Principles and process of polymerisation in plastics production

Condensation polymerisation and addition polymeri­sation are the two main processes in plastics production. The manufacture of plastics depends upon the building of chains and networks during polymerisation.

A condensation polymer is formed by a synthesis that involves the gradual reaction of reactive molecules with one another, with the elimination of small molecules such as water. The reaction gradually slows down as polymers are built up.

An addition polymer forms chains by the linking of small identical units without elimination of small mol­ecules.

The most important concept in condensation polymers is that of «functionality», i.e., the number of reactive groups in each molecule participating in the chain build­up. Each molecule must have at least two reactive groups, of which hydroxyl (-OH), acidic endings (-COOH), and amine endings (-NH) are the simplest.

Hydroxyl is characteristic of alcohol endings, combin­ing with an acid ending to give an ester, the polymer be­ing known as a polyester. Examples are polyethylene terephthalate obtained by reaction of ethylene glycol con­taining hydroxyl groups at each end and terephthalic acid containing two acidic groups and polycarbonate resins.

Alcohols are a particular class of oxygen-containing chemical compounds with a structure analogous to ethyl alcohol (C-HOH). Amines are various compounds derived from ammonia by replacement of hydrogen by one or more hydrocarbon radicals (molecular groups that act as a unit). Esters are compounds formed by the reaction between an acid and an alcohol or phenol with the elimi­nation of water.

Bulk addition polymerization of pure monomers is mainly confined to styrene and methyl methacrylate The process is highly exothermic, or heat producing. The dis­sipation of heat (necessary to maintain chain length) is achieved in the case of styrene by intensive stirring of the viscous, partially polymerized mixture, which is then passed down a tower through zones of increasing tem­perature. Alternatively, polymerization may be com­pleted in containers that are small enough to avoid an excessive temperature rise as a result of the heat released during polymerization.

Methyl methacrylate is also partially polymerized be­fore being poured into molds consisting of between sheets of plate glass, to produce clear acrylic sheet.

Ethylene is polymerized in tubular reactors about 30 metres long and less than 25 millimetres in diameter at pressures of 600-3, 000 to give 10-20 percent conver­sion to low-density polyethylene. Residual gas is recy­cled.

Polymerization of monomers in solution allows easy temperature control, but the molecular weight of poly­mers formed is reduced because of chain transfer reac­tions

Solvent removal from such a solution may also be very difficult. The process can be applied advantageously to vinyl acetate and acrylic esters.

Suspension polymerization producing beads of plas­tic is extensively applied to styrene, methyl methacr­ylate, vinyl chloride, and vinyl acetate. The monomer, in which the initiator or catalyst must be soluble, is main­tained in droplet form suspended in water by agitation in the presence of a stabilizer such as gelatin, each drop­let of monomer undergoing bulk polymerization.

In emulsion polymerization the monomer is dispersed in water by means of a surface-active agent (a substance slightly soluble in water that reduces the surface tension of a liquid), its bulk aggregating into tiny particles held in suspension. The monomer enters the hydrocarbon part of the surface-active micelles and is polymerized there by a water-soluble catalyst.

This process is particularly useful for the preparation of very high molecular weight polymers.

Exposure of certain substances to X-ray or ultravio­let radiation initiates chain reactions that can be used for manufacture of such thermoplastics as polyethylene and polyvinyl chloride.

RESINS

Resins that cannot be softened by heating include the phenolics, furan resins, aminoplastics, alkyds, allyls, epoxy resins, polyurethanes, some polyesters, and silicones.

Phenolics or phenol-aldehydes

The important commercial phenolic resin Bakelite is based on phenol and formaldehyde. The two processes in general use are the one-step process producing resol res­ins (the first stage in the formation of a phenolic resin) that are either liquid or brittle, soluble, fusible solids, from more than one molecule of formaldehyde per phe­nol molecule; and the two-step process, using an excess of phenol to produce novolacs, resins that have no reac­tive methylol groups and must be mixed with an alde­hyde to undergo further reaction.

Resol resins thermoset on heating and are used for adhesives. Novolacs require a further source of formal­dehyde in the form of hexamethylenetetramine to pro­duce molding powders. Both resins are run out from the reaction vessel, after removal of water by distillation, and ground up, then compounded on heated rolls with fillers that vary from wood flour to mica; for strength and heat resistance fibrous asbestos is used as a filler (hexamethylenetetramine is also added at this stage in the case of the two-step resin). Final grinding produces the molding powders, which on further heat treatment will yield the typical thermoset resin.

Phenolic moldings are resistant to heat, chemicals, and moisture and are preferred for wet-dry applications as in washing machines. Their stability to heat and low heat conductivity suit them for use in appliance parts, and their electrical insulation qualities qualify them for electric fittings such as switches, plugs, and distributor caps; resistance to hydraulic fluids has led to their use in automotive parts. All these applications have been made more economical by the development of injection molding and extrusion methods. Complex phenols are used in manufacture of brake linings.

Furan resins

Furfural is a five-membered ring compound (i.e., the basic molecule has a ring shape and contains five atoms) of four carbon atoms and one oxygen atom, carrying the aldehyde group, — CHO; it reacts like formaldehyde with phenols in the presence of an acid catalyst to give a rigid polymer with high chemical resistance, used for coatings in industry. It can be prepared in semiliquid form with a low viscosity and remarkable penetrating power when applied to porous forms such as foundry sand cores or graphite blocks, being in this respect superior to other liquid resins.

Aminoplastics

Urea resins are made by the condensation in aqueous solution of formaldehyde and urea in the presence of ammonia as an alkaline catalyst, giving a colourless so­lution to which cellulose filler is added to yield a molding powder upon drying, which when heated in a mold gives a water-white (transparent) molding unless previously coloured by pigment.

The filler confers considerable strength, so that thin sections such as in cups and tumblers can be molded. Very large quantities of urea-formaldehyde resin are used in kitchen and bathroom hardware details, and electric ap­pliance housings and fittings.

Melamine behaves in the same way as urea, but the prod­uct is more moisture resistant, harder and stronger, lead­ing to wide use for plates and food containers. Melamine moldings are glossy and harder than any other plastic and retain a dust-free surface. Solutions of the thermoplastic forms of urea-formaldehyde resins are widely used as bonding agents for plywood and wood-fibre products.

Alkyds

Alkyds are polyesters, generally of phthalic acid (with two acid groups) and glycerol, a triol — i. e., an alcohol with three hydroxyl groups. The solid resins are molded at high speed under low pressure, cured quickly, and are used where insulating properties, strength, and dimen­sional stability over a wide range of voltage, frequency, temperature, and humidity are required, as in vacuum-tube bases and automotive ignition parts and with glass-fibre reinforcement for switch gear and housings for portable tools.

Polyesters of unsaturated alcohols

The resins known as DAP and DAIP, are crossliked allyl esters of phthalic and isophthalic acid, respectively. They are notable for maintaining rigidity and excellent electrical properties at temperatures up to 230 С, prорerties also manifested by allylic resin-impregnated glass cloth, used in aircraft and missile parts. Other advan­tages are good storage life and absence of gas evolution during polymerization. The resin allyl diglycol carbon­ate, optically clear and colourless, is used for making cast objects; fully cured castings are more heat and abrasion resistant than other cast resins.

Epoxy resins

Epoxy resins have outstanding mechanical and elec­trical properties, dimensional stability, resistance to heat and chemicals, and adhesion to other materials. They are used for casting, encapsulation, protective coat­ings, and adhesives, and for reinforced moldings and laminates of the highest quality. Popular adhesives (epoxy glues) contain the resin components and the cur­ing agent, usually an amine or an anhydride, in separate packages. The two are mixed just before use.