Commodity Thermoplastics

Polymer Technology

Thermoplastics
What are Thermoplastics? Classification of Thermoplastics Commodity Thermoplastics Engineering Thermoplastics

What are Thermoplastics?

Linear polymers whose molecules are not linked by covalent bonds and can slide past each other on the application of heat and pressure. Polymers that soften on heating and can be processed into a desired form by a variety of fabrication methods. Polymers are often soluble and can be manipulated as solutions.

Classification of Thermoplastics

Commodity Thermoplastics

High Volume Usage Low Cost Low Volume Usage High Cost Better Properties

Engineering Thermoplastics

Commodity Thermoplastics

Polyolefins

Polyethylene (PE) Polypropylene (PP) Polyvinyl Chloride (PVC) Polystyrene (PS) Polymethyl Methacrylate (PMMA)

Vinyl Polymers

Polyolefins

Polyethylene (PE)

Low Density Polyethylene (LDPE) High Density Polyethylene (HDPE) Linear Low Density Polyethylene (LLDPE) Very Low Density Polyethylene (VLDPE) High Molecular Weight High density Polyethylene (HMW-HDPE) Ultra High Molecular Weight Polyethylene (UHMWPE)

Polypropylene (PP)

Polyethylene (PE)

Polyethylene or polythene is the most common and widely used plastic worldwide. Polyethylene is a thermoplastic polymer consisting of long hydrocarbon chains. Annual production is approximately 80 million metric tons with primary use in packaging.

Development

PE first commercially produced by British Company Imperial Chemical Industries (ICI) in 1939. Preparation required high temperatures up to 200o C and high pressures up to 2000 atm resulting in a material with shorter, branched chains, which was waxy and easily deformed. In 1953 Ziegler (Germany), Phillips Petroleum Company (USA) and Standard Oil (USA) almost simultaneously prepared high molecular weight PE at low temperatures and low pressures which was linear, hard and rigid. Giulio Natta extended Zieglers research, eventually showing how the geometry of polyethylene could be controlled by certain catalysts. New material became known as HDPE and older material as LDPE.

Chemical Structure

PE is an addition polymer made by the polymerisation of ethylene monomer, C2H4.

Different classes of PE are available, with the general chemical formula (C2H4)n

Classification

Low Density Polyethylene (LDPE) High Density Polyethylene (HDPE) Linear Low Density Polyethylene (LLDPE) Very Low Density Polyethylene (VLDPE) High Molecular Weight High Density Polyethylene (HMW-HDPE) Ultra High Molecular Weight Polyethylene (UHMWPE)

Properties

Properties dependent on:

Chemical Structure Molecular Weight

Chemical Resistance

Excellent chemical resistance Resistant to strong acids or strong bases Resistant to gentle oxidants and reducing agents.

Solubility

Crystalline samples do not dissolve at room temperature. Soluble at elevated temperatures in aromatic hydrocarbons (toluene or xylene), or in chlorinated solvents (tricholoroethane or trichlorobenzene).

LDPE: Preparation

Made by free radical polymerisations with oxygen or peroxide as initiator. Polymerisation carried out at temperatures of 80 350oC and pressures of 1500 - 3500 atm. Choice of initiator determines the appropriate reaction conditions. High pressures necessary to achieve high molecular weights. High molecular weights favoured by increased pressures which result in higher monomer concentration.

LDPE: Physical Properties

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Property

LDPE

_____________________________________________________________________ Specific Gravity 0.91 - 0.93 Crystallinity, % 50 - 70 Melt Temperature, oC 98 - 120 Tensile Strength, MPa 4.1 - 16 Tensile Modulus, GPa 0.10 - 0.26 Elongation-to-Break, % 90 - 800 Impact Strength No Break Notched Izod, J m-1 Heat Deflection 38 - 49 oC, at 455 kPa (66 psi) _____________________________________________________________________

HDPE: Preparation

Ziegler Process

Pressures of 2 4 atm and temperatures of 50 75 oC. Polymerisation in the presence of Ziegler Natta catalysts. Pressures of 30 - 40 atm and temperatures of 90 160 oC. Polymerisation in the presence of Chromium Oxide catalysts.

Phillips Process

Standard Oil Process

Pressures of 40 100 atm and temperatures of 200 - 300 oC. Polymerisation in the presence of metal oxide catalysts
Pressures of 7 20 atm and temperatures of ca. 100 oC. Polymerisation in the presence of metal oxide catalysts.

Union Carbide Process

HDPE: Properties

Physical Properties

Translucent material Reduced branching results in a more closely packed structure, more crystalline, higher density. Chemical resistance slightly higher than that of LDPE. Resists alcohols, acids, bases, esters, and aldehydes.

Chemical Resistance

Physical Properties
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Property

LDPE

HDPE

_____________________________________________________________________ Specific Gravity 0.91 - 0.93 0.94 - 0.97 Crystallinity, % 50 - 70 80 - 95 Melt Temperature, oC 98 - 120 127 - 125 Tensile Strength, MPa 4.1 - 16 21 - 38 Tensile Modulus, GPa 0.10 - 0.26 0.41 - 1.24 Elongation-to-Break, % 90 - 800 20 - 130 Impact Strength No Break 27 - 1068 Notched Izod, J m-1 Heat Deflection 38 - 49 60 - 88 oC, at 455 kPa (66 psi) _____________________________________________________________________

Applications

Packaging Film Pipes

Milk bottles, toys, beer crate, food packaging, Shrink wrap, squeeze tubes, disposable clothing, plastic bags, paper coatings, cable insulation, artificial joints, Fibers - low cost ropes and packing tape reinforcement.

LLDPE

Preparation

Produced through catalyst selection & regulation of reactor conditions Contains little if any branching Densities range between 0.916 and 0.930 Good Flex Life Low Warpage Improved Stress-Crack Resistance

Properties

Applications

Films for ice, trash, garment, and produce bags

VLDPE

Preparation

Produced through catalyst selection and regulation of reactor conditions Densities range between 0.890 and 0.915 Disposable gloves, shrink packages, vacuum cleaner hoses, tuning, bottles, shrink wrap, diaper film liners, and other health care products.

Applications

HMW-HDPE

Preparation

Produced through catalyst selection & regulation of reactor conditions Densities are 0.941 or greater MW range from 200,000 to 500,000 Improved toughness, chemical resistance, impact strength, and high abrasion resistance, high viscosities. Trash liners, grocery bags, industrial pipe, gas tanks, and shipping containers.

Properties

Applications

UHMW-HDPE

Preparation

Produced through catalyst selection & regulation of reactor conditions Densities are 0.960 or greater MW range from 300,000,000 to 600,000,000 Improved high wear resistance, chemical inertness, and low coefficient of friction. High viscosities result in material not flowing or melting. Pump parts, seals, surgical implants, pen tips, and butcher-block cutting surfaces.

Properties

Applications

Polypropylene (PP)

Polypropylene (PP), also known as polypropene, is a thermoplastic polymer used in a wide variety of applications. PP is an addition polymer made from the monomer propylene, it is rugged and unusually resistant to many chemical solvents, bases and acids. In 2008, the global market for polypropylene had a volume of 45.1 million metric tonnes.

Development

Propylene was first polymerized to a crystalline isotactic polymer by Giulio Natta in 1954. This pioneering discovery led to large-scale commercial production of isotactic PP in 1957. Syndiotactic polypropylene was also first synthesized by Natta and his co-workers. PP is second most important plastic with revenues expected to exceed US$145 billion by 2019. The demand for PP was growing at a rate of 4.4% per year between 2004 and 2012.

Chemical Structure

PP is an addition polymer made by the polymerisation of propylene monomer, C 3H 6.

PP has the chemical formula (C3H6)n

Preparation

Polypropylene produced with low pressure process (Ziegler) Polypropylene produced with linear chains Polypropylene is similar in manufacturing method and in properties to PE Commercial PP is 90% to 95% isotactic. Isotactic PP - CH3 group on one side of the polymer chain.

Classification

The most important way to classify polypropylene is based on its chemical structure: Atactic Isotactic Syndiotactic

Isotactic PP

Most commercially important in comparison with the atactic and syndiotactic forms. Isotactic propylene has the most stereo-regular structure of polypropylenes and therefore achieves a high degree of crystallinity. Mechanical properties and the processability of polypropylene are highly determined by the level of isotacticity and crystallinity. Isotactic PP

Atactic PP

The atactic polymer is sticky, amorphous and has a low molecular weight. These polymers provide the same effect as a plasticizer, reducing the crystallinity of polypropylene. A small amount of atactic polymer at the end of the polymer can be used to provide certain mechanical properties such as performance at lower temperatures, elongation, and optical and processable properties.

Syndiotactic PP

The syndiotactic polypropylene has recently been developed commercially, with the methyl radicals staggered along the chain in an orderly manner stereochemically. Syndiotactic PP

Physical Properties
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Property

PP

_____________________________________________________________________ Specific Gravity 0.90 - 0.91 Crystallinity, % 82 Melt Temperature, oC 165 - 171 Tensile Strength, MPa 31 - 41 Tensile Modulus, GPa 1.10 - 1.55 Elongation-to-break, % 100 - 600 Impact Strength 21 - 53 Notched Izod, J m-1 Heat Deflection 225 - 250 oC, at 455 kPa (66 psi) _____________________________________________________________________

Properties of Commodity Polyolefins

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Property

LDPE

HDPE

PP

_____________________________________________________________________ Specific Gravity 0.91 - 0.93 0.94 - 0.97 0.90 - 0.91 Crystallinity, % 50 - 70 80 - 95 82 Melt Temperature, oC 98 - 120 127 - 125 165 - 171 Tensile Strength, MPa 4.1 - 16 21 - 38 31 - 41 Tensile Modulus, GPa 0.10 - 0.26 0.41 - 1.24 1.10 - 1.55 Elongation-to-Break, % 90 - 800 20 - 130 100 - 600 Impact Strength No Break 27 - 1068 21 - 53 Notched Izod, J m-1 Heat Deflection 38 - 49 60 - 88 225 - 250 oC, at 455 kPa (66 psi) _____________________________________________________________________

Properties

Light and ductile but it has low strength. It is more rigid than PE and can be used at higher temperatures. The properties of PP are similar to those of HDPE but it is stiffer and melts at a higher temperature (165 - 170 C). Stiffness and strength can be improved further by reinforcing with glass, chalk or talc. When drawn to fibre PP has exceptional strength and resilience; this, together with its resistance to water, makes it attractive for ropes and fabric. It is more easily moulded than PE, has good transparency and can accept a wider, more vivid range of colours.

Advantages of PP

Low Cost Excellent Flexural Strength Good Impact Strength Low Coefficient of Friction Excellent Electrical Insulation Good Fatigue Resistance Excellent Moisture Resistance Service Temperature to 126 oC Very Good Chemical Resistance

Disadvantages of PP

High Thermal Expansion UV Degradation Poor Weathering Resistance Poor Resistance to Chlorinated Solvents & Aromatics Difficulty to Bond or Paint Oxidizes Readily Flammable

Applications

Packaging Clothing Medical Applications

Ropes, general polymer engineering, automobile air ducting, parcel shelving and air-cleaners, garden furniture, washing machine tank, wet-cell battery cases, pipes and pipe fittings, beer bottle crates, chair shells, capacitor dielectrics, cable insulation, kitchen kettles, car bumpers, shatter proof glasses, crates, suitcases, artificial turf, thermal underwear.

Vinyl Polymers

Polystyrene (PS) Poly(Vinyl Chloride) (PVC) Poly(Methyl Methacrylate) (PMMA)

Polystyrene (PS)

Polystyrene is a synthetic aromatic polymer made from the monomer styrene, a liquid petrochemical. Polystyrene can be rigid or foamed. General purpose polystyrene is clear, hard and brittle. PS is a very inexpensive resin per unit weight.

Chemical Structure

PS is an addition polymer made by the polymerisation of styrene monomer, C8H8. PS has the chemical formula (C8H8)n

Properties

PS does not crystallize, and the resulting material is transparent with a high refractive index. The benzene ring absorbs UV light, exploited in the PS screening of fluorescent lights but causes the polymer to discolor in sunlight. Excellent electrical resistance and dielectric strength, exploited in switchgear.

Properties of Styrenic Polymers

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Property

GPPS

HIPS

ABS

_____________________________________________________________________ Specific Gravity 1.04 1.05 1.03 1.06 1.03 1.58 Tensile Strength, MPa 36.6 54.5 22.1 33.8 41.4 51.7 Tensile Modulus, GPa 2.41 3.38 1.79 3.24 2.07 2.76 Elongation-to-Break, % 1-2 13 - 50 5 - 25 Impact Strength 13.3 21.4 26.7 - 587 160 - 320 Notched Izod, J m-1 Heat Deflection 75 - 100 75 - 95 102 - 107 oC, at 455 kPa (66 psi) _____________________________________________________________________

Applications

Packaging Construction Medical Applications Art and Craft Toys; light diffusers; beakers; cutlery; general household appliances; video/audio cassette cases; electronic housings; refrigerator liners.

Polyvinyl Chloride (PVC)

Polyvinyl chloride is the third-most widely produced plastic after polyethylene and polypropylene. PVC is used in construction because it is more effective than traditional materials such as copper, iron or wood in pipe and profile applications. It can be made softer and more flexible by the addition of plasticisers, the most widely used being phthalates. In this form, it is also used in clothing and upholstery, electrical cable insulation, inflatable products and many applications in which it replaces rubber.

Chemical Structure

Polyvinyl Chloride is an addition polymer made by the polymerisation of vinyl chloride monomer, C2H3Cl. Polyvinyl Chloride has the chemical formula: (CH2CHCl)n

Physical Properties
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Property
Specific Gravity Tensile Strength, MPa Tensile Modulus, GPa Elongation-to-Break, % Impact Strength Notched Izod, J m-1 Heat Deflection oC, at 455 kPa (66 psi)

Rigid
1.03 1.58 41.4 51.7 2.41 - 4.14 2 - 80 21.4 - 1068 57 - 82

Flexible
1.16 1.35 22.1 33.8 1.79 3.24 13 - 50 26.7 - 587 75 - 95

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Properties

Pure PVC is a white, brittle solid. PVC is insoluble in alcohol, but slightly soluble in tetrahydrofuran. Excellent resistance to acids and bases Good barrier properties to atmospheric gasses. Poor resistance to some solvents.

Applications

uPVC
Pipes, Fittings, Profiles, Road Signs. Window and Cladding, Door Frames. Garden hoses, vinyl flooring, vinyl records, dolls, medical tubes.

pPVC
Artificial leather, wire insulation, film. Sheet, fabric, car upholstery.

Applications

Polymethyl Methacrylate (PMMA)

PMMA is a transparent thermoplastic, often used as a lightweight or shatterresistant alternative to glass. Although it is not technically a type of glass, the substance has sometimes historically been called acrylic glass.

Development

The first acrylic acid was made in 1843 and methacrylic acid, derived from acrylic acid, was formulated in 1865. The reaction between methacrylic acid and methanol results in the ester methyl methacrylate. German chemist Wilhelm Rudolph Fittig and co-workers in 1877 polymerised methyl methacrylate into polymethyl methacrylate. In 1933 German chemist, Otto Rhm, patented and registered the brand name PLEXIGLAS. In 1936 the first commercially viable production of acrylic safety glass began by ICI Acrylics. During World War II acrylic glass was used for submarine periscopes, windshields, canopies, and gun turrets for airplanes

Chemical Structure

PMMA is an addition polymer made by the polymerisation of methyl methacrylate monomer, C5O2H8.
PMMA has the chemical formula (C5O2H8)n

Preparation

PMMA is routinely produced by emulsion, solution and bulk polymerisation. Generally, radical initiation is used, including living polymerisation, but anionic polymerization of PMMA can also be performed. PMMA produced by radical polymerisation is atactic and completely amorphous.

Properties

PMMA is a strong and lightweight material. It has a density of 1.17 1.20 g/cm3, which is less than half that of glass. Good impact strength, higher than both glass and polystyrene. PMMA swells and dissolves in many organic solvents. Poor resistance to many other chemicals on account of its easily hydrolysed ester groups. Environmental stability is superior to most other plastics such as polystyrene and polyethylene, and PMMA is therefore often the material of choice for outdoor applications.

Applications

Automotive Industry Transparent Glass Substitute Electrical Applications Medical Applications

Light Fixtures, Car Lamps, Signs, Counter tops, Decorative pieces, Floor waxes, Paint, Fingernail polishes, Contact lenses, Glasses

Applications

The End
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