The S5mthesis. Modification and Characterization of Nano-Sized Emulsion Pol3rmers Using Functional Vinyl Monomers. Phd Thesis, istanbul YUdiz Technical University. 

Johnson, L. K. Mecking, S. Brookhart, M. Copolymerization of ethylene and propylene with functionalized vinyl monomers by palladium(II) catalysts. J. Am. Chem. Soc. 1996,118, 267-268. 

Often it has been possible to prepare the same functionalized polymer by two different methods. For example, the polymer may be prepared by functionalization of a suitably cross-linked styrene polymer, or by copolymerization of preformed (substituted or functionalized) vinyl monomers in the presence of DVB. Typical examples are benzoic acid-group-bearing polymers and triarylphosphine-group-bearing polymers that have been synthesized either by functionalization of styrene polymers or by copolymerization of the respective functionalized monomers (Schemes 2-1 and 2-2). In one case (Guthrie et al., 1971), the monomer was loaded with the reactant, which was supposed to undergo subsequent reaction on the polymer support, and then the resulting preloaded monomer was polymerized. (For more details, see Chapter 6.)... 

Major commercial synthetic specialty polymers are made by chain-growth polymerization of functionalized vinyl monomers, carbonyl monomers, or strained ring compounds. Depending on monomer structure, the polymerization may be initiated free radically, anionically, or cationically. Copolymers or terpolymers with random, alternating, block, or graft sequences can be prepared under appropriate reaction conditions. There are numerous mediods used to prepare specialty polymers in the research laboratory. However, only a few are of commercial interest. Of particular commercial interest is synthesis of specialty polymers in solutions, dispersions, suspensions, or emulsions. 

Abstract The in vitro enzyme-mediated polymerization of vinyl monomers is reviewed with a scope covering enzymatic polymerization of vitamin C functionalized vinyl monomers, styrene, derivatives of styrene, acrylates, and acrylamide in water and water-miscible cosolvents. Vitamin C functionalized polymers were synthesized via a two-step biocatalytic approach where vitamin C was first regioselectively coupled to vinyl monomers and then subsequently polymerized. The analysis of this enzymatic cascade approach to functionalized vinyl polymers showed that the vitamin C in polymeric form retained its antioxidant property. Kinetic and mechanistic studies revealed that a ternary system (horseradish peroxidase, H2O2, initiator fS-diketone) was required for efficient polymerization and that the initiator controls the characteristics of the polymer. The main attributes of enzymatic approaches to vinyl polymerization when compared with more traditional synthetic approaches include facile ambient reaction environments of temperature and pressure, aqueous conditions, and direct control of selectivity to generate functionalized materials as described for the ascorbic acid modified polymers. 

Keywords Biocompatible hydrogels Complex architectures Functionalized vinyl monomers lanus-type dendrimers Modular nature Passerini three-component reaction PEGylation of proteins Photo-responsive polymers Sequence-defined structures Tailor-made materials Ugi four-component reaction... 

We have achieved a variety of living cationic polymerizations on the basis of the two principles for stabilization of the growing car-bocations, either by nucleophilic counternanions or by added bases. These living processes allow us to prepare, by simple procedures and in most cases at room temperature, various types of new polymers from functionalized vinyl monomers, specifically vinyl ethers and styrene derivatives. 

Ananikov VP, Orlov NV, Zalesskiy SS, Beletskaya IP, Khrustalev VN, Morokuma K, Musaev DG (2012) Catalytic adaptive recognition of thiol (SH) and selenol (SeH) groups toward synthesis of functionalized vinyl monomers. J Am Chem Soc 134(15) 6637-6649... 

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