ACRYLIC POLYMERS

Polymethyl methacrylate

It is a clear, colorless transparent plastic with a higher softening point, better impact strength, and better weatherability than polystyrene. It is available in molding and extrusion compositions, syrups, and cast sheets, rods and tubes.

 Monomers

The principal commercial processes for the production of acrylate esters are based on ethylene cyanohydrin, the carbonylation of acetylene, or the polymerization and depolymerization of B-propiolactone to give acrylic acid or an acrylate ester.

 Methyl methacrylate is made by heating acetone cyanohydrin

(from the addition of hydrocyanic acid to acetone) with sulfuric acid to form methacrylamide sulfate. OH CH3 l H2SO4 CH3OH l CH3-C-CN--------CH2=CCNH2.H2SO4--------> l 125oC ll H 2O CH3 O CH3 l CH2=CCOCH3 ll O

 Polymerization

Poly methyl methacrylate for molding or extrusion is made by bulk or suspension polymerization. The production of cast sheets, rods, and tubes is carried out by bulk polymerization starting in most cases with a syrup of partially polymerized methyl methacrylate with a convenient viscosity for handling.

Properties Polymethyl methacrylate is a linear thermoplastic, about 70-75% syndiotactic. Because of its lack of complete stereoregularity and its bulky sidegroups, it is amorphous. Both isotactic and syndiotactic polymethyl methacrylate have been prepared but have not been offered commercially. Polymethyl methacrylate is resistant to many aqueous inorganic reagents, including dilute alkalis and acids.

 It is quite resistant to alkali saponification, in

contrast to the polyacrylates. It undergoes pyrolysis almost completely to monomer by a chain reaction. Perthaps the outstanding property of polymethyl methacrylate is its optical clarity and lack of color. Coupled with its unsually good outdoor weathering behavior, its optical properties make it highly useful in all applications where light transmission is important.

 The mechanical and thermal properties of the

polymer are also good. Tensile strength ranges as high as 10,000 psi. Impact strength is about equal to that of the impact-resistant styrene copolymaers. Heat deflection temperatures are above 90 oC for the heat resistant grades of polymethyl methacrylate molding powder. Electrical properties are good but not outstanding. Fabricability is quite good; only slightly higher temperatures are needed fro molding polymethyl methacrylate than for polystyrene. Polymethyl methacrylate is less susceptible to crazing than is polystyrene.

 A limitation to the optical uses of the material

is its poor abrasion resistance compared to glass. Despite considerable effort, attempts to improve the scratch resistance or surface hardness of polymethyl methacrylate have so far been accompanied by deterioration in other properties, such as impact strength.

 Application

Injection-molded acrylic articles include automotive lenses, reflective devices. Instrument and appliance covers, optical equipment, and home furnishings. Acrylic sheeting is used for signs, glazing (in particular, aircraft windows), furniture, partitions, and lighting-fixture diffusers. About 0.5billion of acrylic plastics was sold in 1982.

 Ciopolymers of methyl methacrylate, ethyl

acrylate, and monomers containing reactive functional groups are widely used as thermosetting resins in baked enamel applications. The functionality can be derived from amines (acrylamide, methyl methacrylates or methacrylates).

POLYVINYL CHLORIDE
Monomer Vinyl chloride is a gas boiling at -14oC. It is produced by the dechlorination o9f ethylene dichloride, which is made by reacting ethylene with chlorine. Almost all the vinyl chloride produced is used in polymerization, with greater care being taken throughout because of the carcinogenic nature of the monomer.

 Polymerization

Suspension polymerization is used for the production of well over 80% of polyvinyl chloride. Small amounts are made by solution emulsion, and bulk polymerization, despite difficulties in the latter process resulting from the insolubility of the polymer in its monomer.

 Structure

Polyvinyl chloride is a partially syndiotactic material, with sufficient irregularity of structure that crystallinity is quite low. Its structural characterization is complicated by the possibility of chain branching and the tendency of the polymer to associate in solution.

 Stability

Polyvinyl chloride is relatively unstable to heat and light. Thermal initiation involves loss of chlorine atom adjacent to some structural abnormailty which reduces the stability of C-Cl bond. The chlorine radical so formed abstracts a hydrogen to form HCl; the resulting chain radical then reacts to form chain unsaturation with regeneration of a chlorine radical.

 The reaction can also be initiated by ultra

violet light which is absorbed at unsaturated structures with liberation of an adjacent chlorine atom. In the presence of oxygen, both chain reactions are accelerated, and ketonic structures are formed in the chain.

 Stabilizers are almost invariably added to

improve the heat and light stability of the polymer. Metallic salts of lead, barium, tin, or cadmium are used. Oxides, hydroxides, or fatty-acids are most effective. Epoxy plasticizers aid materially in stabilizing the resin. Free radical acceptance appears to be a prominent mechanism or stabilization.

 Vinyl Resins

a) Rigid compounds the term rigid vinyls usually refer to unplasticized polyvinyl chloride or compositions with only a few percent of a plasticizer such as epoxy resin. Often other polymers are mixed physically with the polyvinyl chloride to improve impact resistance.

 Copolymers

The advantages in polymer properties resulting from the copolymerization of small amounts of vinyl acetate with vinyl chloride were discovered around 1928. The lower softening point and higher solubility of the copolymers make fabrication very much easier. Stability is improved over that of homopolymer, color and clarity are also better. Polymerization methods are similar to those for vinyl chloride homopolymer except that emulsion polymerization has had less success.

 Polymers containing around 10% vinylidene

chloride have better tensile properties than pure polyvinyl chloride. Copolymers containing 10-20% diethyl fumarate or diethyl maleate have improved workablity and toughness and retain the high softening point of polyvinyl chloride. Acrylic esters have also been used to impart improvements in solubility and workability.

 Plasticization

Many properties of polyvinyl chloride and vinyl chloride vinyl acetate copolymers are improved by plasticization. The large majority of commercial production of vinyl resins is in the form of plasticized compositions. The first important plasticizer for the vinyls was tricresyl phosphate, which has since been replaced by other esters because of its tendency to cause low-temperature brittleness in plasticized compounds.

 The plasticizer content varies widely with the

end use of the material, but typically may be around 30% by weight.

 Plastisols and Organisols

These liquid compositions are produced by spray drying lattices obtained from the emulsion polymerization of vinyl chloride. The latex particles are dispersed into plasticizers to make plastisols, or into mixtures of plasticizers and volatile organic liquids to make organisols. Other ingredients such as stabilizers, fillers, colorants, surfactants, and possibly blowing agents or gelling agents are also present. The polymer particles do not dissolve in the liquids, but remain dispersed until the mixture is heated. Fusion plus loss of solvent then yield the final product.

 Application

About 55% of polyvinyl chloride is used as rigid resins, the remainder plasticized. The single largest use, in the rigid field, is pipe, accounting for 40% of production. It is used for water supply distribution, agricultural irrigation, chemical processing, drain, waste, and vent pipe, sewer systems, and conduits for electrical and telephone cables.

 The building construction market accounts for

about another 30% of polyvinyl chloride production, including siding, window frames, gutters, and interior molding and trim (12%); flooring (5%); wire and cable insulation (7%); and wall coverings, upholstery, shower curtains, gaskets, and so on (5%). Automotive uses, meat and food packaging, bottles, footwear, outerwear, phonograph records, sporting goods, and toys are other significant matrkets.

 Properties and Uses

Polyvinyl chloride are insensitive to moisture and have high wrinkle resistance and good resistance to chemicals, insects, fungi, and the like. They have poorer dimensional stability at high temperatures, and somewhat less strength, elasticity, and abrasion resistance.