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Cabral, Charlette A. Francisco, Janine Therese J. Mellendrez, Kristine Jhalene M. Pineda, Jermaine Marianne F.

Plastics
The word plastics is from the Greek word Plastikos, meaning able to be shaped and molded Plastics is a material that contains a polymerized organic substance of large molecular weight as an essential ingredient, is solid in its finished state, and at some stage in its manufacture or its processing into finished articles can be shaped by flow. Toughness Water Resistance Excellent resistance to corrosion Ease of fabrication Remarkable color range

Plastics
Basic Raw Materials:
Coal Petrochemicals Cotton Wood Gas Air Salt Water

Synthetic Resins are the largest source of plastics with Cellulose derivatives ranking next

History of Plastics

Commercial phenolic resin (1990) by Baekland was the start of the synthetic plastic industry. Cellulose Nitrate(Celluloid)
First plastic of industrial significance and was discovered about the middle of the 19th century. First used in 1869 by Hyatt who was searching for an ivory substitute.

History of Plastics

Cellulose Acetate
Developed in 1894 as a less flammable material and was used extensively as a base for photographic film and as a dope for airplane coverings during World War I.

Early History of Polymers


Polymer Year Introduced 1868 1894 1909 1912 1927 1929 1931 1934 1937 1938 1939 1942

Cellulose nitrate Cellulose acetate


Phenol-formaldehyde Cellulose ethers Vinyls Urea-formaldehyde Acrylates Furans Polystyrene Polyamides Melamine-formaldehyde Polyesters

Silicone
Polyethylene Fluorocarbons Epoxy Cystalline polypropylene Phenoxy

1942
1943 1946 1948 1957 1962

Classification of Plastics

Plastics are often divided into:


Thermosetting Thermoplastics Oil soluble Protein products

Classification of Plastics Thermoplastics


Account for the majority of industry output and they solidify by cooling and may be re-melted repeatedly to form new shapes. The process is reversible. Tougher (more impact strength) Less brittle High Tensile elongation High viscosity (when liquid)

Examples include:
Chemical-resistant containers e.g. Food Containers

Hinges

Polypropene/ Polypropylene
Fishing nets Bottle crates Medical equipment e.g. syringes

HDPE: Bottles Pipes Bowls Milk Crates Buckets

Polyethene/ Polyethylene
LDPE: Packaging film Carrier bags TV cable Toys Detergent 'squeezy' bottles

Classification of Plastics Thermosetting plastics


Account for about 12% of output. Unlike thermoplastics, thermosets harden by chemical reaction and cannot be melted and shaped after they are created. More mature and less dynamic segment of the industry. Stronger More brittle Low tensile elongation Low viscosity (in liquid form) Higher temperature resistance The process is irreversible.

Electrical fittings i.e. plugs

Wood adhesives

Textiles i.e. clothing

Urea-Formaldehyde

Coding of Plastics Application:


The Plastics Coding System is designed to be easy to read at a glance and distinguishable from other marks put on rigid plastic containers by manufacturers for use in processing and identification. The system uses a triangular-shaped symbol composed of three arrows, with a number in the centre indicating the material from which the bottle is made, as follows:

Range of Products
Plastics Bags Plastic Packaging Film and Sheet Non-packaging Film and Sheet Plastics Profile Shapes Plastics Pipe & Pipe Fittings Laminated Plate, Sheet and Shape Polystyrene Foam Products Urethane and Other Foam Products Plastic Bottles Plastic Plumbing Fixtures Resilient Floor Covering Plastics Products, Not Classified Elsewhere
(Source: Probe Economics, Inc. 2004)

Engineering Plastics

High-strength high performance materials that can be substituted for many metal uses These materials show better resistance to:
Wear Impact Corrosive chemicals Excellent electrical properties

Engineering Plastics

Some uses:
Automobile bumpers and dashboards Pumps Valves Gears Driveshafts and transmission in heavy-duty equipment

Engineering Plastics

Common resins use:


Acetal Fluoroplastics Nylon Polyphenylene oxide Polycarbonate Polyphenylene sulfide Polysulfone Polyether-imide Polyethersulfone Nylon-polyether block amides Several other copolymers

Raw Materials(Chemical Intermediates and Monomers)

Phenol
The principal process in use in US is the Peroxidation of Cumene (isopropyl benzene),

Chemical Intermediates and Monomers

Formaldehyde
Results from the exothermic oxidation and endothermic dehydrogenation of methanol

Chemical Intermediates and Monomers

Hexamethylenetetramine
Evaporation of the reaction product of formaldehyde and ammonia

Uses
Urinary Antiseptic (Urotropine) Rubber Industry Preparation of Explosive Cyclonite Phenol-Formaldehyde Resins

Chemical Intermediates and Monomers

Vinyl Esters
Addition of acids to acetylene furnishes esters

Usually prepared by:


Chlorination Oxychlorination Dehydrochlorination

Chemical Intermediates and Monomers

Phthalic Anhydride
One of the most important intermediates for plastics industry Preparation of phthalic anhydride are controlled oxidation of o-xylene or naphthalene

Chemical Intermediates and Monomers

Methyl Acrylate and Methacrylate


Following Dow-Badische-Reppe Synthesis
CH2=CH2 + CO + ROH CH2CH COOR

The conventional method for preparing MMA has been by the reaction of hydrogen cyanide with acetone and subsequent treatment with methyl alcohol

Other Raw Materials

Natural Products
Cellulose
The structural material of the plant world, is itself a polymer composed of 50 to 100 units of the disaccharide cellobiose

Other Raw Materials

Plasticizers
Organic compounds added to plastics
To improve workability during fabrication To extend or modify the natural properties of the plastics To develop new, improved properties no present in the original resin

Reduce the viscosity and make shaping and forming easier Also impart flexibility and other desired properties to finished product

Other Raw Materials

Fillers and Reinforcements


Many materials may be added to plastics to increase strength, thermal conductivity, resistance to heat distortion, and lower thermal expansion. Formerly asbestos was used, but due to its human carcinogenic properties, it is no longer acceptable filler.

Other Raw Materials

Manufacturing Processes

General Polymerization Processes


Bulk Polymerization Solution Polymerization Suspension polymerization Emulsion Polymerization

Polymerization

a process of reacting monomer molecules together in a chemical reaction to form three-dimensional networks or polymer chains.

Bulk Polymerization

commonly referred to as mass polymerization in the industry May be carried out in liquid/vapor state carried out by adding a soluble initiator to pure monomer into liquid state. Monomers & activator are mixed in a reactor and heated or cooled as needed

Solution Polymerization

Often used when exothermic heat is too great to be controlled in bulk polymerization Monomer & initiator are dissolved in a nonreactive solvent The polymer concentration has to be low to avoid too high viscosity Produces polymers of low to medium MW

Flow Diagram

Suspension Polymerization

Monomer is suspended in water by agitation and stabilizers such as talk, fullers earth and bentonite are added Initiator is soluble in the monomer Each monomer globule polymerizes as a spherical pearl of high MW This process is used in the production of most PVC

Process flow diagram

Emulsion Polymerization

Similar to suspension polymerization but monomer Is broken up into droplets that form aggregates called micelles Are rapid and can be carried out at relatively low temp Monomer is on the interior of the micelles, initiator is in the water Soap is used to stabilize micelles Initiator diffuses into the micelle to start polymerization Produces polymers of very high MW

Process flow diagram

Condensation-Polymerization Products

Phenolics Amino resins Polyester resins Alkyd resins Polycarbonates Epoxy Resins Polyimides

Condensation polymerization,

a form of step-growth polymerization, process by which two molecules join together, resulting loss of small molecules which is often water. The type of end product resulting the reaction is dependent on the number of functional end groups of the monomer which can react.

Phenolics

Phenol formaldehyde resins (PF) include synthetic thermosetting resins such as obtained by the reaction of phenols with formaldehyde are formed by a step-growth polymerization reaction that can be either acid- or base-catalysed Initial reaction HOC6H5 + CH2O ortho/para HOC6H4CH2OH

Amino Resins

a thermosetting resinous product made by condensation of a compound containing an amine (e.g., melamine or urea) with an aldehyde (e.g., formaldehyde): is used in making permanent-press fabrics and other products Urea formaldehyde and melamineformaldehyde condensates are the commercially important amino resins

A typical low-stage resin is formed when urea (or melamine) is mixed with formaldehyde

Polyester Resins

Complex esters formed when a difunctional alcohol is reacted with a dibasic acid or anhydride Since rxn takes place at both ends of the chain, long molecules are possible and a plurality of ester groups is obtained Unsaturated polyesters are produced when any of the reactants contain unsaturation, such as

Alkyd Resins

any synthetic resin made from a dicarboxylic acid, such as phthalic acid, and diols or triols: used in paints and adhesives Formed by the reaction of polyhydric alcohols and polybasic acids The most common method of preparation is the fatty acid method in w/c glyceride oil is catalytically treated w/ glycerol at 25250oC

Polycarbonates

Special variety of polyester in w/d a derivative of carbonic acid Is substituted for adipic, phthalic and a diphenol is substituted for the more conventional glycols

Epoxy Resins

Formed by the reaction of bisphenol with epichlorohydrin. Have excellent chemical resistance; excellent adhesion and electrical insulating poperties Epoxy resins have many different uses. For example, resins that are cured through exposure to ultraviolet light are commonly used in fiber optics, optoelectronics, and dentistry.

Polyimides
Very stable, linear polymers Compounds containing two anhydride groups w/c reacts with primary amines or isocyanates The polyimide materials are lightweight, flexible, resistant to heat and chemicals. Therefore, they are used in the electronics industry for flexible cables, as an insulating film on magnet wire and for medical tubing.

Polysulfones

Polysulfone describes a family of thermoplastic polymers. These polymers are known for their toughness and stability at high temperatures. Resistance to autoclave sterilization makes them useful for medical instruments and trays Other uses: microwave cookware, coffee decanters, and corrosion-resistant piping

Addition Polymerization

Polyolefins Vinyl resins Vinyl alcohol resins Vinylidene resins Styrene resins Acrylic resins and plastics

Addition polymerization

A chemical reaction in which simple molecules (monomers) are added to each other to form long-chain molecules (polymers) without by-products. The molecules of the monomer join together to form a polymeric product in which the molecular formula of the repeating unit is identical with that of the monomer. The molecular weight of the polymer so formed is thus the total of the molecular weights of all of the combined monomer units.

Polyolefins
a polymer produced from a simple olefin (also called an alkene with the general formula CnH2n) as a monomer. Industrial polyolefins: PE, PP have excellent chemical resistance and can only be adhesively bonded after surface treatment because they have very low surface energies used for blown film and heatshrink electrical insulation sleeves for crimped wire terminals, as well as rash guards or under garments for wetsuits. Polyolefin elastomer POE is used as a main ingredient in seat cushions, arm rests, spa pillows, etc.

Vinyl Resins

Synthetic materials made from cpds having a vinyl group Polyvinyl acetate, PVC, polyvinyl alcohol, polyvinyl acetals Largest branch of vinyl family is PVC due to wide range of applications, ease of processing and relatively low cost

PVC manufacture

Alloying and Bending

Blends-mixtures that are not fully compatible Alloys-mixtures that are fully compatibles such as polyethylene oxide and polystyrene
appear as separate phases when viewed under microscope Problem: to make components adhere together Approach: to introduce compatibilizers Major polymer alloys are polyphenylene oxide/polystyrene, polycarbonate, PET

Natural Products

Cellulose Derivatives Cellulose Nitrate-a compound made by treating cellulose with nitric and sulphuric acids, used in plastics, lacquers, and explosives Cellulose Acetate-synthetic compound derived from the acetylation of the plant substance cellulose. Can be molded into solid plastic parts such as tool handles or cast into film for photography or food wrapping

Ethyl Cellulose plastics- thermoplastic and are noted for their ease of molding, light weight, and good dielectric strength. applications include football helmets, equipment housings, refrigerator parts, and luggage. Shellac- a resin secreted by the female lac bug, on trees in the forests of India and Thailand. It is processed and sold as dry flakes (pictured at right), which are dissolved in ethyl alcohol to make liquid shellac, which is used as a brush-on colorant, food glaze and wood finish.

Laminates

A laminate is a material that can be constructed by uniting two or more layers of material together. Laminated plastics are made largely from the thermosetting class of resins and have fibrous fillers such as glass, carbon, metal and some polymer Resin is dissolved in a suitable solvent (alcohol or water) with w/c the filler is coated

Vehicle windshields are commonly made by laminating a tough plastic film between two layers of glass. Plywood is a common example of a laminate using the same material in each layer. Glued and laminated dimensioned timber is used in the construction industry to make wooden beams

Foams

Cellular plastics available in two types


Closed cell- have higher compressive strength due to their structures Open cell- contain pores that are connected to each other and form an interconnected network which is relatively soft. Formed by adding blowing or foaming agents to the resin and then heating to cause the additives to foam Common foaming agents are cpds w/c give off CO2 or N gases

Syntactic Foams- A special class of closedcell which contains hollow particles embedded in a matrix material. Possible applications, such as dynamic structural support, flexible foam core, and expandable foam fill Integral skin foam- is a type of foam with a high-density skin and a low-density core. Examples of items produced using this process include arm rests, baby seats, shoe soles, and mattresses.