Hubbry Logo
PolyethylenePolyethyleneMain
Open search
Polyethylene
Community hub
Polyethylene
logo
8 pages, 0 posts
0 subscribers
Be the first to start a discussion here.
Be the first to start a discussion here.
Polyethylene
Polyethylene
from Wikipedia

Polyethylene
Skeletal formula of a ris monomer
Skeletal formula of a ris monomer
Spacefill model of polyethylene
Spacefill model of polyethylene
Sample of granulated polyethylene
Sample of granulated polyethylene
Names
IUPAC name
Polyethene or poly(methylene)[1]
Other names
Polyethylene
Polythene
Identifiers
Abbreviations PE
ChemSpider
  • none
ECHA InfoCard 100.121.698 Edit this at Wikidata
KEGG
MeSH Polyethylene
UNII
Properties
(C2H4)n
Density 0.88–0.96 g/cm3[2]
Melting point 115–135 °C (239–275 °F; 388–408 K)[2]
Not soluble
log P 1.02620[3]
−9.67×10−6 (HDPE, SI, 22 °C)[4]
Thermochemistry
−28 to −29 kJ/mol[5]
650–651 kJ/mol, 46 MJ/kg[5]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
The repeating unit within polyethylene in the most stable[6] staggered conformation

Polyethylene or polythene (abbreviated PE; IUPAC name polyethene or poly(methylene)) is the most commonly produced plastic.[7] It is a polymer, primarily used for packaging (plastic bags, plastic films, geomembranes and containers including bottles, cups, jars, etc.). As of 2017, over 100 million tonnes of polyethylene resins are being produced annually, accounting for 34% of the total plastics market.[8][9]

Many kinds of polyethylene are known, with most having the chemical formula (C2H4)n. PE is usually a mixture of similar polymers of ethylene, with various values of n. It can be low-density or high-density and many variations thereof. Its properties can be modified further by crosslinking or copolymerization. All forms are nontoxic as well as chemically resilient, contributing to polyethylene's popularity as a multi-use plastic. However, polyethylene's chemical resilience also makes it a long-lived and decomposition-resistant pollutant when disposed of improperly.[10] Being a hydrocarbon, polyethylene is colorless to opaque (without impurities or colorants) and combustible.[11]

History

[edit]

Polyethylene was first synthesized by the German chemist Hans von Pechmann, who prepared it by accident in 1898 while investigating diazomethane.[12][a][13][b] When his colleagues Eugen Bamberger and Friedrich Tschirner characterized the white, waxy substance that he had created, they recognized that it contained long −CH2− chains and termed it polymethylene.[14]

A pill box presented to a technician at ICI in 1936 made from the first pound of polyethylene

The first industrially practical polyethylene synthesis (diazomethane is a notoriously unstable substance that is generally avoided in industrial syntheses) was again accidentally discovered in 1933 by Eric Fawcett and Reginald Gibson at the Imperial Chemical Industries (ICI) works in Northwich, England.[15] Upon applying extremely high pressure (several hundred atmospheres) to a mixture of ethylene and benzaldehyde they again produced a white, waxy material. Because the reaction had been initiated by trace oxygen contamination in their apparatus, the experiment was difficult to reproduce at first. It was not until 1935 that another ICI chemist, Michael Perrin, developed this accident into a reproducible high-pressure synthesis for polyethylene that became the basis for industrial low-density polyethylene (LDPE) production beginning in 1939. Because polyethylene was found to have very low-loss properties at very high frequency radio waves, commercial distribution in Britain was suspended on the outbreak of World War II, secrecy imposed, and the new process was used to produce insulation for UHF and SHF coaxial cables of radar sets. During World War II, further research was done on the ICI process and in 1944, DuPont at Sabine River, Texas, and Union Carbide Corporation at South Charleston, West Virginia, began large-scale commercial production under license from ICI.[16][17]

The landmark breakthrough in the commercial production of polyethylene began with the development of catalysts that promoted the polymerization at mild temperatures and pressures. The first of these was a catalyst based on chromium trioxide discovered in 1951 by Robert Banks and J. Paul Hogan at Phillips Petroleum.[18] In 1953 the German chemist Karl Ziegler developed a catalytic system based on titanium halides and organoaluminium compounds that worked at even milder conditions than the Phillips catalyst. The Phillips catalyst is less expensive and easier to work with, however, and both methods are heavily used industrially. By the end of the 1950s both the Phillips- and Ziegler-type catalysts were being used for high-density polyethylene (HDPE) production. In the 1970s, the Ziegler system was improved by the incorporation of magnesium chloride. Catalytic systems based on soluble catalysts, the metallocenes, were reported in 1976 by Walter Kaminsky and Hansjörg Sinn. The Ziegler- and metallocene-based catalysts families have proven to be very flexible at copolymerizing ethylene with other olefins and have become the basis for the wide range of polyethylene resins available today, including very-low-density polyethylene and linear low-density polyethylene. Such resins, in the form of UHMWPE fibers, have (as of 2005) begun to replace aramids in many high-strength applications.

Properties

[edit]

The properties of polyethylene depend strongly on type. The molecular weight, crosslinking, and presence of comonomers all strongly affect its properties. It is for this structure-property relation that intense effort has been invested into diverse kinds of PE.[7][19] LDPE is softer and more transparent than HDPE. For medium- and high-density polyethylene the melting point is typically in the range 120 to 130 °C (248 to 266 °F). The melting point for average commercial low-density polyethylene is typically 105 to 115 °C (221 to 239 °F). These temperatures vary strongly with the type of polyethylene, but the theoretical upper limit of melting of polyethylene is reported to be 144 to 146 °C (291 to 295 °F). Combustion typically occurs above 349 °C (660 °F).

Most LDPE, MDPE, and HDPE grades have excellent chemical resistance, meaning that they are not attacked by strong acids or strong bases and are resistant to gentle oxidants and reducing agents. Crystalline samples do not dissolve at room temperature. Polyethylene (other than cross-linked polyethylene) usually can be dissolved at elevated temperatures in aromatic hydrocarbons such as toluene or xylene, or in chlorinated solvents such as trichloroethane or trichlorobenzene.[7]

Polyethylene absorbs almost no water. The permeability for water vapor and polar gases of is lower than for most plastics. On the other hand, non-polar gases such as Oxygen, carbon dioxide, and flavorings can pass it easily.

Polyethylene burns slowly with a blue flame having a yellow tip and gives off an odour of paraffin (similar to candle flame). The material continues burning on removal of the flame source and produces a drip.[20]

Polyethylene cannot be imprinted or bonded with adhesives without pretreatment. High-strength joints are readily achieved with plastic welding.

Electrical

[edit]

Polyethylene is a good electrical insulator. It offers good electrical treeing resistance; however, it becomes easily electrostatically charged (which can be reduced by additions of graphite, carbon black or antistatic agents). When pure, the dielectric constant is in the range 2.2 to 2.4 depending on the density[21] and the loss tangent is very low, making it a good dielectric for building capacitors. For the same reason it is commonly used as the insulation material for high-frequency coaxial and twisted pair cables.

Optical

[edit]

Depending on thermal history and film thickness, PE can vary between almost clear (transparent), milky-opaque (translucent) and opaque. LDPE has the greatest, LLDPE slightly less, and HDPE the least transparency. Transparency is reduced by crystallites if they are larger than the wavelength of visible light.[22]

Manufacturing process

[edit]

Monomer

[edit]
ethylene skeleton
ethylene 3D model
Ethylene (ethene)

The ingredient or monomer is ethylene (IUPAC name ethene), a gaseous hydrocarbon with the formula C2H4, which can be viewed as a pair of methylene groups (−CH
2
−) connected to each other. Typical specifications for PE purity are <5 ppm for water, oxygen, and other alkenes contents. Acceptable contaminants include N2, ethane (common precursor to ethylene), and methane. Ethylene is usually produced from petrochemical sources, but is also generated by dehydration of ethanol.[7]

Polymerization

[edit]

Polymerization of ethylene to polyethylene is described by the following chemical equation:

n CH
2
=CH
2
(gas) → [−CH
2
−CH
2
]
n
(solid) ΔH/n = −25.71 ± 0.59 kcal/mol (−107.6 ± 2.5 kJ/mol)[23]

Ethylene is a stable molecule that polymerizes only upon contact with catalysts. The conversion is highly exothermic. Coordination polymerization is the most pervasive technology, which means that metal chlorides or metal oxides are used. The most common catalysts consist of titanium(III) chloride, the so-called Ziegler–Natta catalysts. Another common catalyst is the Phillips catalyst, prepared by depositing chromium(VI) oxide on silica.[7] Polyethylene can be produced through radical polymerization, but this route has only limited utility and typically requires high-pressure apparatus.

Joining

[edit]

Commonly used methods for joining polyethylene parts together include:[24]

Pressure-sensitive adhesives (PSA) are feasible if the surface chemistry or charge is modified with plasma activation, flame treatment, or corona treatment.

Classification

[edit]

Polyethylene is classified by its density and branching. Its mechanical properties depend significantly on variables such as the extent and type of branching, the crystal structure, and the molecular weight. There are several types of polyethylene:

With regard to sold volumes, the most important polyethylene grades are HDPE, LLDPE, and LDPE.

Ultra-high-molecular-weight (UHMWPE)

[edit]
Stainless steel and ultra-high-molecular-weight polyethylene hip replacement

UHMWPE is polyethylene with a molecular weight numbering in the millions, usually between 3.5 and 7.5 million amu.[25] The high molecular weight makes it a very tough material, but results in less efficient packing of the chains into the crystal structure as evidenced by densities of less than high-density polyethylene (for example, 0.930–0.935 g/cm3). UHMWPE can be made through any catalyst technology, although Ziegler catalysts are most common. Because of its outstanding toughness and its cut, wear, and excellent chemical resistance, UHMWPE is used in a diverse range of applications. These include can- and bottle-handling machine parts, moving parts on weaving machines, bearings, gears, artificial joints, edge protection on ice rinks, steel cable replacements on ships, and butchers' chopping boards. It is commonly used for the construction of articular portions of implants used for hip and knee replacements. As fiber, it competes with aramid in bulletproof vests.

High-density (HDPE)

[edit]
HDPE pipe on site during installation in outback Western Australia. The white outer layer, Acu-Therm, is co-extruded to provide a reduction of thermal heating.

HDPE is defined by a density of greater or equal to 0.941 g/cm3. HDPE has a low degree of branching. The mostly linear molecules pack together well, so intermolecular forces are stronger than in highly branched polymers. HDPE can be produced by chromium/silica catalysts, Ziegler–Natta catalysts or metallocene catalysts; by choosing catalysts and reaction conditions, the small amount of branching that does occur can be controlled. These catalysts prefer the formation of free radicals at the ends of the growing polyethylene molecules. They cause new ethylene monomers to add to the ends of the molecules, rather than along the middle, causing the growth of a linear chain.

HDPE has high tensile strength. It is used in products and packaging such as milk jugs, detergent bottles, butter tubs, garbage containers, and water pipes.

Cross-linked (PEX or XLPE)

[edit]

PEX is a medium- to high-density polyethylene containing cross-link bonds introduced into the polymer structure, changing the thermoplastic into a thermoset. The high-temperature properties of the polymer are improved, its flow is reduced, and its chemical resistance is enhanced. PEX is used in some potable-water plumbing systems because tubes made of the material can be expanded to fit over a metal nipple and it will slowly return to its original shape, forming a permanent, water-tight connection.

Medium-density (MDPE)

[edit]

MDPE is defined by a density range of 0.926–0.940 g/cm3. MDPE can be produced by chromium/silica catalysts, Ziegler–Natta catalysts, or metallocene catalysts. MDPE has good shock and drop resistance properties. It also is less notch-sensitive than HDPE; stress-cracking resistance is better than HDPE. MDPE is typically used in gas pipes and fittings, sacks, shrink film, packaging film, carrier bags, and screw closures.

Linear low-density (LLDPE)

[edit]

LLDPE is defined by a density range of 0.915–0.925 g/cm3. LLDPE is a substantially linear polymer with significant numbers of short branches, commonly made by copolymerization of ethylene with short-chain alpha-olefins (for example, 1-butene, 1-hexene, and 1-octene). LLDPE has higher tensile strength than LDPE, and it exhibits higher impact and puncture resistance than LDPE. Lower-thickness (gauge) films can be blown, compared with LDPE, with better environmental stress cracking resistance, but they are not as easy to process. LLDPE is used in packaging, particularly film for bags and sheets. Lower thickness may be used compared to LDPE. It is used for cable coverings, toys, lids, buckets, containers, and pipe. While other applications are available, LLDPE is used predominantly in film applications due to its toughness, flexibility, and relative transparency. Product examples range from agricultural films, Saran wrap, and bubble wrap to multilayer and composite films.

Low-density (LDPE)

[edit]

LDPE is defined by a density range of 0.910–0.940 g/cm3. LDPE has a high degree of short- and long-chain branching, which means that the chains do not pack into the crystal structure as well. It has, therefore, less strong intermolecular forces as the instantaneous-dipole induced-dipole attraction is less. This results in a lower tensile strength and increased ductility. LDPE is created by free-radical polymerization. The high degree of branching with long chains gives molten LDPE unique and desirable flow properties. LDPE is used for both rigid containers and plastic film applications such as plastic bags and film wrap.

The radical polymerization process used to make LDPE does not include a catalyst that "supervises" the radical sites on the growing PE chains. (In HDPE synthesis, the radical sites are at the ends of the PE chains, because the catalyst stabilizes their formation at the ends.) Secondary radicals (in the middle of a chain) are more stable than primary radicals (at the end of the chain), and tertiary radicals (at a branch point) are more stable yet. Each time an ethylene monomer is added, it creates a primary radical, but often these will rearrange to form more stable secondary or tertiary radicals. Addition of ethylene monomers to the secondary or tertiary sites creates branching.

Very-low-density (VLDPE)

[edit]

VLDPE is defined by a density range of 0.880–0.915 g/cm3. VLDPE is a substantially linear polymer with high levels of short-chain branches, commonly made by copolymerization of ethylene with short-chain alpha-olefins (for example, 1-butene, 1-hexene and 1-octene). VLDPE is most commonly produced using metallocene catalysts due to the greater co-monomer incorporation exhibited by these catalysts. VLDPEs are used for hose and tubing, ice and frozen food bags, food packaging and stretch wrap as well as impact modifiers when blended with other polymers.

Much research activity has focused on the nature and distribution of long chain branches in polyethylene. In HDPE, a relatively small number of these branches, perhaps one in 100 or 1,000 branches per backbone carbon, can significantly affect the rheological properties of the polymer.

Copolymers

[edit]

In addition to copolymerization with alpha-olefins, ethylene can be copolymerized with a wide range of other monomers and ionic composition that creates ionized free radicals. Common examples include vinyl acetate (the resulting product is ethylene-vinyl acetate copolymer, or EVA, widely used in athletic-shoe sole foams) and a variety of acrylates. Applications of acrylic copolymer include packaging and sporting goods, and superplasticizer, used in cement production.

Types of polyethylenes

[edit]

The particular material properties of "polyethylene" depend on its molecular structure. Molecular weight and crystallinity are the most significant factors; crystallinity in turn depends on molecular weight and degree of branching. The less the polymer chains are branched, and the lower the molecular weight, the higher the crystallinity of polyethylene. Crystallinity ranges from 35% (PE-LD/PE-LLD) to 80% (PE-HD). Polyethylene has a density of 1.0 g/cm3 in crystalline regions and 0.86 g/cm3 in amorphous regions. An almost linear relationship exists between density and crystallinity.[19]

The degree of branching of the different types of polyethylene can be schematically represented as follows:[19]

PE-HD Schematic representation of PE-HD (high-density polyethylene)
PE-LLD

Schematic representation of PE-LLD (linear low-density polyethylene)

PE-LD Schematic representation of PE-LD (low-density polyethylene)

The figure shows polyethylene backbones, short-chain branches and side-chain branches. The polymer chains are represented linearly.

Chain branches

[edit]

The properties of polyethylene are highly dependent on type and number of chain branches. The chain branches in turn depend on the process used: either the high-pressure process (only PE-LD) or the low-pressure process (all other PE grades). Low-density polyethylene is produced by the high-pressure process by radical polymerization, thereby numerous short chain branches as well as long chain branches are formed. Short chain branches are formed by intramolecular chain transfer reactions, they are always butyl or ethyl chain branches because the reaction proceeds after the following mechanism:

Mechanism for the emergence of side chains during synthesis of polyethylene (PE-LD).

Environmental issues

[edit]
A recyclable bag manufactured from polyethylene, resin identification code
Say no to polythene. Sign. Nako, Himachal Pradesh, India.

The widespread usage of polyethylene poses potential difficulties for waste management because it is not readily biodegradable. Since 2008, Japan has increased plastic recycling, but still has a large amount of plastic wrapping which goes to waste. Plastic recycling in Japan is a potential US$90 billion market.[26]

It is possible to rapidly convert polyethylene to hydrogen and graphene by heating. The energy needed is much less than for producing hydrogen by electrolysis.[27][28]

Biodegradability

[edit]

Several experiments have been conducted aimed at discovering an enzyme or organisms that will degrade polyethylene. Several plastics - such as polyesters, polycarbonates, and polyamides - degrade either by hydrolysis or air oxidation. In some cases the degradation is increased by bacteria or various enzyme cocktails. The situation is very different with polymers where the backbone consists solely of C-C bonds. These polymers include polyethylene, but also polypropylene, polystyrene and acrylates. At best, these polymers degrade very slowly, but degradation experiments are difficult because yields and rates are very slow.[29] Further confusing the situation, even preliminary successes are greeted with enthusiasm by the popular press.[30][31][32] Some technical challenges in this area include the failure to identify enzymes responsible for the proposed degradation. Another issue is that organisms are incapable of importing hydrocarbons of molecular weight greater than 500.[29]

Bacteria and insect case studies

[edit]

The Indian mealmoth larvae are claimed to metabolize polyethylene based on observing that plastic bags at a researcher's home had small holes in them. Deducing that the hungry larvae must have digested the plastic somehow, he and his team analyzed their gut bacteria and found a few that could use plastic as their only carbon source. Not only could the bacteria from the guts of the Plodia interpunctella moth larvae metabolize polyethylene, they degraded it significantly, dropping its tensile strength by 50%, its mass by 10% and the molecular weights of its polymeric chains by 13%.[33][34]

The caterpillar of Galleria mellonella is claimed to consume polyethylene. The caterpillar is able to digest polyethylene due to a combination of its gut microbiota[35] and its saliva containing enzymes that oxidise and depolymerise the plastic.[36]

Climate change

[edit]

When exposed to ambient solar radiation the plastic produces trace amounts of two greenhouse gases, methane and ethylene. The plastic type which releases gases at the highest rate is low-density polyethylene (LDPE). Due to its low density it breaks down more easily over time, leading to higher surface areas. When incubated in air, LDPE emits gases at rates ~2 times and ~76 times higher in comparison to incubation in water for methane and ethylene, respectively. However, based on the rates measured in the study methane production by plastics is presently an insignificant component of the global methane budget.[37]

Chemically modified polyethylene

[edit]

Polyethylene may either be modified in the polymerization by polar or non-polar comonomers or after polymerization through polymer-analogous reactions. Common polymer-analogous reactions are in case of polyethylene crosslinking, chlorination and sulfochlorination.

Non-polar ethylene copolymers

[edit]

α-olefins

[edit]

In the low pressure process α-olefins (e.g. 1-butene or 1-hexene) may be added, which are incorporated in the polymer chain during polymerization. These copolymers introduce short side chains, thus crystallinity and density are reduced. As explained above, mechanical and thermal properties are changed thereby. In particular, PE-LLD is produced this way.

Metallocene polyethylene (PE-MC)

[edit]

Metallocene polyethylene (PE-M) is prepared by means of metallocene catalysts, usually including copolymers (z. B. ethene / hexene). Metallocene polyethylene has a relatively narrow molecular weight distribution, exceptionally high toughness, excellent optical properties and a uniform comonomer content. Because of the narrow molecular weight distribution it behaves less pseudoplastic (especially under larger shear rates). Metallocene polyethylene has a low proportion of low molecular weight (extractable) components and a low welding and sealing temperature. Thus, it is particularly suitable for the food industry.[19]: 238 [38]: 19 

Polyethylene with multimodal molecular weight distribution

[edit]

Polyethylene with multimodal molecular weight distribution consists of several polymer fractions, which are homogeneously mixed. Such polyethylene types offer extremely high stiffness, toughness, strength, stress crack resistance and an increased crack propagation resistance. They consist of equal proportions higher and lower molecular polymer fractions. The lower molecular weight units crystallize easier and relax faster. The higher molecular weight fractions form linking molecules between crystallites, thereby increasing toughness and stress crack resistance. Polyethylene with multimodal molecular weight distribution can be prepared either in two-stage reactors, by catalysts with two active centers on a carrier or by blending in extruders.[19]: 238 

Cyclic olefin copolymers (COC)

[edit]

Cyclic olefin copolymers are prepared by copolymerization of ethene and cycloolefins (usually norbornene) produced by using metallocene catalysts. The resulting polymers are amorphous polymers and particularly transparent and heat resistant.[19]: 239 [38]: 27 

Polar ethylene copolymers

[edit]

The basic compounds used as polar comonomers are vinyl alcohol (Ethenol, an unsaturated alcohol), acrylic acid (propenoic acid, an unsaturated acid) and esters containing one of the two compounds.

Ethylene copolymers with unsaturated alcohols

[edit]

Ethylene/vinyl alcohol copolymer (EVOH) is (formally) a copolymer of PE and vinyl alcohol (ethenol), which is prepared by (partial) hydrolysis of ethylene-vinyl acetate copolymer (as vinyl alcohol itself is not stable). However, typically EVOH has a higher comonomer content than the VAC commonly used.[39]: 239 

EVOH is used in multilayer films for packaging as a barrier layer (barrier plastic). As EVOH is hygroscopic (water-attracting), it absorbs water from the environment, whereby it loses its barrier effect. Therefore, it must be used as a core layer surrounded by other plastics (like LDPE, PP, PA or PET). EVOH is also used as a coating agent against corrosion at street lights, traffic light poles and noise protection walls.[39]: 239 

Ethylene/acrylic acid copolymers (EAA)

[edit]

Copolymer of ethylene and unsaturated carboxylic acids (such as acrylic acid) are characterized by good adhesion to diverse materials, by resistance to stress cracking and high flexibility.[40] However, they are more sensitive to heat and oxidation than ethylene homopolymers. Ethylene/acrylic acid copolymers are used as adhesion promoters.[19]

If salts of an unsaturated carboxylic acid are present in the polymer, thermo-reversible ion networks are formed, they are called ionomers. Ionomers are highly transparent thermoplastics which are characterized by high adhesion to metals, high abrasion resistance and high water absorption.[19]

Ethylene copolymers with unsaturated esters

[edit]

If unsaturated esters are copolymerized with ethylene, either the alcohol moiety may be in the polymer backbone (as it is the case in ethylene-vinyl acetate copolymer) or of the acid moiety (e. g. in ethylene-ethyl acrylate copolymer). Ethylene-vinyl acetate copolymers are prepared similarly to LD-PE by high pressure polymerization. The proportion of comonomer has a decisive influence on the behaviour of the polymer.

The density decreases up to a comonomer share of 10% because of the disturbed crystal formation. With higher proportions it approaches to the one of polyvinyl acetate (1.17 g/cm3).[39]: 235  Due to decreasing crystallinity ethylene vinyl acetate copolymers are getting softer with increasing comonomer content. The polar side groups change the chemical properties significantly (compared to polyethylene):[19]: 224  weather resistance, adhesiveness and weldability rise with comonomer content, while the chemical resistance decreases. Also mechanical properties are changed: stress cracking resistance and toughness in the cold rise, whereas yield stress and heat resistance decrease. With a very high proportion of comonomers (about 50%) rubbery thermoplastics are produced (thermoplastic elastomers).[39]: 235 

Ethylene-ethyl acrylate copolymers behave similarly to ethylene-vinyl acetate copolymers.[19]: 240 

Crosslinking

[edit]

A basic distinction is made between peroxide crosslinking (PE-Xa), silane crosslinking (PE-Xb), electron beam crosslinking (PE-Xc) and azo crosslinking (PE-Xd).[41]

Shown are the peroxide, the silane and irradiation crosslinking

Shown are the peroxide, the silane and irradiation crosslinking. In each method, a radical is generated in the polyethylene chain (top center), either by radiation (h·ν) or by peroxides (R-O-O-R). Then, two radical chains can either directly crosslink (bottom left) or indirectly by silane compounds (bottom right).

  • Peroxide crosslinking (PE-Xa): The crosslinking of polyethylene using peroxides (e. g. dicumyl or di-tert-butyl peroxide) is still of major importance. In the so-called Engel process, a mixture of HDPE and 2%[42] peroxide is at first mixed at low temperatures in an extruder and then crosslinked at high temperatures (between 200 and 250 °C).[41] The peroxide decomposes to peroxide radicals (RO•), which abstract (remove) hydrogen atoms from the polymer chain, leading to radicals. When these combine, a crosslinked network is formed.[43] The resulting polymer network is uniform, of low tension and high flexibility, whereby it is softer and tougher than (the irradiated) PE-Xc.[41]
  • Silane crosslinking (PE-Xb): In the presence of silanes (e.g. trimethoxyvinylsilane) polyethylene can initially be Si-functionalized by irradiation or by a small amount of a peroxide. Later Si-OH groups can be formed in a water bath by hydrolysis, which condense then and crosslink the PE by the formation of Si-O-Si bridges. [16] Catalysts such as dibutyltin dilaurate may accelerate the reaction.[42]
  • Irradiation crosslinking (PE-Xc): The crosslinking of polyethylene is also possible by a downstream radiation source (usually an electron accelerator, occasionally an isotopic radiator). PE products are crosslinked below the crystalline melting point by splitting off hydrogen atoms. β-radiation possesses a penetration depth of 10 mm, ɣ-radiation 100 mm. Thereby the interior or specific areas can be excluded from the crosslinking.[41] However, due to high capital and operating costs radiation crosslinking plays only a minor role compared with the peroxide crosslinking.[39] In contrast to peroxide crosslinking, the process is carried out in the solid state. Thereby, the cross-linking takes place primarily in the amorphous regions, while the crystallinity remains largely intact.[42]
  • Azo crosslinking (PE-Xd): In the so-called Lubonyl process polyethylene is crosslinked preadded azo compounds after extrusion in a hot salt bath.[39][41]

Chlorination and sulfochlorination

[edit]

Chlorinated Polyethylene (PE-C) is an inexpensive material having a chlorine content from 34 to 44%. It is used in blends with PVC because the soft, rubbery chloropolyethylene is embedded in the PVC matrix, thereby increasing the impact resistance. It also increases the weather resistance. Furthermore, it is used for softening PVC foils, without risking the migrate of plasticizers. Chlorinated polyethylene can be crosslinked peroxidically to form an elastomer which is used in cable and rubber industry.[39] When chlorinated polyethylene is added to other polyolefins, it reduces the flammability.[19]: 245 

Chlorosulfonated PE (CSM) is used as starting material for ozone-resistant synthetic rubber.[44]

Bio-based polyethylene

[edit]

Braskem and Toyota Tsusho Corporation started joint marketing activities to produce polyethylene from sugarcane. Braskem will build a new facility at their existing industrial unit in Triunfo, Rio Grande do Sul, Brazil with an annual production capacity of 200,000 short tons (180,000,000 kg), and will produce high-density and low-density polyethylene from bioethanol derived from sugarcane.[45]

Nomenclature and general description of the process

[edit]

The name polyethylene comes from the ingredient and not the resulting chemical compound, which contains no double bonds. The scientific name polyethene is systematically derived from the scientific name of the monomer.[46][47] The alkene monomer converts to a long, sometimes very long, alkane in the polymerization process.[47] In certain circumstances it is useful to use a structure-based nomenclature; in such cases IUPAC recommends poly(methylene) (poly(methanediyl) is a non-preferred alternative).[46] The difference in names between the two systems is due to the opening up of the monomer's double bond upon polymerization.[48] The name is abbreviated to PE. In a similar manner polypropylene and polystyrene are shortened to PP and PS, respectively. In the United Kingdom and India the polymer is commonly called polythene, from the ICI trade name, although this is not recognized scientifically.

Footnotes

[edit]

References

[edit]

Bibliography

[edit]
[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
Polyethylene (PE) is a synthetic formed by the addition of (ethene) monomers, consisting of long chains of repeating -CH₂-CH₂- units with the (C₂H₄)ₙ. It is classified into variants such as (LDPE), which features branched chains leading to flexibility and lower crystallinity, and (HDPE), characterized by linear chains that enhance density, strength, and rigidity. These structural differences arise from production methods: LDPE via high-pressure free-radical introducing branches, and HDPE through low-pressure coordination catalysis like Ziegler-Natta processes yielding more ordered structures. Accidentally discovered in 1933 by chemists Reginald Gibson and Eric Fawcett at Imperial Chemical Industries (ICI) during high-pressure experiments with ethylene and benzaldehyde, polyethylene was initially a waxy solid whose potential was recognized for electrical insulation, particularly in wartime radar cables during World War II. Post-war commercialization and innovations in catalysis propelled its growth, making it the most produced plastic worldwide, with global capacity surpassing demand by approximately 30 million metric tons per year as of 2024 due to expansions in regions like Asia. Its key properties—light weight, moisture resistance, chemical stability, and ease of processing—underpin applications in packaging films, bottles, pipes, geomembranes, and consumer goods. While polyethylene's durability and recyclability (via mechanical or chemical means) support its economic utility, its resistance to stems from strong carbon-carbon and carbon-hydrogen bonds, leading to long-term persistence in environments and contributions to plastic waste accumulation, including from fragmentation. Empirical studies confirm low but highlight ecological risks from by and leaching of additives under certain conditions, prompting ongoing research into degradation enhancements and alternatives without compromising performance.

Chemical Structure and Nomenclature

Monomer and Basic Polymer Chain

Polyethylene is produced through the addition of , the with C₂H₄ and structure H₂C=CH₂, a colorless gas at . 's between the two carbon atoms enables the polymerization reaction, where the breaks to form new sigma bonds with adjacent monomers, initiating chain growth under catalytic conditions such as Ziegler-Natta or free radical mechanisms. The resulting basic polymer chain consists of a linear sequence of repeating –CH₂–CH₂– units, yielding the general formula –(CH₂–CH₂)ₙ–, where n denotes the , often exceeding 1,000 for commercial grades, corresponding to molecular weights from tens of thousands to over a million daltons. Each carbon atom in the chain is sp³ hybridized, bonded to two hydrogens and two carbons, forming a flexible, non-polar backbone with tetrahedral geometry that allows for conformational variations like gauche and trans arrangements. In its ideal form, the polyethylene chain lacks branches or functional groups, distinguishing it as a simple alkane polymer, though real-world synthesis introduces minor variations depending on process conditions.

Naming Conventions and Molecular Weight Metrics

Polyethylene is commonly abbreviated as PE in industrial and scientific contexts, with the trivial name "polyethylene" retained for widespread use despite systematic nomenclature alternatives. The source-based IUPAC name is poly(ethene), reflecting its derivation from the ethylene monomer, while the structure-based name is poly(methylene), based on the constitutional repeating unit -CH₂-. This dual nomenclature arises from polymer naming conventions that prioritize either the monomer source or the repeating unit structure, with polyethylene's retained name persisting due to historical and practical adoption in standards like ISO and ASTM. Subtype abbreviations, such as HDPE for high-density polyethylene, follow by prefixing descriptors to PE, though full names expand to reflect density or branching characteristics. Molecular weight metrics for polyethylene are essential for defining its processability and mechanical properties, typically expressed through averages rather than a single value due to polydispersity. The number-average molecular weight (Mₙ) represents the of chain lengths, calculated as total mass divided by total number of chains, while the weight-average molecular weight (Mₓ) weights longer chains more heavily, given by the sum of (chain mass squared) over total mass. The polydispersity index (PDI = Mₓ/Mₙ) quantifies distribution breadth, with values near 1 indicating narrow distributions from controlled and higher values (e.g., 5-10) common in free-radical processes yielding branched structures. Characterization methods include (GPC) for absolute Mₓ and full molecular weight distribution via size exclusion, often calibrated against polyethylene standards for accuracy in high-molecular-weight samples. Viscosity-average molecular weight (Mᵥ) derives from measurements in solvents like trichlorobenzene, correlating empirically with chain entanglement. Industrially, melt mass-flow rate (MFR) serves as an inverse proxy for molecular weight, with low MFR (e.g., <1 g/10 min) denoting high-molecular-weight grades suitable for films or pipes, standardized under ASTM D1238. For ultra-high-molecular-weight polyethylene (UHMWPE), Mₓ exceeds 3 × 10⁶ g/mol, verified by light scattering or advanced GPC to account for entanglement limiting dissolution.

History

Discovery and Early Synthesis

In 1898, German chemist Hans von Pechmann heated diazomethane and obtained a waxy solid with a methylene chain structure akin to polyethylene, though its polymeric composition was not recognized until later analyses. This early material, termed polymethylene, represented an accidental precursor but lacked connection to ethylene polymerization or practical utility. The modern discovery of polyethylene occurred accidentally on March 24, 1933, during experiments by Reginald Gibson and Eric Fawcett at Imperial Chemical Industries (ICI) in Northwich, England. The chemists subjected a mixture of ethylene and benzaldehyde to high pressure (several hundred atmospheres) and temperature (170°C) in a reaction vessel, intending to produce a lubricant. A trace oxygen impurity, likely from a leak, initiated free radical polymerization of pure ethylene, yielding a white, waxy solid identified as polyethylene after purification and analysis. This breakthrough demonstrated the feasibility of synthesizing long-chain hydrocarbons from ethylene under extreme conditions. Initial reproducibility proved challenging due to the uncontrolled role of oxygen initiators, prompting further ICI research. By 1935, Michael Perrin developed a controlled high-pressure process using deliberate peroxide initiators, enabling consistent production of low-density polyethylene (LDPE) without benzaldehyde. This free radical mechanism under pressures of 1000-3000 bar and temperatures of 100-300°C formed branched chains characteristic of early LDPE, setting the stage for industrial scaling.

Commercialization and Scale-Up

Imperial Chemical Industries (ICI) initiated commercial production of polyethylene, branded as "Polythene," with the opening of its first full-scale plant at Wallerscote, England, on September 1, 1939, featuring an initial capacity of 100 tonnes per year. This timing coincided with the outbreak of World War II, which rapidly elevated polyethylene's strategic importance due to its excellent electrical insulation properties, leading to its classified use in coating radar cables for airborne interception systems. Production remained under wartime secrecy, with ICI scaling output to meet military demands, though exact figures were not publicly disclosed until after the war. Following the war's end in 1945, polyethylene was declassified, enabling civilian commercialization and rapid scale-up. ICI expanded domestic facilities, while licensing agreements facilitated international production; in the United States, began large-scale manufacturing at its Sabine River, Texas plant in 1944, followed by at South Charleston, West Virginia. Post-war applications proliferated in packaging, piping, and consumer goods, driving demand; by the early 1950s, global capacity had surged beyond initial wartime levels, with polyethylene becoming the first plastic to exceed one billion pounds in annual U.S. sales. This expansion was supported by process improvements in high-pressure polymerization for low-density polyethylene (LDPE), allowing economical production for films and moldings. Further scale-up in the 1950s involved innovations like the introduction of high-density polyethylene (HDPE) via Ziegler-Natta catalysis in 1953, which lowered production costs and broadened applications, though initial commercialization built on ICI's LDPE foundation. By the late 1950s, annual global production reached several hundred thousand tonnes, reflecting polyethylene's transition from niche wartime material to a cornerstone of the plastics industry.

Post-2000 Innovations and Expansions

Following the maturation of Ziegler-Natta catalysis, post-2000 advancements in polyethylene synthesis centered on metallocene and single-site catalysts, which produced resins with more precise control over molecular architecture, resulting in superior uniformity, reduced gel formation, and enhanced end-use performance such as improved puncture resistance in films. By the early 2000s, these catalysts were economically scaled for commercial production, with Univation Technologies commercializing its bimodal UNIPOL process around 2000 to generate high-density polyethylene (HDPE) in a single reactor, yielding bimodal molecular weight distributions that balanced stiffness and processability for demanding applications like pipes and blow-molded containers. ExxonMobil introduced its Enable series of metallocene polyethylenes in 2008, specifically engineered to replicate the melt strength and optical properties of low-density polyethylene (LDPE)/metallocene linear low-density polyethylene (mLLDPE) blends while using less material, thereby optimizing resource efficiency in flexible packaging. A pivotal sustainability-driven innovation emerged with bio-based polyethylene, produced from ethylene derived via dehydration of bio-ethanol sourced from sugarcane, achieving chemical indistinguishability from petrochemical counterparts while incorporating renewable carbon. Braskem pioneered commercial-scale production in 2010 at its Triunfo facility in Brazil, the first such plant globally, with an initial capacity of 200,000 metric tons per year, enabling drop-in replacement in existing infrastructure and spurring further investments in renewable feedstocks amid rising environmental pressures. This development coincided with broader capacity expansions, as global polyethylene production surged from approximately 70 million metric tons in 2000 to over 110 million metric tons by 2023, propelled by Asia-Pacific demand for packaging and infrastructure, where new facilities in China and the Middle East adopted advanced bimodal and metallocene technologies to meet volume growth. Parallel efforts addressed end-of-life management through catalytic chemical recycling, with post-2000 research yielding processes to depolymerize back to monomers or waxes via hydrogenolysis or pyrolysis, enhancing circularity without compromising virgin resin quality. These innovations, including ExxonMobil's 2020s-era performance polyethylene grades for recyclable full-PE laminates, reflected ongoing refinements in resin design to support higher recycled content while maintaining barrier properties. By 2025, metallocene-capable (LLDPE) capacity exceeded 26 million metric tons annually worldwide, underscoring the technology's dominance in high-value segments.

Physical and Chemical Properties

Mechanical and Thermal Properties

Polyethylene exhibits a range of mechanical properties influenced primarily by its molecular structure, density, and crystallinity. High-density polyethylene (HDPE), with its linear chains and high crystallinity (typically 60-80%), demonstrates greater stiffness and tensile strength compared to branched low-density polyethylene (LDPE), which has lower crystallinity (40-50%) and thus higher ductility but reduced rigidity. For HDPE, tensile yield strength ranges from 20 to 31 MPa, Young's modulus from 0.8 to 1 GPa, and elongation at break exceeding 500%. LDPE, by contrast, offers tensile strength around 10 MPa, a lower modulus of approximately 0.2 GPa, and elongation up to 600%, enabling greater flexibility for applications like films. Ultra-high-molecular-weight polyethylene (UHMWPE), featuring extremely long chains (molecular weight >3 million g/mol), provides exceptional impact resistance and abrasion tolerance, with tensile strength of 20-40 MPa and elongation often >300%, though its modulus remains comparable to HDPE at 0.8-1.6 GPa due to reduced crystallinity from chain entanglement. Thermal properties of polyethylene are characterized by low temperatures (Tg) and points that vary with branching and . The Tg for HDPE lies between -100°C and -130°C, rendering it rubbery at , while LDPE's Tg is around -60°C to -120°C. points range from 105-115°C for LDPE to 120-130°C for HDPE and UHMWPE, reflecting higher crystallinity in linear variants that requires more energy to disrupt ordered regions. conductivity is low across types, at 0.33 W/m·K for LDPE and 0.45-0.52 W/m·K for HDPE, making polyethylene an effective insulator; is approximately 1.9-2.3 kJ/kg·K for HDPE and similar for LDPE. These properties stem from the non-polar backbone, which limits intermolecular forces and heat transfer efficiency.
PropertyLDPEHDPEUHMWPE
Tensile Strength (MPa)~1020-3120-40
Young's Modulus (GPa)~0.20.8-10.8-1.6
Elongation at Break (%)500-600>500>300
Melting Point (°C)105-115120-130120-130
Thermal Conductivity (W/m·K)0.330.45-0.52~0.4-0.5
Data sourced from standard polymer specifications; values can vary with processing and additives.

Electrical, Optical, and Barrier Properties

Polyethylene exhibits favorable electrical properties that render it an effective insulator in applications such as cable coatings and electronic components. Its dielectric constant typically ranges from 2.25 to 2.3 at frequencies around 1 MHz, reflecting low polarizability due to the non-polar nature of its hydrocarbon chains. Dielectric strength varies by type and thickness but generally falls between 20 and 50 kV/mm for low- and high-density variants, with low-density polyethylene (LDPE) often achieving around 27 kV/mm under standard conditions. High-density polyethylene (HDPE) demonstrates comparable or slightly higher values in some formulations, up to 70 kV/mm in tested composites, attributed to denser packing that reduces void formation under electric fields. These properties stem from polyethylene's high volume resistivity, exceeding 10^15 ohm-cm, minimizing current leakage. Optically, polyethylene is characterized by a of 1.51–1.52 for LDPE and 1.53–1.54 for HDPE at visible wavelengths, influenced by and crystallinity. Lower- forms like LDPE display greater transparency due to smaller sizes that scatter less , allowing visible up to 50% in thin films, whereas HDPE's higher crystallinity results in translucency with reduced transmission. This variation arises from scattering at crystalline-amorphous interfaces, with overall mid-infrared transparency supporting uses in optical components, though visible opacity limits clarity in denser grades. In barrier performance, polyethylene provides excellent resistance to , with low transmission rates (typically 1–2 g·m⁻²·day⁻¹ at 38°C and 90% RH for 25 μm films) owing to its hydrophobic, non-polar structure that repels . However, it shows moderate to poor barrier to non-polar gases like oxygen, with permeability coefficients around 10–20 (or transmission rates of 1500–6000 cm³·m⁻²·day⁻¹·atm⁻¹ for LDPE films), enabling through amorphous regions. HDPE outperforms LDPE in both and gas barriers due to higher crystallinity reducing free volume for , though neither suffices for highly oxygen-sensitive without additives or laminates.
PropertyLDPEHDPE
Dielectric Constant (1 MHz)~2.26~2.34
~27~20–70
1.51–1.521.53–1.54
Water Vapor Barrier (qualitative)GoodExcellent
Oxygen PermeabilityHigher (~2000–6000 cm³/m²/day/atm)Lower

Chemical Resistance and Stability

Polyethylene exhibits strong chemical resistance to a broad array of dilute acids, bases, salts, and aqueous solutions at , attributable to its non-polar, saturated structure that minimizes interactions with polar . (HDPE) generally outperforms (LDPE) in this regard, showing minimal swelling or degradation when exposed to , dilute , or up to concentrations of 30-50% for extended periods. Resistance to organic solvents is more variable: polyethylene tolerates aliphatic hydrocarbons like or with only moderate swelling and no dissolution at 20-50°C, but aromatic solvents such as or induce significant softening, permeation, or dissolution above 60°C, particularly in LDPE variants. Strong oxidizing agents, including concentrated (>70%), fuming , or like , cause oxidative degradation, chain scission, or embrittlement even at ambient conditions, compromising long-term integrity. In terms of stability, polyethylene maintains inertness in neutral aqueous environments and resists hydrolysis or microbial attack under standard conditions, with no significant weight loss or mechanical property decline after immersion in water or dilute electrolytes for years. However, exposure to environmental stressors like combined chemical permeation and mechanical stress can induce environmental stress cracking (ESC), especially in branched LDPE, where tensile strength may drop by 50% or more after 1000 hours in surfactants or detergents at 50°C. Oxidative stability is limited without additives; pure polyethylene undergoes slow auto-oxidation in air above 100°C, forming hydroperoxides that lead to carbonyl groups and reduced molecular weight, as evidenced by FTIR spectroscopy showing peak increases at 1710 cm⁻¹ after accelerated aging tests.
Chemical ClassResistance Level (HDPE at 20-50°C)ExamplesNotes
Dilute AcidsExcellentHCl (37%), H₂SO₄ (dilute), HNO₃ (dilute)No degradation after 30 days immersion.
BasesExcellentNaOH (50%), NH₄OH (30%)Minimal swelling; suitable for storage tanks.
Alcohols/GlycolsGoodEthanol (100%), Ethylene glycolSlight weight gain (<5%) but retains strength.
Aromatic SolventsPoorBenzene, TolueneDissolution or severe swelling >60°C.
OxidantsPoorConcentrated HNO₃, Cl₂Oxidative attack; avoid prolonged contact.
This table summarizes qualitative resistance ratings derived from immersion tests, where "excellent" indicates no observable effect, "good" minor reversible changes, and "poor" irreversible damage. Actual performance depends on factors like , crystallinity, exposure duration, and temperature, with HDPE's linear structure conferring superior barrier properties over LDPE's branched chains. Stabilizers such as hindered phenols or phosphites are often incorporated to enhance oxidative resistance during or service, extending useful life in chemically aggressive settings by inhibiting radical chain reactions.

Classification by Structure and Density

Ultra-High-Molecular-Weight Polyethylene (UHMWPE)

Ultra-high-molecular-weight polyethylene (UHMWPE) consists of linear polyethylene chains with molecular masses typically between 2 and 6 million g/mol, distinguishing it from other polyethylene variants by conferring exceptional toughness and resistance to wear. This elevated molecular weight, approximately ten times that of high-density polyethylene (HDPE), arises from controlled polymerization processes that minimize chain termination, leading to extended polymer chains that enhance entanglement and load distribution under stress. UHMWPE is synthesized through low-pressure using Ziegler-Natta or metallocene catalysts, with commercialization beginning in the by entities such as Ruhrchemie AG. The process requires precise control of reaction conditions to achieve molecular weights exceeding 1 million g/mol while avoiding excessive that complicates handling; recent catalytic advancements have enabled molecular weights up to 3.7 × 10^6 g/mol with high activity rates. Unlike conventional polyethylenes, UHMWPE cannot be processed via standard melt or injection molding due to its high melt ; instead, techniques like , ram , or of powder forms are employed. Mechanically, UHMWPE exhibits the highest abrasion resistance and notched impact strength among commercial plastics, surpassing in sliding wear tests and providing durability in demanding environments. Its tensile strength and support applications requiring fatigue resistance, though oxidation can reduce these properties over time in exposed conditions. and biocompatible, UHMWPE demonstrates low moisture absorption and resistance to most solvents, making it suitable for harsh industrial and biomedical uses. Key applications leverage these attributes: in orthopedics, UHMWPE has served as a bearing surface in total hip and knee replacements since , with its wear resistance minimizing debris generation and extending . Industrially, it forms liners, conveyor components, and resistant to abrasion; high-strength fibers derived from gel-spun UHMWPE, such as Dyneema, provide ballistic protection and mooring ropes due to their superior . Despite these advantages, challenges include thermal instability during processing and potential creep under sustained loads, necessitating stabilized formulations for long-term performance.

High-Density Polyethylene (HDPE)

is a derived from , characterized by a predominantly linear molecular structure with minimal branching, which enables high crystallinity levels typically exceeding 80%. This structure contrasts with branched variants like (LDPE), resulting in a range of 0.94 to 0.97 g/cm³. The material's high strength-to-density ratio stems from its ordered crystalline domains, providing rigidity and without significant short-chain branches that disrupt packing in less dense polyethylenes. HDPE is produced via low-pressure processes, primarily using Ziegler-Natta catalysts, which coordinate insertion onto sites to favor linear chain growth at temperatures of 70–110 °C and pressures of 10–30 bar. Alternative Phillips catalysts, based on oxides, achieve similar outcomes in or gas-phase reactors, minimizing branching compared to high-pressure free-radical methods used for LDPE. Commercial development began in the 1950s, with Karl Ziegler's 1953 discovery of effective catalysts enabling controlled synthesis, followed by Phillips Petroleum's 1954 market introduction under the Marlex brand. Mechanically, HDPE exhibits tensile strengths of 20–30 MPa and elongations at break up to 500%, balancing with impact resistance suitable for load-bearing uses. Thermally, it withstands continuous service up to 80–90 °C, with a around 130–135 °C due to its crystalline structure. Chemically, HDPE demonstrates resistance to dilute acids, bases, alcohols, and , attributed to its non-polar backbone, though it is susceptible to strong oxidants and aromatic solvents at elevated temperatures. Common applications leverage HDPE's durability and barrier properties, including blow-molded bottles for and detergents, extrusion-formed for and gas distribution, and injection-molded containers for chemicals and consumer goods. Its resistance and low permeability make it ideal for geomembranes and tanks, while recyclability under resin code 2 supports widespread use in exceeding billions of pounds annually.

Medium-Density Polyethylene (MDPE)

Medium-density polyethylene (MDPE) is a characterized by a range of 0.926 to 0.940 g/cm³, positioning it between (LDPE) and (HDPE). This arises from a molecular structure featuring moderate short-chain branching, which reduces crystallinity compared to the highly linear HDPE while maintaining greater linearity than the highly branched LDPE produced via free-radical processes. The semi-crystalline nature imparts balanced mechanical properties, including good tensile strength, impact resistance, and environmental stress crack resistance (ESCR), with typical melt flow rates tailored for specific applications like 0.2 to 5 g/10 min. MDPE is synthesized through of , often copolymerized with small amounts of α-olefins such as or to introduce controlled branching and adjust downward from HDPE levels. This process typically employs Ziegler-Natta or Phillips catalysts in , gas-phase, or solution reactors, enabling production across a broad spectrum including MDPE via variations in comonomer content and catalyst selectivity. Unlike LDPE's high-pressure free-radical mechanism that generates extensive long-chain branching, MDPE's structure results from shorter branches (C4-C6), yielding narrower molecular weight distributions and improved processability for and molding. In applications, MDPE excels in pressure piping systems, particularly for natural gas distribution, where its flexibility, toughness, and slow crack growth resistance outperform more rigid HDPE under dynamic loads and environmental stresses. Developed in the 1970s specifically for gas pipelines, MDPE pipes comply with standards such as ASTM D2513, which specifies requirements for dimensions, hydrostatic strength, and chemical resistance, supporting hydrostatic design bases up to 1000 psi at 73°F. It is also used in water supply networks for municipal and rural systems, leveraging corrosion resistance and suitability for potable water per NSF standards, as well as in geomembranes and blown films requiring tear resistance and sealability. These attributes stem from MDPE's intermediate crystallinity (around 50-60%), providing ductility without excessive softness.

Linear Low-Density Polyethylene (LLDPE)

(LLDPE) is produced through the copolymerization of with higher alpha-olefins, such as , , or , resulting in a substantially linear chain with short branches that disrupt crystallinity without the long chain branching characteristic of (LDPE). This structure provides a balance of flexibility and strength, distinguishing it from (HDPE), which features fewer branches and higher crystallinity, and LDPE, which relies on random long branches formed during high-pressure free-radical . The density of LLDPE typically falls in the range of 0.915 to 0.925 g/cm³, achieved by varying the comonomer content and type, with longer branches from octene allowing for lower densities within this spectrum compared to shorter branches from . The short chain branches reduce packing efficiency, lowering relative to HDPE (0.941–0.965 g/cm³) while enhancing elongation and puncture resistance over LDPE (0.910–0.940 g/cm³). LLDPE is manufactured using coordination catalysts like Ziegler-Natta or metallocene systems in gas-phase, , or solution processes at lower pressures and temperatures than LDPE production, enabling precise control over branch distribution and molecular weight. This method yields resins with densities as low as 0.910 g/cm³ in some variants, though standard LLDPE maintains the 0.915–0.925 g/cm³ range for optimal film properties such as improved tensile strength and tear resistance.

Low-Density Polyethylene (LDPE)

(LDPE) is a characterized by a highly branched molecular structure, consisting of long-chain branches that reduce crystallinity and compared to linear polyethylene variants. This branching arises during free-radical , where intramolecular hydrogen abstraction and events create side chains, typically butyl or longer, disrupting chain packing and yielding densities of 0.910 to 0.940 g/cm³. The amorphous regions imparted by branching confer flexibility and toughness, distinguishing LDPE from (HDPE), which exhibits minimal branching and higher rigidity. LDPE was first synthesized in 1933 by researchers at (ICI) through high-pressure , with commercial production commencing on September 1, 1939, at a 100-tonne-per-year plant in . The industrial process employs free-radical initiation with at pressures of 1,000 to 3,000 bar and temperatures of 150 to 300°C in tubular or reactors, promoting rapid chain growth interspersed with branching via mechanisms. This high-pressure method, unlike Ziegler-Natta used for linear PEs, inherently produces the branched architecture essential to LDPE's properties, though it demands robust equipment to handle extreme conditions and potential exothermic runaway reactions. Mechanically, LDPE exhibits a of 105 to 115°C, tensile strength around 1,400 psi, and elongation at break exceeding 500%, enabling applications requiring over . Thermally stable from -50 to 85°C in service, it demonstrates low reactivity to most chemicals except strong oxidizers and certain solvents, with good moisture barrier properties due to its non-polar nature. These attributes stem causally from the branched structure, which lowers temperature and enhances chain entanglement, facilitating flow during processing while maintaining resilience post-extrusion. In applications, LDPE dominates flexible , including shrink films, grocery bags, and squeeze bottles, leveraging its clarity, sealability, and impact resistance. It also serves in wire and cable insulation, corrosion-resistant linings, and molded toys or containers, where weldability and machinability are advantageous. Annual global production exceeds millions of tonnes, underscoring its role in cost-effective, lightweight alternatives to or metal in consumer goods.

Very-Low-Density Polyethylene (VLDPE)

Very-low-density polyethylene (VLDPE) constitutes a subclass of polyethylene distinguished by its range of 0.880 to 0.915 g/cm³, achieved through elevated incorporation of short-chain branches that impede tight molecular packing. This material features a substantially linear backbone copolymerized from and alpha-olefins such as , , or , with branch concentrations spanning 17 to 100 per 1000 backbone carbon atoms, fostering uniformity in branch distribution unlike the broader variability in (LLDPE). The high short-chain branching content in VLDPE markedly lowers crystallinity relative to LLDPE or (LDPE), as branches disrupt lamellar formation and reduce ordered crystalline domains, yielding densities below the 0.915 g/cm³ threshold typical of LLDPE. This structural attribute contrasts with LDPE's irregular long-chain branching from high-pressure free-radical , whereas VLDPE relies on controlled low-pressure processes to maintain linearity while maximizing comonomer-induced short branches for density reduction. Mechanically, VLDPE's reduced crystallinity confers superior flexibility, elongation under stress, and low-temperature impact resistance over denser polyethylenes, with properties like and stretchability stemming directly from the amorphous regions enhanced by branching. In comparison to LLDPE, which balances strength and flexibility at higher densities (0.915–0.940 g/cm³), VLDPE prioritizes pliability through greater comonomer levels, though it may exhibit slightly lower tensile strength due to diminished crystalline .

Cross-Linked Polyethylene (PEX/XLPE)

Cross-linked polyethylene (XLPE), also known as PEX in contexts, is produced by chemically or physically linking polymer chains via covalent bonds, transforming the into a thermoset material with enhanced durability. This cross-linking process, typically applied to (HDPE) or (MDPE) bases, increases resistance to creep, heat, and chemical degradation compared to uncross-linked variants. The primary cross-linking methods include peroxide-initiated radical formation, silane grafting followed by moisture curing, and electron beam or gamma irradiation. In peroxide cross-linking, organic peroxides decompose at elevated temperatures (around 150–200°C) to generate free radicals that abstract hydrogen from polyethylene chains, forming carbon radicals that recombine into C–C cross-links; this method yields high cross-link density but requires precise control to minimize chain scission. Silane cross-linking, often via the two-step Sioplas process, involves grafting vinylsilane onto the polymer using peroxides, then hydrolyzing silane groups in the presence of water and catalysts to form Si–O–Si bridges; it is favored for cable insulation due to economic viability and uniform cross-linking. Irradiation cross-linking exposes polyethylene to high-energy radiation, creating radicals without additives, suitable for thin films or foams, though it demands specialized equipment and can induce oxidative degradation if not conducted in inert atmospheres. Cross-linking imparts superior thermal stability, with XLPE sustaining continuous use up to 90°C and short-term exposure to 250°C, alongside improved tensile strength (20–30 MPa) and elongation at break (300–600%) over linear polyethylene. Electrically, XLPE exhibits low and high insulation resistance, making it preferable for medium-voltage cables where uncross-linked LDPE suffers from under electrical stress. In plumbing applications as PEX, the material offers flexibility, burst pressures exceeding 500 psi at low temperatures, and resistance, outperforming in freeze tolerance due to expansion capabilities up to 3–4 times its diameter before failure. PEX tubing adheres to standards such as ASTM F876 and F877, ensuring performance in residential distribution with projections of 50 years under typical conditions (73°C, 80 psi). However, vulnerabilities include susceptibility to UV degradation, damage, and potential disinfectant byproduct permeation in chlorinated , necessitating barriers or protections; cross-linking also renders traditional mechanical challenging due to insolubility, though emerging chemical methods like imine-based reversible links show promise for up to 97% recovery. Applications span XLPE-insulated power cables rated for 5–500 kV, PEX hot/cold , and radiation-cross-linked foams for , where the enhanced properties justify the added costs over polyethylene.

Production Processes

Ethylene Monomer Synthesis

Ethylene, the for , is predominantly synthesized industrially through of feedstocks such as , , and . This thermal process involves mixing the feedstock with steam to dilute the hydrocarbons, reducing coke formation, and heating the mixture in tubular reactors within furnaces to temperatures typically exceeding 800°C for short residence times of seconds. The uncatalyzed decomposition breaks C-C bonds, yielding as the primary product along with byproducts like , , and . Feedstock selection influences yield and coproduct distribution: cracking achieves yields up to 80%, favored in regions like the with abundant liquids, while , derived from crude oil refining, yields about 30% but produces more valuable aromatics and heavier olefins, common in and . Post-cracking, the is rapidly quenched to halt further reactions, compressed, dried to remove , and separated via and absorption towers to isolate high-purity (>99.9%) suitable for . Global production capacity reached approximately 225 million metric tons per annum by the mid-2020s, with annual output exceeding 200 million metric tons, underscoring its role as a foundational . Alternative synthesis routes, such as of derived from bio-sources or conversion, exist but constitute less than 5% of global supply due to higher costs and lower scalability compared to . 's —requiring about 25-30 GJ per of —and reliance on feedstocks drive ongoing research into and renewable alternatives, though conventional processes dominate production for polyethylene feed.

Polymerization Mechanisms

Free-radical polymerization predominates in the production of (LDPE), operating under high pressures of 1,000–3,500 bar and temperatures of 150–350 °C, with initiators such as or oxygen generating radicals that initiate chain growth. The mechanism proceeds in three stages: , where the initiator decomposes homolytically to form radicals that add to 's π-bond, creating a polyethylene radical; , involving rapid successive additions of ethylene monomers to the growing radical chain; and termination, primarily via radical combination or , yielding branched structures due to intramolecular hydrogen abstraction () that forms short-chain branches. This branching reduces crystallinity and density (typically 0.91–0.94 g/cm³), distinguishing LDPE from linear variants. Coordination polymerization, responsible for high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE), employs transition metal catalysts at moderate pressures (1–100 bar) and temperatures (50–150 °C), enabling linear chain growth with minimal branching. The Ziegler-Natta process, developed in the 1950s using titanium tetrachloride (TiCl₄) activated by triethylaluminum (AlEt₃), follows the Cossee-Arlman mechanism: ethylene coordinates to a vacant site on the titanium center, followed by migratory insertion into the metal-alkyl bond, propagating the chain via repeated coordination-insertion cycles at stereospecific active sites on the catalyst surface. This heterogeneous catalysis produces high-molecular-weight, linear polymers with densities of 0.94–0.97 g/cm³ and high crystallinity. Metallocene catalysis, a single-site homogeneous variant introduced in the 1980s, utilizes group 4 bent metallocenes (e.g., zirconocene dichloride) activated by methylaluminoxane (MAO), offering precise control over molecular weight distribution (typically polydispersity index ~2) and comonomer incorporation for tailored copolymers like LLDPE. The mechanism mirrors Ziegler-Natta insertion but occurs in solution or slurry, with the constrained metallocene geometry ensuring uniform chain propagation and reduced branching variability compared to multi-site Ziegler-Natta systems. Phillips catalysts, chromium-based silica-supported systems, provide an alternative coordination route for HDPE via chromyl species activation and ethylene insertion, emphasizing high activity and broad molecular weight control. These mechanisms collectively account for over 99% of global polyethylene production, with coordination methods dominating due to energy efficiency and product versatility.

Industrial Manufacturing Techniques

Polyethylene production employs two primary industrial approaches: high-pressure free-radical for (LDPE) and low-pressure for (HDPE), (LLDPE), and related variants. High-pressure processes operate at 1000–3000 and 420–570 K, using oxygen or as initiators in tubular or reactors to yield branched LDPE chains. In the tubular process, flows through a long, water-jacketed tube where initiators trigger , producing LDPE with higher melt strength suitable for film extrusion. The method utilizes stirred reactors in series, allowing better control over molecular weight distribution via multiple reaction zones and pressure drops. Low-pressure processes, conducted at 10–80 atm and 350–420 K, rely on Ziegler-Natta (titanium-based with aluminum alkyls) or Phillips (chromium oxide on silica) catalysts to form linear polymers with minimal branching. The loop , prominent for HDPE, circulates a like in a closed-loop tubular reactor where catalyst and form a solid ; settling legs concentrate the slurry for flashing and drying, as commercialized by Phillips Petroleum (now Chevron Phillips MarTECH®). Gas-phase , widely used for LLDPE and HDPE, employs fluidized-bed reactors where gaseous and comonomers (e.g., or ) on catalyst particles, growing resin beds continuously removed and purified, as in the . Solution processes, less common, dissolve monomers and catalysts in for high-throughput production of copolymers but require energy-intensive recovery. Post-polymerization, all techniques involve separating unreacted monomers, devolatilizing, and extruding molten into pellets via strand or underwater cutting, followed by cooling and packaging; often regulates chain length, while comonomers tailor . Modern variants incorporate metallocene catalysts across these reactors for narrower molecular weight distributions and enhanced properties. These methods enable global production exceeding 100 million tons annually, with low-pressure routes dominating due to energy efficiency and versatility.

Applications and Societal Benefits

Packaging and Preservation

Polyethylene serves as a primary in and product due to its chemical inertness, flexibility, and low permeability to moisture and gases, enabling effective preservation of perishables. (LDPE) films, commonly used for shrink wraps, bags, and liners, form barriers that minimize oxygen ingress and transmission, thereby slowing oxidation and microbial growth in items like fruits, vegetables, and meats. (HDPE) is favored for rigid containers such as bottles and jugs, offering superior strength and resistance to cracking under stress, which maintains integrity during storage and transport. In , the global LDPE packaging market reached USD 21.04 billion, while HDPE packaging was valued at USD 18.90 billion, reflecting widespread adoption driven by these protective qualities. The preservative efficacy of polyethylene stems from its molecular structure, which provides a hydrophobic surface that repels water and limits diffusion of spoilage-inducing agents like ethylene gas from ripening produce. Studies demonstrate that polyethylene-based films can extend shelf life by preventing contamination and flavor loss; for instance, LDPE wraps protect against drying and oxidation, preserving aroma and nutritional value in stored foods. Active variants, incorporating controlled-release antimicrobials like thyme oil in LDPE matrices, further inhibit lipid oxidation and bacterial proliferation, as evidenced by reduced spoilage in tested food products over extended periods. This barrier functionality contributes to societal benefits by curbing food waste, with empirical assessments indicating that optimized packaging reduces overall environmental impacts through lower resource consumption compared to unpackaged spoilage scenarios. Beyond food, polyethylene preserves non-perishables like pharmaceuticals and chemicals by shielding contents from environmental contaminants and physical damage, enhancing reliability. Its lightweight nature—typically 20-50% lighter than or metal alternatives—lowers transportation emissions while maintaining durability, supporting efficient global distribution. These attributes underscore polyethylene's role in minimizing economic losses from product degradation, with market data projecting continued growth to USD 27.25 billion for HDPE by 2032, predicated on sustained demand for preservation-focused applications.

Infrastructure and Construction

(HDPE) is extensively utilized in infrastructure and construction for piping systems due to its corrosion resistance, flexibility, and longevity exceeding 100 years under typical operating conditions. serve in distribution, transmission, sewer mains, and drainage, offering leak-free heat-fused joints that eliminate infiltration issues common in alternative materials like or . Their lightweight nature reduces transportation costs and simplifies installation without , while seismic flexibility minimizes damage during earthquakes. In civil engineering applications, HDPE facilitates large-diameter pipes for municipal water systems and force mains, withstanding live, dead, and surcharge loads in underground installations. Since the 1960s, these systems have provided durable, maintenance-free water infrastructure globally, contributing to reduced leakage rates compared to aging metal or clay alternatives. Their chemical resistance suits sewage and industrial waste transport, preventing degradation from H2S or other corrosives. HDPE geomembranes function as impermeable liners in construction, barring migration into soil and to mitigate environmental . These sheets exhibit high tensile strength, UV stability, and resistance to a broad spectrum of chemicals, enabling long-term containment in sites. By forming robust barriers, they support sustainable , reducing CO2, SO2, and NO2 emissions associated with unmanaged dumps.

Medical, Agricultural, and Consumer Uses

Ultra-high molecular weight polyethylene (UHMWPE), with a molecular weight typically between 3 and 6 million g/mol, serves as the primary bearing material in total hip and knee arthroplasties due to its exceptional wear resistance, ductility, biocompatibility, and low coefficient of friction, which minimize particle-induced osteolysis and implant failure. Introduced in orthopedic applications in the 1960s, UHMWPE acetabular cups pair with metal femoral heads to withstand physiological loads while resisting abrasion over decades of implantation. Highly crosslinked variants, developed to further reduce wear rates to below 0.1 mm/year in hip simulator tests, have extended implant longevity, with clinical studies reporting cumulative survival rates exceeding 95% at 10-15 years post-surgery. In , (LDPE) films function as covers to suppress growth, retain , and moderate temperature fluctuations, resulting in yield increases of 20-50% for crops like tomatoes and peppers in field trials across arid and temperate regions. Black LDPE films, opaque to , prevent emergence while allowing soil warming, with typical thicknesses of 20-50 micrometers enabling mechanical strength against tearing during installation and harvest. Polyethylene films, often co-extruded with UV stabilizers for service lives of 2-4 years, transmit 85-90% of visible light while blocking harmful UV rays, thereby protecting high-value crops from , , and pests in controlled environments spanning millions of hectares globally. Consumer applications of polyethylene leverage its chemical inertness and moldability for durable items, including , buckets, and flexible tubing, where LDPE provides impact resistance and HDPE offers rigidity for loads up to 50 kg without deformation. (HDPE) components in recreational products, such as slides and kayaks, endure outdoor exposure with minimal degradation, maintaining structural integrity through repeated UV and mechanical stress cycles. These uses prioritize polyethylene's low and recyclability, with post-consumer grades reprocessed into similar to conserve virgin inputs by up to 80% in terms.

Processing and Fabrication

Joining and Welding Methods

Polyethylene, as a , is predominantly joined through heat fusion techniques that exploit its ability to soften and remelt without significant degradation, creating homogeneous bonds stronger than mechanical fasteners in many applications. These methods avoid adhesives or solvents, which are less effective due to polyethylene's low and chemical inertness. ensures leak-proof, high-strength joints, particularly for (HDPE) pipes used in pressure systems, where joint failure rates are minimized when procedures adhere to standards like ASTM F2620. Butt fusion is the most widely used method for joining straight lengths of polyethylene pipe, involving clamping two pipe ends in a , facing them to ensure squareness, and pressing them against a heated plate at approximately 200–250°C to melt the surfaces. The plate is removed, and the molten ends are pressed together under controlled pressure (typically 0.15–0.35 MPa, depending on pipe and ) for a cooling period of 10–30 minutes, forming a bead of fused around the joint. This technique achieves tensile strengths comparable to the parent pipe , with typically occurring in the base rather than the weld zone during . Procedures must account for ambient conditions, such as reducing heater plate temperature by 10–20°C in winds exceeding 16 km/h to prevent uneven heating. Electrofusion welding employs pre-fabricated fittings with embedded resistive heating coils; the pipe ends are inserted into the fitting, and an (typically 20–40 V for 30–600 seconds, varying by fitting size) generates localized heat to melt the interface, fusing the assembly upon cooling under minimal pressure from pipe expansion. This method excels in confined spaces, repairs, or connections to fittings like elbows and tees, where butt fusion is impractical, and is qualified per ASTM F1055 through bend or tensile tests showing weld retention above 50% of base material. Electrofusion joints exhibit lower sensitivity to operator skill compared to butt fusion but require precise scraping of oxidation layers to ensure melt interdiffusion, with failure risks increasing if voltage fluctuations exceed 10%. Socket fusion, suitable for smaller diameters (up to 63 mm), mirrors butt fusion but uses a heated tool with matching male and female sockets to simultaneously melt pipe and fitting ends before assembly. welding, applied to sheets or large repairs, extrudes a molten polyethylene rod onto the joint while heating the base, achieving depths up to 15 mm with overlap passes. All fusion methods demand material compatibility (e.g., matching and melt index) to prevent weak interphases, with non-destructive assessment via ultrasonic or testing per ISO 13954, though destructive qualification remains the benchmark for pressure-rated applications.

Extrusion, Molding, and Forming

Polyethylene resins, typically in pellet form, undergo by feeding into a single-screw extruder where and shear melt the at temperatures around 200-260°C, homogenizing it before passage through a die to form profiles like pipes, tubes, sheets, or . For (HDPE), extrusion produces pipes with diameters up to several meters, leveraging the material's stiffness and impact resistance for water and gas distribution systems. (LDPE) suits blown film extrusion, where molten is extruded into a tube, inflated, and cooled to create thin films for , with output speeds exceeding 100 m/min in modern lines. Injection molding of polyethylene involves injecting molten into a closed mold under , suitable for HDPE parts like bottle caps and containers due to its flow properties, though low melt viscosity limits thin-wall precision compared to stiffer polymers. , prevalent for HDPE, extrudes a hollow parison that is clamped in a mold and inflated with air at 20-40 bar to conform to the mold cavity, yielding seamless bottles and drums with capacities from 0.1 to 1000 liters. uses polyethylene powder loaded into a mold rotated biaxially in an oven at 250-350°C, allowing and gravity to distribute the melt evenly for large, hollow items like storage tanks, minimizing seams and enabling wall thicknesses of 3-10 mm. Thermoforming processes polyethylene sheets, first produced via flat-die , by heating to 120-160°C and or pressure forming over molds for trays and containers, particularly effective with LDPE for its flexibility and clarity in applications. These methods exploit polyethylene's nature, enabling high-volume production with cycle times as low as 10-30 seconds for injection and , while supports continuous output rates of 100-1000 kg/hour depending on equipment scale.

Modified Polyethylenes

Non-Polar Copolymers and Metallocene Variants

Non-polar copolymers of polyethylene consist primarily of (LLDPE), formed by the copolymerization of with short-chain alpha-olefins such as , , or . These comonomers introduce short branches into the otherwise linear polyethylene chain, reducing crystallinity and density to a range of 0.91–0.94 g/cm³ while maintaining substantial linearity. The process occurs at lower temperatures and pressures compared to (LDPE) production, typically using Ziegler-Natta catalysts to achieve controlled branching. LLDPE exhibits superior mechanical properties over LDPE, including higher tensile strength, improved impact and puncture resistance, and enhanced environmental stress crack resistance due to its linear structure with uniform short-chain branches. It retains excellent chemical resistance and electrical insulation properties inherent to polyethylene, making it suitable for demanding applications requiring durability without long-chain branching. Metallocene variants, often denoted as mLLDPE or mPE, employ single-site metallocene catalysts—organometallic compounds based on cyclopentadienyl ligands coordinated to transition metals like or —for . These catalysts, developed from research in the 1980s and commercialized in the mid-1990s, enable precise control over molecular architecture, yielding polymers with narrower molecular weight distributions (typically polydispersity index of 2–3 versus 3–5 for Ziegler-Natta) and more uniform comonomer incorporation along the chain. Compared to Ziegler-Natta catalyzed LLDPE, metallocene variants demonstrate reduced heterogeneity in branch distribution, leading to enhanced , higher puncture resistance, improved clarity, and better draw-down ratios in film processing. This uniformity arises from the single of metallocene catalysts, which minimizes variations in chain length and branching that occur with multi-site Ziegler-Natta systems, thereby optimizing performance in stretch films and high-strength packaging. Commercial adoption accelerated post-1995 with innovations from producers like and Dow, driven by these property advantages despite initial processing challenges like higher melt strength.

Polar Copolymers and Functional Modifications

Polar copolymers of ethylene incorporate comonomers bearing polar functional groups, such as or , into the polyethylene backbone via free-radical or processes, thereby introducing dipole moments that enhance intermolecular interactions with polar substrates. These modifications disrupt the inherent crystallinity and hydrophobicity of homopolymer polyethylene, yielding materials with tailored melt viscosities, improved to metals or , and reduced permeability to gases and moisture compared to non-polar variants. For instance, (EVA) copolymers, synthesized under high-pressure conditions with vinyl acetate contents typically ranging from 5% to 40% by weight, exhibit rubber-like elasticity at higher comonomer levels due to reduced chain packing density. Ethylene-acrylic acid (EAA) copolymers, produced similarly with fractions up to 20 mol%, demonstrate ionomer-like behavior upon partial neutralization, conferring enhanced tensile strength and impact resistance through ionic crosslinks. Coordination catalysts, including late-transition metals like or , enable lower-pressure copolymerizations with polar monomers, achieving higher molecular weights and narrower polydispersity indices while minimizing homopolymer contamination—advances reported in studies from 2021 onward that overcome traditional by polar groups. These polar variants maintain ethylene's chemical inertness but gain compatibility with fillers or adhesives, as evidenced by EVA's widespread use in hot-melt formulations where vinyl acetate content inversely correlates with crystallinity and crystallinity (e.g., 18% VA yields ~40% crystallinity). Functional modifications of polyethylene involve post-polymerization reactions to graft or substitute polar groups onto the chain, often via free-radical initiation with peroxides or irradiation, to impart specific functionalities without altering bulk polymerization economics. Maleic anhydride grafting (PE-g-MA), achieved by melt-blending polyethylene with 0.5–2 wt% maleic anhydride and peroxide initiators, yields anhydride functionalities (graft degrees of 0.1–1 mol%) that react with amines or hydroxyls, improving interfacial adhesion in composites with polar reinforcements like wood flour or glass fibers. Chlorination of polyethylene, typically in solution or gas-solid phases with chlorine gas at 40–60°C, introduces 20–50 wt% chlorine content, transforming the material into chlorinated polyethylene (CPE) with enhanced flame retardancy, oil resistance, and flexibility suitable for cable sheathing, as chlorine atoms disrupt chain regularity and increase polarity. These modifications preserve polyethylene's processability while enabling causal enhancements in end-use performance, such as sulfonation for antistatic properties or silane grafting for crosslinkable insulation, with reaction efficiencies verified through FTIR spectroscopy showing characteristic carbonyl or Cl peaks. Empirical data from 2023 studies confirm that grafting distributions vary with chain microstructure, influencing uniform functionalization and avoiding excessive degradation.

Bio-Based and Chemically Altered Forms

Bio-based polyethylene (bio-PE) is produced by polymerizing derived from bio-, typically extracted from or other , rather than sources. This process begins with fermenting plant sugars to yield , followed by to and subsequent , resulting in a material chemically identical to conventional polyethylene in and properties. Braskem's I'm green™ bio-PE, launched commercially in 2010 from a facility in Triunfo, , utilizes and achieves over 80% renewable carbon content, with production capacity exceeding 250,000 metric tons annually as of recent expansions. Unlike PE, bio-PE exhibits a negative , as growth sequesters approximately 3.1 tons of CO2 per ton of produced, offsetting emissions during manufacturing and use. It maintains equivalent mechanical strength, density (0.91–0.96 g/cm³), and processability for applications like films and bottles, while being fully compatible with existing streams. Chemically altered polyethylenes involve post-polymerization modifications to enhance specific traits, such as thermal stability or resistance to degradation. Cross-linked polyethylene (XLPE or PEX) is formed by inducing covalent bonds between polymer chains via peroxides, silane grafting, or electron-beam irradiation, increasing crystallinity and molecular weight to yield gel contents of 60–90%. This alteration elevates the material's melting point to 130–140°C, short-term temperature resistance to 250°C, and resistance to cracking under stress, making XLPE suitable for high-voltage cable insulation (withstanding 90–150 kV) and hot-water piping systems. Chlorinated polyethylene (CPE), produced by reacting polyethylene with chlorine gas at 50–100°C to incorporate 34–44% chlorine, transitions the thermoplastic to a rubber-like elastomer with improved flexibility (Shore A hardness 40–90) and tensile strength up to 25 MPa. CPE demonstrates superior ozone resistance, flame retardancy (limiting oxygen index >27%), and oil compatibility per ASTM D2000 standards, finding use in wire jacketing, roofing membranes, and impact modifiers for PVC at loadings of 5–20%. These modifications do not alter the base hydrocarbon backbone fundamentally but introduce functional enhancements verified through empirical testing, such as differential scanning calorimetry for XLPE cross-link density and dynamic mechanical analysis for CPE elasticity.

Environmental Considerations

Life Cycle Impacts and Efficiency Gains

Life cycle assessments (LCAs) of polyethylene (PE) reveal that its production from feedstocks, such as derived from of or , generates cradle-to-gate (GHG) emissions of approximately 1.8–2.2 kg CO₂-equivalent per kg of (HDPE), with (LDPE) slightly higher due to additional branching processes. These emissions stem primarily from inputs in cracking (about 60–70%) and (20–30%), alongside feedstock-derived CO₂. Water and consumption in production averages 20–50 m³ and 50–80 MJ per kg, respectively, varying by regional mixes and . Use-phase impacts are mitigated by PE's low density (0.91–0.97 g/cm³), which reduces transport fuel demands; for instance, PE packaging weighs 50–80% less than or metal equivalents, lowering emissions by up to 40% per unit volume shipped. Comparative LCAs demonstrate PE's advantages over alternatives like , , aluminum, or in applications, with PE exhibiting 70% lower (GWP) on average across 15 material substitutions, driven by reduced material mass and for manufacturing. alternatives, for example, require 3–4 times more for and forming, amplifying GHG by 2–5 kg CO₂e per kg despite recyclability, while 's higher use (up to 100 m³ per ton) exacerbates impacts. End-of-life burdens include landfilling (dominant for non-recycled PE, contributing of 0.5–1 kg CO₂e per kg over 100 years) or (recovering 20–30 MJ/kg but emitting 2–3 kg CO₂e per kg), though mechanical diverts 70–90% of virgin production impacts by consuming 70–80% less . Efficiency gains in PE systems arise from process innovations, including metallocene catalysts that boost yield by 10–20% and reduce energy intensity from 80 MJ/kg in 1990s high-pressure LDPE to under 60 MJ/kg today via low-pressure gas-phase methods. Cogeneration and heat integration in modern plants recover 20–30% of thermal energy, cutting fossil fuel use, while lightweighting designs in applications like pipes or films have decreased material needs by 15–25% since 2000 without compromising durability. Recycling advancements, such as sorted HDPE streams achieving 85–95% purity, yield closed-loop products with 50–60% lower GWP than virgin PE, conserving 5,000–6,000 kWh per ton recycled and reducing oil feedstock demand equivalent to 1–2 barrels per ton. These gains underscore causal trade-offs: while fossil dependence ties emissions to energy prices, empirical data affirm PE's net efficiency in resource-scarce scenarios over bulkier substitutes, provided recycling rates exceed 30%.

Waste, Recycling, and Degradation Dynamics

Polyethylene arises predominantly from applications, which account for over 40% of its usage, leading to high volumes entering streams globally. In 2023, global production exceeded 450 million tonnes, with polyethylene comprising roughly one-third, much of which becomes due to its single-use nature in films, bottles, and containers. In the United States, plastics generation reached 35.7 million tons in 2018, with polyethylene variants like HDPE and LDPE forming a substantial share, primarily landfilled or incinerated rather than recovered. Worldwide, an estimated 70% of plastic , including polyethylene, remains uncollected and risks environmental leakage, exacerbating accumulation in landfills and oceans. Recycling of polyethylene occurs mainly through mechanical processes, involving collection, sorting by resin identification codes (e.g., #2 for HDPE, #4 for LDPE), shredding, to remove contaminants, and melt-extrusion into pellets for . Global rates, encompassing polyethylene, hovered at approximately 9% as of recent assessments, with polyethylene benefiting from its relative ease of processing compared to mixed resins but still facing low recovery due to inadequate . In , installed plastics capacity grew to 13.2 million tonnes in 2023, yet actual polyethylene yields are constrained by post-consumer contamination from food residues and adhesives, which degrade material purity and necessitate into lower-value products like rather than virgin-equivalent resin. Chemical methods, such as to break polyethylene into monomers or waxes, offer potential for higher circularity but remain economically unviable at scale owing to and byproduct variability. Sorting challenges persist, as polyethylene films entangle in machinery and multilayer resists separation, resulting in rejection rates exceeding 20% in many facilities. Degradation of polyethylene in the environment proceeds slowly via abiotic mechanisms, including photodegradation from ultraviolet radiation, which initiates carbonyl formation and chain scission, embrittling the polymer and promoting mechanical fragmentation into microplastics. Thermo-oxidative degradation accelerates under heat and oxygen exposure, generating free radicals that propagate cracks, while hydrolysis plays a minor role due to polyethylene's hydrophobic nature. Empirical data indicate degradation rates for polyethylene films at 0.1-1% mass loss per year in marine or soil settings, far slower than biodegradable alternatives, with full mineralization requiring centuries under natural conditions. Biological degradation is minimal, as polyethylene's stable C-C backbone resists microbial enzymes absent engineered catalysts; isolated bacterial strains like Rhodococcus achieve only surface erosion over months in lab settings, not scalable to field persistence. This recalcitrance drives microplastic formation, with polyethylene particles persisting indefinitely and accumulating in ecosystems, as evidenced by abundances up to 10^4 particles per cubic meter in ocean subsurface layers. Landfill and incineration dominate end-of-life fates, with incineration recovering energy but emitting CO2 equivalent to 1.5-2.5 tonnes per tonne of polyethylene processed.

Pollution Debates and Empirical Mitigation Data

Polyethylene constitutes approximately 25% of identified microplastics in aquatic environments, primarily originating from degraded packaging and consumer products, contributing to physical hazards like ingestion by marine life. Debates persist over the material's net environmental footprint, with lifecycle assessments indicating that polyethylene packaging yields 70% lower global warming potential compared to alternatives like paper or glass, due to its lightweight nature reducing transportation emissions and food waste. Critics emphasize its persistence, fragmenting into microplastics over centuries rather than biodegrading, potentially exacerbating biodiversity loss, though empirical toxicity studies reveal minimal chemical leaching from pure polyethylene, with effects largely physical or amplified by adsorbed pollutants. Proponents argue that pollution stems more from inadequate waste management in developing regions than inherent material flaws, noting that replacing polyethylene often increases overall emissions, as alternatives require more resources in production and use. Bans on single-use polyethylene bags have demonstrably reduced shoreline litter by up to significant proportions in affected areas, such as in where bag debris dropped post-2016 policy, yet global rates for plastics, including polyethylene, hover below 10%, limiting broader . In the United States, high-density polyethylene bottle reached 29.3% in 2018, but overall polyethylene waste diversion remains low, with mechanical challenged by and sorting difficulties. Empirical mitigation strategies include enhanced collection systems and additives promoting photo-oxidative degradation, though natural breakdown rates for polyethylene average less than 1% mass loss per year under environmental conditions. Policies combining fees with investments show greater efficacy than outright bans, potentially boosting recovery rates without substituting higher-impact materials, as evidenced by reduced usage in jurisdictions with dual approaches. Ongoing into enzymatic and microbial degradation offers promise, but current data underscore that improved waste yields more verifiable reductions in polyethylene than material substitution alone.

Economic and Market Dynamics

Global Production and Demand Statistics

Global polyethylene reached approximately 126 million metric tons in 2024, reflecting a slowdown in growth to 2.2% from prior years amid economic uncertainties and oversupply pressures. Production volumes increased by about 2.5 million metric tons globally in 2024, driven primarily by expansions (1.6 million metric tons) and (0.5 million metric tons), which accounted for 85% of the net gain. Capacity significantly outpaced , with virgin polyethylene capacity exceeding consumption by roughly 30 million metric tons annually, exacerbating market imbalances. Asia-Pacific dominates both production and demand, holding the largest share due to rapid industrialization and packaging sector expansion, followed by and the . Leading producers include , Dow Chemical, and Chemical, with combined revenues exceeding $35 billion from polyethylene operations in recent assessments. Projections indicate modest demand recovery at 2.4% in 2024 followed by 1.2% in 2025, tempered by destocking, trade tensions, and new capacity additions that could sustain oversupply into the mid-2020s. Global capacity is forecast to expand by over 20% from 2025 to 2030, primarily in low-cost regions, potentially pressuring utilization rates below 90%.

Supply Chain, Trade, and Future Projections

The supply chain for polyethylene begins with the extraction and refining of hydrocarbon feedstocks, primarily naphtha from crude oil or ethane from natural gas, which are processed via steam cracking to produce ethylene monomer. This ethylene undergoes polymerization in high-pressure or low-pressure processes to yield various polyethylene grades, with operations concentrated in petrochemical complexes operated by major firms such as Dow Chemical Company, ExxonMobil Chemical, LyondellBasell Industries, SABIC, INEOS, and Sinopec. These producers maintain integrated facilities linking cracking units to polymerization reactors, minimizing logistics costs, though disruptions in feedstock supply—such as those from geopolitical tensions in oil-producing regions—can propagate upstream pressures. Downstream, polyethylene resins are pelletized and shipped to converters for extrusion into films, pipes, and packaging, with granulated forms facilitating bulk transport via rail, barge, or ocean vessels. Global trade in polyethylene reached significant volumes in recent years, with linear polyethylene exports projected at 22.4 million tons in 2025, reflecting a 2% increase from levels. emerged as a key exporter, with U.S. Gulf Coast polyethylene shipments setting records exceeding 5 billion pounds monthly from July 2023 through January , driven by abundant from and directed primarily to , which overtook traditional markets like and in 2023. Middle Eastern producers, including those backed by , contribute substantially to exports, while China's push for self-sufficiency has moderated import reliance, though it remains a major importer amid domestic capacity expansions. Trade flows are vulnerable to tariffs and bottlenecks, as evidenced by U.S. growth of 12% forecasted for in high-density and low-density variants. Looking ahead, the polyethylene market faces oversupply pressures into 2025, with global capacity additions—led by China accounting for one-third of projects starting by 2030—outpacing demand growth, which slowed to 2.2% in 2024 from prior years. Market value is projected to expand from USD 118.5 billion in 2024 to USD 197.3 billion by 2034 at a compound annual growth rate of approximately 5.2%, fueled by packaging and construction demand in emerging economies, though tempered by economic slowdowns and trade disputes. Empirical data indicate record capacity builds and China's reduced import needs could sustain surpluses, potentially pressuring margins unless offset by efficiency gains or substitution limits; nonetheless, petrochemical-derived polyethylene's cost advantages over alternatives support sustained dominance absent major policy shifts.

References

Add your contribution
Related Hubs
User Avatar
No comments yet.