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Polypropylene (PP), also known as polypropene, is a thermoplastic polymer used in a wide variety of applications including packaging and labeling,

textiles (e.g., ropes, thermal underwear and carpets), stationery, plastic parts and reusable containers of various types, laboratory equipment, loudspeakers, automotive components, and polymer banknotes. 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 tons, which led to a turnover of about $65 billion (~ 47.4 billion).[1]

Contents

1 Chemical and physical properties o 1.1 Degradation 2 History 3 Synthesis 4 Industrial processes 5 Manufacturing 6 Biaxially oriented polypropylene (BOPP) 7 Development trends 8 Applications
o o o

8.1 Clothing 8.2 Medical 8.3 EPP model aircraft

9 Recycling 10 Repairing 11 Health concerns 12 References 13 External links

Chemical and physical properties

Micrograph of polypropylene Most commercial polypropylene is isotactic and has an intermediate level of crystallinity between that of low-density polyethylene (LDPE) and high-density polyethylene (HDPE). Polypropylene is normally tough and flexible, especially when copolymerized with ethylene. This allows polypropylene to be used as an engineering plastic, competing with materials such as ABS. Polypropylene is reasonably economical, and can be made translucent when uncolored but is not as readily made transparent as polystyrene, acrylic, or certain other plastics. It is often opaque or colored using pigments. Polypropylene has good resistance to fatigue. The melting point of polypropylene occurs at a range, so a melting point is determined by finding the highest temperature of a differential scanning calorimetry chart. Perfectly isotactic PP has a melting point of 171 C (340 F). Commercial isotactic PP has a melting point that ranges from 160 to 166 C (320 to 331 F), depending on atactic material and crystallinity. Syndiotactic PP with a crystallinity of 30% has a melting point of 130 C (266 F).[2] The melt flow rate (MFR) or melt flow index (MFI) is a measure of molecular weight of polypropylene. The measure helps to determine how easily the molten raw material will flow during processing. Polypropylene with higher MFR will fill the plastic mold more easily during the injection or blow-molding production process. As the melt flow increases, however, some physical properties, like impact strength, will decrease. There are three general types of polypropylene: homopolymer, random copolymer, and block copolymer. The comonomer is typically used with ethylene. Ethylene-propylene rubber or EPDM added to polypropylene homopolymer increases its low temperature impact strength. Randomly polymerized ethylene monomer added to polypropylene homopolymer decreases the polymer crystallinity and makes the polymer more transparent.

Degradation
Polypropylene is liable to chain degradation from exposure to heat and UV radiation such as that present in sunlight. Oxidation usually occurs at the tertiary carbon atom present in every repeat unit. A free radical is formed here, and then reacts further with oxygen, followed by chain scission to yield aldehydes and carboxylic acids. In external applications, it shows up as a network of fine cracks and crazes that become deeper and more severe with time of exposure.

For external applications, UV-absorbing additives must be used. Carbon black also provides some protection from UV attack. The polymer can also be oxidized at high temperatures, a common problem during molding operations. Anti-oxidants are normally added to prevent polymer degradation.

History
Propylene was first polymerized to a crystalline isotactic polymer by Giulio Natta as well as by the German chemist Karl Rehn in March 1954.[3] This pioneering discovery led to large-scale commercial production of isotactic polypropylene by the Italian firm Montecatini from 1957 onwards.[4] Syndiotactic polypropylene was also first synthesized by Natta and his coworkers. Polypropylene is the second most important plastic with revenues expected to exceed US$145 billion by 2019. The demand for this material was growing at a rate of 4.4% per year between 2004 and 2012.[5]

Synthesis
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Short segments of polypropylene, showing examples of isotactic (above) and syndiotactic (below) tacticity. An important concept in understanding the link between the structure of polypropylene and its properties is tacticity. The relative orientation of each methyl group (CH3 in the figure) relative to the methyl groups in neighboring monomer units has a strong effect on the polymer's ability to form crystals. A Ziegler-Natta catalyst is able to restrict linking of monomer molecules to a specific regular orientation, either isotactic, when all methyl groups are positioned at the same side with respect to the backbone of the polymer chain, or syndiotactic, when the positions of the methyl groups alternate. Commercially available isotactic polypropylene is made with two types of ZieglerNatta catalysts. The first group of the catalysts encompases solid (mostly supported) catalysts and certain types of soluble metallocene catalysts. Such isotactic macromolecules coil into a helical shape; these helices then line up next to one another to form the crystals that give commercial isotactic polypropylene many of its desirable properties.

A ball-and-stick model of syndiotactic polypropylene. Another type of metallocene catalysts produce syndiotactic polypropylene. These macromolecules also coil into helices (of a different type) and form crystalline materials. When the methyl groups in a polypropylene chain exhibit no preferred orientation, the polymers are called atactic. Atactic polypropylene is an amorphous rubbery material. It can be produced commercially either with a special type of supported Ziegler-Natta catalyst or with some metallocene catalysts. Modern supported Ziegler-Natta catalysts developed for the polymerization of propylene and other 1-alkenes to isotactic polymers usually use TiCl4 as an active ingredient and MgCl2 as a support.[6][7][8] The catalysts also contain organic modifiers, either aromatic acid esters and diesters or ethers. These catalysts are activated with special cocatalysts containing an organoaluminum compound such as Al(C2H5)3 and the second type of a modifier. The catalysts are differentiated depending on the procedure used for fashioning catalyst particles from MgCl2 and depending on the type of organic modifiers employed during catalyst preparation and use in polymerization reactions. Two most important technological characteristics of all the supported catalysts are high productivity and a high fraction of the crystalline isotactic polymer they produce at 7080 C under standard polymerization conditions. Commercial synthesis of isotactic polypropylene is usually carried out either in the medium of liquid propylene or in gasphase reactors. Commercial synthesis of syndiotactic polypropylene is carried out with the use of a special class of metallocene catalysts. They employ bridged bis-metallocene complexes of the type bridge(Cp1)(Cp2)ZrCl2 where the first Cp ligand is the cyclopentadienyl group, the second Cp ligand is the fluorenyl group, and the bridge between the two Cp ligands is -CH2-CH2-, >SiMe2, or >SiPh2. [9] These complexes are converted to polymerization catalysts by activating them with a special organoaluminum cocatalyst, methylaluminoxane (MAO).[10]

Industrial processes

Traditionally, three manufacturing process are the most representative ways to produce polypropylene.[11] Hydrocarbon slurry or suspension: Uses a liquid inert hydrocarbon diluent in the reactor to facilitate transfer of propylene to the catalyst, the removal of heat from the system, the deactivation/removal of the catalyst as well as dissolving the atactic polymer. The range of grades that could be produced was very limited. (The technology has fallen into disuse). Bulk (or bulk slurry): Uses liquid propylene instead of liquid inert hydrocarbon diluent. The polymer does not dissolve into a diluent, but rather rides on the liquid propylene. The formed polymer is withdrawn and any unreacted monomer is flashed off. Gas phase: Uses gaseous propylene in contact with the solid catalyst, resulting in a fluidized-bed medium.