Vinyl Polymers

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  • Vinyl polymers are a group of polymers derived from vinyl monomers

  • Their backbone is an extended alkane chain, made polymerizing an alkene group (C=C) into a chain (..-C-C-C-C-..). In popular usage, "vinyl" refers only to polyvinyl chloride (PVC).

  • Vinyl polymers are the most common type of plastic.

  • For amorphous polymers, the transition from liquid-like to glass-like behavior is called the glass transition.

  • There are several means to modify polymers properties, viz. blending, grafting, and curing.

  • Blending is the physical mixture of two (or more) polymers to obtain the requisite properties.

  • Grafting is a method wherein monomers are covalently bonded (modified) onto the polymer chain

  • Whereas in curing, the polymerization of an oligomer mixture forms a coating which adheres to the substrate by physical forces.

  • Curing gives a smooth finish by filling in the valleys in the surface.

  • In rubber/elastomer industries, crosslinking is the most important reaction of vinyl polymers
    •Vulcanization: using peroxide, sulfur or sulfur containing compounds
    •Free radical reactions by ionizing radiation
    •Photolysis involving photo sensitive funcitonal groups
    •Chemical reactions of labile functional groups

  • Photoinitiated free radical polymerization consists of four distinct steps:
    1. Photoinitiation: Absorption of light by a photosensitive compound or transfer of electronic excitation energy from a light absorbing sensitizer to the photo sensitive compound. Homolytic bond rupture leads to the formation of a radical, that reacts with one monomer unit.
    2. Propagation: Repeated addition of monomer units to the chain radical produces the polymer backbone.
    3. Chain transfer: Termination of growing chains by hydrogen abstraction from various species (e.g., from solvent) and concomitant production of a new radical capable of initiating another chain reaction.
    4. Termination: Chain radicals are consumed by disproportionation or recombination reactions.

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