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Polypropylene
Polypropylen.svg
Identifiers
CAS number 9003-07-0 YesY
Properties
Molecular formula (C3H6)n
Density 0.855 g/cm3, amorphous

0.946 g/cm3, crystalline

Melting point

130–171 °C

 YesY (what is this?)  (verify)
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Polypropylene (PP), also known as polypropene, is a thermoplastic polymer, made by the chemical industry and used in a wide variety of applications, including packaging, 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 2007, the global market for polypropylene had a volume of 45.1 million tons, which led to a turnover of about 65 billion US-dollars (47.4 billion Euro).[1]

Chemical and physical propertiesEdit

Polypropene migrograph

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); its Young's modulus is also intermediate. 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 of polypropylene occurs as 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 Template:Convert/Dual/LoffAonDbSoffT, 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 used is typically 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.

DegradationEdit

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.

HistoryEdit

Propylene was first polymerized to a crystalline isotactic polymer by Giulio Natta and his coworkers in March of 1954[3]. This pioneering discovery led to large-scale commercial production of isotactic polypropylene from 1957 onwards.[4] Syndiotactic polypropylene was also first synthesized by Giulio Natta and his coworkers.

SynthesisEdit

Polypropylene tacticity

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 Ziegler-Natta 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.

Syndiotactic polypropene

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.[5],[6],[7] 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 70-80°C under standard polymerization conditions. Commercial synthesis of isotactic polypropylene is usually carried out either in the medium of liquid propylene or in gas-phase 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).[8] These complexes are converted to polymerization catalysts by activating them with a special organoaluminum cocatalyst, methylalumoxane MAO[9]

ManufacturingEdit

Melt processing of polypropylene can be achieved via extrusion and molding. Common extrusion methods include production of melt-blown and spun-bond fibers to form long rolls for future conversion into a wide range of useful products, such as face masks, filters, nappies (diapers) and wipes.

The most common shaping technique is injection molding, which is used for parts such as cups, cutlery, vials, caps, containers, housewares, and automotive parts such as batteries. The related techniques of blow molding and injection-stretch blow molding are also used, which involve both extrusion and molding.

The large number of end-use applications for polypropylene are often possible because of the ability to tailor grades with specific molecular properties and additives during its manufacture. For example, antistatic additives can be added to help polypropylene surfaces resist dust and dirt. Many physical finishing techniques can also be used on polypropylene, such as machining. Surface treatments can be applied to polypropylene parts in order to promote adhesion of printing ink and paints.

ApplicationsEdit

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Mint box polypropylene lid

Polypropylene lid of a Tic Tacs box, with a living hinge and the resin identification code under its flap

Since polypropylene is resistant to fatigue, most plastic living hinges, such as those on flip-top bottles, are made from this material. However, it is important to ensure that chain molecules are oriented across the hinge to maximize strength.

Very thin sheets of polypropylene are used as a dielectric within certain high-performance pulse and low-loss RF capacitors.

High-purity piping systems are built using polypropylene. Stronger, more rigid piping systems, intended for use in potable plumbing, hydronic heating and cooling, and reclaimed water applications, are also manufactured using polypropylene.[10] This material is often chosen for its resistance to corrosion and chemical leaching, its resilience against most forms of physical damage, including impact and freezing, its environmental benefits, and its ability to be joined by heat fusion rather than gluing.[11][12][13]

Red Polypropylene Chair with Stainless Steel Structure

A polypropylene chair

Many plastic items for medical or laboratory use can be made from polypropylene because it can withstand the heat in an autoclave. Its heat resistance also enables it to be used as the manufacturing material of consumer-grade kettles. Food containers made from it will not melt in the dishwasher, and do not melt during industrial hot filling processes. For this reason, most plastic tubs for dairy products are polypropylene sealed with aluminum foil (both heat-resistant materials). After the product has cooled, the tubs are often given lids made of a less heat-resistant material, such as LDPE or polystyrene. Such containers provide a good hands-on example of the difference in modulus, since the rubbery (softer, more flexible) feeling of LDPE with respect to polypropylene of the same thickness is readily apparent. Rugged, translucent, reusable plastic containers made in a wide variety of shapes and sizes for consumers from various companies such as Rubbermaid and Sterilite are commonly made of polypropylene, although the lids are often made of somewhat more flexible LDPE so they can snap on to the container to close it. Polypropylene can also be made into disposable bottles to contain liquid, powdered, or similar consumer products, although HDPE and polyethylene terephthalate are commonly also used to make bottles. Plastic pails, car batteries, wastebaskets, cooler containers, dishes and pitchers are often made of polypropylene or HDPE, both of which commonly have rather similar appearance, feel, and properties at ambient temperature.

A common application for polypropylene is as biaxially oriented polypropylene (BOPP). These BOPP sheets are used to make a wide variety of materials including clear bags. When polypropylene is biaxially oriented, it becomes crystal clear and serves as an excellent packaging material for artistic and retail products.

Polypropylene, highly colorfast, is widely used in manufacturing carpets, rugs and mats to be used at home.[14]

Polypropylene is widely used in ropes, distinctive because they are light enough to float in water.[15] For equal mass and construction, polypropylene rope is similar in strength to polyester rope. Polypropylene costs less than most other synthetic fibers.

Polypropylene is also used as an alternative to polyvinyl chloride (PVC) as insulation for electrical cables for LSZH cable in low-ventilation environments, primarily tunnels. This is because it emits less smoke and no toxic halogens, which may lead to production of acid in high-temperature conditions.

Polypropylene is also used in particular roofing membranes as the waterproofing top layer of single-ply systems as opposed to modified-bit systems.

Polypropylene is most commonly used for plastic moldings, wherein it is injected into a mold while molten, forming complex shapes at relatively low cost and high volume; examples include bottle tops, bottles, and fittings.

Recently[when?], it has been produced in sheet form, which has been widely used for the production of stationery folders, packaging, and storage boxes. The wide color range, durability, and resistance to dirt make it ideal as a protective cover for papers and other materials. It is used in Rubik's cube stickers because of these characteristics.

The availability of sheet polypropylene has provided an opportunity for the use of the material by designers. The light-weight, durable, and colorful plastic makes an ideal medium for the creation of light shades, and a number of designs have been developed using interlocking sections to create elaborate designs.

Polypropylene sheets are a popular choice for trading card collectors; these come with pockets (nine for standard-size cards) for the cards to be inserted and are used to protect their condition and are meant to be stored in a binder.

In 2008, Researchers in Canada asserted that quaternary ammonium biocides and oleamide were leaking out of certain polypropylene labware, affecting experimental results.[16] Since polypropylene is used in a wide number of food containers such as those for yogurt, Health Canada media spokesman Paul Duchesne, said the department will be reviewing the findings to determine whether steps are needed to protect consumers.[17]

Expanded polypropylene (EPP) is a foam form of polypropylene. EPP has very good impact characteristics due to its low stiffness; this allows EPP to resume its shape after impacts. EPP is extensively used in model aircraft and other radio controlled vehicles by hobbyists. This is mainly due to its ability to absorb impacts, making this an ideal material for RC aircraft for beginners and amateurs.

Polypropylene is used in the manufacture of loudspeaker drive units. Its use was pioneered by engineers at the BBC and the patent rights subsequently purchased by Mission Electronics for use in their Mission Freedom Loudspeaker and Mission 737 Renaissance loudspeaker.

Polypropylene fibres are used as a concrete additive to increase strength and reduce cracking and spalling.[18]

ClothesEdit

Polypropylene is a major polymer used in nonwovens, with over 50% used[citation needed] for diapers or sanitary products where it is treated to absorb water (hydrophilic) rather than naturally repelling water (hydrophobic). Other interesting non-woven uses include filters for air, gas, and liquids in which the fibers can be formed into sheets or webs that can be pleated to form cartridges or layers that filter in various efficiencies in the 0.5 to 30 micrometre range. Such applications could be seen in the house as water filters or air-conditioning-type filters. The high surface area and naturally hydrophilic polypropylene nonwovens are ideal absorbers of oil spills with the familiar floating barriers near oil spills on rivers.

In New Zealand, in the US military, and elsewhere, polypropylene, or 'polypro' (New Zealand 'polyprops'), has been used for the fabrication of cold-weather base layers, such as long-sleeve shirts or long underwear (More recently, polyester has replaced polypropylene in these applications in the U.S. military, such as in the ECWCS [19]). Polypropylene is also used in warm-weather gear such as some Under Armour clothing, which can easily transport sweat away from the skin. Although polypropylene clothes are not easily flammable, they can melt, which may result in severe burns if the service member is involved in an explosion or fire of any kind.[20]. Polypropylene undergarments are known for retaining body odors which are then difficult to remove. The current generation of polyester does not have this disadvantage.[21]

The material has recently been introduced into the fashion industry through the work of designers such as Anoush Waddington, who have developed specialized techniques to create jewelry and wearable items from polypropylene.

MedicalEdit

Its most common medical use is in the synthetic, nonabsorbable suture Prolene, manufactured by Ethicon Inc.

Polypropylene has been used in hernia and pelvic organ prolapse repair operations to protect the body from new hernias in the same location. A small patch of the material is placed over the spot of the hernia, below the skin, and is painless and is rarely, if ever, rejected by the body. However, a polypropylene mesh will erode over the uncertain period from days to years. Therefore, the FDA has issued several warnings on the use of polypropylene mesh medical kits for certain applications in pelvic organ prolapse, specifically when introduced in close proximity to the vaginal wall due to a continued increase in number of mesh erosions reported by patients over the past few years.[22]

RecyclingEdit

Polypropylene is commonly recycled, and has the number "5" as its resin identification code: Resin-identification-code-5-PP.[23]

Repairing Edit

Solid objects in PP may be joined with a two part epoxy glue.

ReferencesEdit

  1. "Market Study: Polypropylene". Ceresana Research. http://www.ceresana.com/en/market-studies/plastics/polypropylene/. 
  2. Maier, Clive; Calafut, Teresa (1998), Polypropylene: the definitive user's guide and databook, William Andrew, p. 14, ISBN 9781884207587, http://books.google.com/books?id=AWaSJd9Non8C&pg=PA14. 
  3. Peter J. T. Morris (2005). Polymer Pioneers: A Popular History of the Science and Technology of Large Molecules. Chemical Heritage Foundation. p. 76. ISBN 0941901033. http://books.google.com/books?id=GjtJfmxvSWgC&pg=PA76. 
  4. This week 50 years ago in New Scientist, 28 April 2007, p. 15
  5. Y. V. Kissin Alkene Polymerization Reactions with Transition Metal Catalysts, Elsevier, 2008, Chapter 4
  6. J. Severn, R. L. Jones Handbook of Transition Metal Polymerization Catalysts, R. Hoff, R. T. Mathers, eds, Wiley, 2010, Chapter 7
  7. E. P. Moore Polypropylene Handbook. Polymerization, Characterization, Properties, Processing, Applications, Hanser Publishers: New York, 1996
  8. G. M. Benedikt, B. L. Goodall, eds. Metallocene Catalyzed Polymers, ChemTech Publishing: Toronto, 1998
  9. H. Sinn, W. Kaminsky, H. Höker, eds. Alumoxanes, Macromol. Symp. 97, Huttig & Wepf: Heidelberg, 1995
  10. ASTM Standard F2389, 2007, "Standard Specification for Pressure-rated Polypropylene (PP) Piping Systems", ASTM International, West Conshohocken, PA, 2007, DOI:10.1520/F2389-07E01, www.astm.org.
  11. Green pipe helps miners remove the black Contractor Magazine, 10 January 2010
  12. Contractor Retrofits His Business the News, 2 November 2009
  13. What to do when the piping replacement needs a replacement? Engineered Systems, 1 November 2009
  14. Rug fibers
  15. Rope Materials
  16. Plastic additives leach into medical experiments, research shows, Physorg.com, 10 November 2008
  17. Scientific tests skewed by leaching plastics, November 6, 2008.
  18. [1] [2]
  19. ECWCS Gen. III
  20. USAF Flying Magazine. Safety. Nov. 2002.
  21. Get Real: The true story of performance next to skin fabrics
  22. FDA Public Health Notification: Serious Complications Associated with Transvaginal Placement of Surgical Mesh in Repair of Pelvic Organ Prolapse and Stress Urinary Incontinence, FDA, October 20, 2008
  23. Plastics recycling information sheet, Waste Online

External linksEdit

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