Polyolefin

A polyolefin is a type of polymer produced from a simple olefin (also called an alkene with the general formula CnH2n) as a monomer. For example, polyethylene is the polyolefin produced by polymerizing the olefin ethylene. Polypropylene is another common polyolefin which is made from the olefin propylene.

Industrial polyolefins

Most polyolefin produced on an industrial scale are made via polymerization through the use of catalysts. One example is the use of Ziegler-Natta catalyst for the polymerization of ethylene to polyethylene.[1]

Properties

Polyolefin properties range from liquidlike to rigid solids, and are primarily determined by their molecular weight and degree of crystallinity. Polyolefin degrees of crystallinity range from 0% (liquidlike) to 60% or higher (rigid plastics). Crystallinity is primarily governed by the lengths of polymer's crystallizable sequences established during polymerization.[2] Examples include adding a small percentage of comonomer like 1-hexene or 1-octene during the polymerization of ethylene,[3] or occasional irregular insertions ("stereo" or "regio" defects) during the polymerization of isotactic propylene.[4] The polymer's ability to crystallize to high degrees decreases with increasing content of defects.

Low degrees of crystallinity (0–20%) are associated with liquidlike-to-elastomeric properties. Intermediate degrees of crystallinity (20–50%) are associated with ductile thermoplastics, and degrees of crystallity over 50% are associated with rigid and sometimes brittle plastics.[5]

Polyolefin surfaces are not effectively joined together by solvent welding because they have excellent chemical resistance and are unaffected by common solvents. They can be adhesively bonded after surface treatment (they inherently have very low surface energies and don't wet-out well (the process of being covered and filled with resin)), and by some superglues (cyanoacrylates) and reactive (meth)acrylate glues.[6] They are extremely inert chemically but exhibit decreased strength at lower and higher temperatures.[7] As a result of this, thermal welding is a common bonding technique.

Practically all polyolefins that are of any practical or commercial importance are poly-alpha-olefin (or poly-α-olefin or polyalphaolefin, sometimes abbreviated as PAO), a polymer made by polymerizing an alpha-olefin. An alpha-olefin (or α-olefin) is an alkene where the carbon-carbon double bond starts at the α-carbon atom, i.e. the double bond is between the #1 and #2 carbons in the molecule. Alpha-olefins such as 1-hexene may be used as co-monomers to give an alkyl branched polymer (see chemical structure below), although 1-decene is most commonly used for lubricant base stocks.[8]

1-hexene, an example of an alpha-olefin

Many poly-alpha-olefins have flexible alkyl branching groups on every other carbon of their polymer backbone chain. These alkyl groups, which can shape themselves in numerous conformations, make it very difficult for the polymer molecules to align themselves up side-by-side in an orderly way. This results in lower contact surface area between the molecules and decreases the intermolecular interactions between molecules.[9] Therefore, many poly-alpha-olefins do not crystallize or solidify easily and are able to remain oily, viscous liquids even at lower temperatures.[10] Low molecular weight poly-alpha-olefins are useful as synthetic lubricants such as synthetic motor oils for vehicles and can be used over a wide temperature range.[8][10]

Even polyethylenes copolymerized with a small amount of alpha-olefins (such as 1-hexene, 1-octene, or longer) are more flexible than simple straight-chain high-density polyethylene, which has no branching.[7] The methyl branch groups on a polypropylene polymer are not long enough to make typical commercial polypropylene more flexible than polyethylene.

Uses

Polyolefins are used for blow moulded or rotationally moulded components, e.g. toys,[11] for heat-shrink tubing used to mechanically and electrically protect connections in electronics,[11] and for rash guards or undergarments for wetsuits.

Polyolefin sheets or foams are used in a wide variety of packaging applications, sometimes in direct contact with food.[12]

Polyolefin elastomer POE is used as a main ingredient in the molded flexible foam technology such as in the fabrication of self skinned footwear (for example, Crocs shoes), seat cushions, arm rests, spa pillows, etc. Hydrogenated polyalphaolefin (PAO) is used as a radar coolant. Head makes polyolefin tennis racket strings. Polyolefin is also used in pharmaceutical and medical industry for HEPA filter certification—a PAO aerosol is passed through the filters and the air that exits is measured with an aerosol detector.[13]

Elastolefin is a fiber used in fabrics.[14] IKEA's Better Shelter uses structural panels made out of polyolefin foam, stating, "They are tough and durable.".[15] Piping systems for the conveyance of water, chemicals or gases are commonly produced in Polypropylene, and to a much greater extent Polyethylene. Piping systems in high-density Polyethylene (HDPE, PE100, PE80) are fast becoming the most commonly used drinking water, waste water and natural gas distribution piping systems in the world.

Polyalphaolefin, commonly referred to as a synthetic hydrocarbon, is used in various types of air compressors and turbines including reciprocating, centrifugal, and rotary screw compressors where high pressures and temperatures can be an issue. These base fluids are the most widely used variety of synthetic oil blends mainly for their ability to maintain performance in spite of temperature extremes and their similarity to—but improved performance over—mineral oil base fluids.[16]

Polyolefin waste can be converted into many different products, including pure polymers, naphtha, clean fuels, or monomers.[17]

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References
  1. Cossee, P (1964-02-01). "Ziegler-Natta catalysis I. Mechanism of polymerization of α-olefins with Ziegler-Natta catalysts". Journal of Catalysis. 3 (1): 80–88. doi:10.1016/0021-9517(64)90095-8.
  2. Tashiro, Stein, Hsu, Macromolecules 25 (1992) 1801-1810
  3. Alizadeh et. al., Macromolecules 32 (1999) 6221-6235
  4. Bond, Eric Bryan; Spruiell, Joseph E.; Lin, J. S. (1 November 1999). "A WAXD/SAXS/DSC study on the melting behavior of Ziegler-Natta and metallocene catalyzed isotactic polypropylene". Journal of Polymer Science Part B: Polymer Physics. 37 (21): 3050–3064. Bibcode:1999JPoSB..37.3050B. doi:10.1002/(SICI)1099-0488(19991101)37:21<3050::AID-POLB14>3.0.CO;2-L.
  5. A. J. Kinloch, R. J. Young, The Fracture Behaviour of Polymers, Chapman & Hall, 1995. pp. 338-369. ISBN 0 412 54070 3
  6. "Properties and Applications of Polyolefin Bonding" " Master Bond Inc." Retrieved on June 24, 2013
  7. James Lindsay White, David D. Choi (2005). Polyolefins: Processing, Structure Development, And Properties. Munich: Hanser Verlag. ISBN 1569903697.
  8. R. M. Mortier, M. F. Fox and S. T. Orszulik, ed. (2010). Chemistry and Technology of Lubricants (3rd ed.). Netherlands: Springer. ISBN 978-1402086618.
  9. "Properties of Alkanes Archived 2013-01-07 at the Wayback Machine." Retrieved on June 24, 2013
  10. L. R. Rudnick and R. L. Shubkin, ed. (1999). Synthetic Lubricants and High-performance Functional Fluids (2nd ed.). New York: Marcel Dekker. ISBN 0-8247-0194-1.
  11. Kucklick, Theodore R. (2012). The Medical Device R&D Handbook, Second Edition. CRC Press. p. 19. ISBN 9781439811894.
  12. Kit L. Yam, ed. (2010). The Wiley Encyclopedia of Packaging Technology. John Wiley & Sons. ISBN 9780470541388. Retrieved 2016-11-20.
  13. "HEPA/ULPA Cleanroom Filter Testing". Clean Air Solutions. Retrieved 15 October 2012.
  14. Mellior International (11th–12th ed.). IBP Business Press Publishers. 2006. p. 4. ISSN 0947-9163.
  15. "Product: Better Shelter". BetterShelter.org. Retrieved 29 March 2015.
  16. "Synthetic PAO Compressor Oils". Petroleum Service Company.
  17. "Millions of tons of plastic waste could be turned into clean fuels, other products: Chemical conversion process could transform polyolefin waste". ScienceDaily. Retrieved 2019-04-18.
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