Linear low-density polyethylene (LLDPE) is a substantially linear
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
(
polyethylene
Polyethylene or polythene (abbreviated PE; IUPAC name polyethene or poly(methylene)) is the most commonly produced plastic. It is a polymer, primarily used for packaging ( plastic bags, plastic films, geomembranes and containers including bo ...
), with significant numbers of short branches, commonly made by
copolymerization
In polymer chemistry, a copolymer is a polymer derived from more than one species of monomer. The polymerization of monomers into copolymers is called copolymerization. Copolymers obtained from the copolymerization of two monomer species are some ...
of
ethylene
Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds).
Ethylene i ...
with longer-chain
olefin
In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond.
Alkene is often used as synonym of olefin, that is, any hydrocarbon containing one or more double bonds.H. Stephen Stoker (2015): General, Organic, an ...
s. Linear low-density polyethylene differs structurally from conventional
low-density polyethylene
Low-density polyethylene (LDPE) is a thermoplastic made from the monomer ethylene. It was the first grade of polyethylene, produced in 1933 by Imperial Chemical Industries (ICI) using a high pressure process via free radical polymerization. Its ...
(LDPE) because of the absence of long chain branching. The linearity of LLDPE results from the different manufacturing processes of LLDPE and LDPE. In general, LLDPE is produced at lower temperatures and pressures by copolymerization of ethylene and such higher
alpha-olefins
In organic chemistry, alpha-olefins (or α-olefins) are a family of organic compounds which are alkenes (also known as olefins) with a chemical formula , distinguished by having a double bond at the primary or alpha (α) position.''Petrochemical ...
as
butene
Butene, also known as butylene, is an alkene with the formula . The word ''butene'' may refer to any of the individual compounds. They are colourless gases that are present in crude oil as a minor constituent in quantities that are too small for ...
,
hexene
In organic chemistry, hexene is a hydrocarbon with the chemical formula . The prefix "hex" is derived from the fact that there are 6 carbon atoms in the molecule, while the "-ene" suffix denotes that there is an alkene present—two carbon atom ...
, or
octene
Octene is an alkene with the formula . Several isomers of octene are known, depending on the position and the geometry of the double bond in the carbon chain.
The simplest isomer is 1-octene, an alpha-olefin used primarily as a co-monomer in p ...
. The copolymerization process produces an LLDPE polymer that has a narrower molecular weight distribution than conventional LDPE and in combination with the linear structure, significantly different
rheological
Rheology (; ) is the study of the flow of matter, primarily in a fluid (liquid or gas) state, but also as "soft solids" or solids under conditions in which they respond with plastic flow rather than deforming elastically in response to an applie ...
properties.
Production and properties
The production of LLDPE is initiated by
transition metal catalysts, particularly
Ziegler or Philips types of catalyst. The actual polymerization process can be done either in solution phase or in gas phase reactors. Usually, octene is the
comonomer In polymer chemistry, a comonomer refers to a polymerizable precursor to a copolymer aside from the principal monomer. In some cases, only small amounts of a comonomer are employed, in other cases substantial amounts of comonomers are used. Furthe ...
in solution phase while butene and hexene are copolymerized with ethylene in a gas phase reactor. LLDPE has higher
tensile strength
Ultimate tensile strength (UTS), often shortened to tensile strength (TS), ultimate strength, or F_\text within equations, is the maximum stress that a material can withstand while being stretched or pulled before breaking. In brittle materials t ...
and higher impact and
puncture resistance
Puncture resistance denotes the relative ability of a material or object to inhibit the intrusion of a foreign object. This is defined by a test method, regulation, or technical specification. It can be measured in several ways ranging from a s ...
than does
LDPE
Low-density polyethylene (LDPE) is a thermoplastic made from the monomer ethylene. It was the first grade of polyethylene, produced in 1933 by Imperial Chemical Industries (ICI) using a high pressure process via free radical polymerization. Its ...
. It is very flexible and elongates under stress. It can be used to make thinner films, with better
environmental stress cracking
Environmental Stress Cracking (ESC) is one of the most common causes of unexpected brittle failure of thermoplastic (especially amorphous) polymers known at present. According to ASTM D883, stress cracking is defined as "an external or intern ...
resistance. It has good resistance to chemicals. It has good electrical properties. However, it is not as easy to process as LDPE, has lower gloss, and narrower range for
heat sealing
In thermodynamics, heat is defined as the form of energy crossing the boundary of a thermodynamic system by virtue of a temperature difference across the boundary. A thermodynamic system does not ''contain'' heat. Nevertheless, the term is al ...
.
Processing
LDPE and LLDPE have unique rheological or melt flow properties. LLDPE is less shear sensitive because of its narrower
molecular weight
A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioch ...
distribution and shorter chain branching. During a shearing process, such as extrusion, LLDPE remains more viscous and, therefore, harder to process than an LDPE of equivalent melt index. The lower shear sensitivity of LLDPE allows for a faster stress relaxation of the polymer chains during extrusion, and, therefore, the physical properties are susceptible to changes in blow-up ratios. In melt extension, LLDPE has lower viscosity at all strain rates. This means it will not strain harden the way LDPE does when elongated. As the deformation rate of the polyethylene increases, LDPE demonstrates a dramatic rise in
viscosity
The viscosity of a fluid is a measure of its resistance to deformation at a given rate. For liquids, it corresponds to the informal concept of "thickness": for example, syrup has a higher viscosity than water.
Viscosity quantifies the inte ...
because of chain entanglement. This phenomenon is not observed with LLDPE because of the lack of long-chain branching in LLDPE allows the chains to slide by one another upon elongation without becoming entangled. This characteristic is important for film applications because LLDPE films can be downgauged easily while maintaining high strength and toughness. The
rheological
Rheology (; ) is the study of the flow of matter, primarily in a fluid (liquid or gas) state, but also as "soft solids" or solids under conditions in which they respond with plastic flow rather than deforming elastically in response to an applie ...
properties of LLDPE are summarized as "stiff in shear" and "soft in extension". LLDPE can be
recycled
Recycling is the process of converting waste materials into new materials and objects. The recovery of energy from waste materials is often included in this concept. The recyclability of a material depends on its ability to reacquire the p ...
though into other things like trash can liners, lumber, landscaping ties, floor tiles, compost bins, and shipping envelopes
Application
LLDPE has penetrated almost all traditional markets for polyethylene; it is used for
plastic bags
A plastic bag, poly bag, or pouch is a type of container made of thin, flexible, plastic film, nonwoven fabric, or plastic textile. Plastic bags are used for containing and transporting goods such as foods, produce, powders, ice, magazines, c ...
and sheets (where it allows using lower thickness than comparable LDPE),
plastic wrap
Plastic wrap, cling film, Saran wrap, cling wrap, Glad wrap or food wrap is a thin plastic film typically used for sealing food items in containers to keep them fresh over a longer period of time. Plastic wrap, typically sold on rolls in boxes ...
,
stretch wrap
Stretch wrap or stretch film is a highly stretchable plastic film that is wrapped around items. The elastic recovery keeps the items tightly bound. In contrast, shrink wrap is applied loosely around an item and shrinks tightly with heat. While ...
, pouches, toys, covers, lids, pipes, buckets and containers, covering of cables,
geomembranes
A geomembrane is very low permeability synthetic membrane liner or barrier used with any geotechnical engineering related material so as to control fluid (liquid or gas) migration in a human-made project, structure, or system. Geomembranes are m ...
, and mainly flexible tubing. In 2013, the world market for LLDPE reached a volume of $40 billion.
LLDPE manufactured by using
metallocene
A metallocene is a compound typically consisting of two cyclopentadienyl anions (, abbreviated Cp) bound to a metallic element, metal center (M) in the oxidation state II, with the resulting general formula Closely related to the metallocenes are ...
catalysts is labeled ''mLLDPE''.
See also
*
Cross-linked polyethylene
Cross-linked polyethylene, commonly abbreviated PEX, XPE or XLPE, is a form of polyethylene with cross-links. It is used predominantly in building services pipework systems, hydronic radiant heating and cooling systems, domestic water piping, ins ...
(XLPE/PEX)
*
Low-density polyethylene
Low-density polyethylene (LDPE) is a thermoplastic made from the monomer ethylene. It was the first grade of polyethylene, produced in 1933 by Imperial Chemical Industries (ICI) using a high pressure process via free radical polymerization. Its ...
(LDPE)
*
High-density polyethylene
High-density polyethylene (HDPE) or polyethylene high-density (PEHD) is a thermoplastic polymer produced from the monomer ethylene. It is sometimes called "alkathene" or "polythene" when used for HDPE pipes. With a high strength-to-density ratio, ...
(HDPE)
*
Medium-density polyethylene
Medium-density polyethylene (MDPE) is a type of polyethylene defined by a density range of 0.926–0.940 g/cm3. It is less dense than HDPE, which is more common.
MDPE can be produced by chromium/silica catalysts, Ziegler-Natta catalysts or meta ...
(MDPE)
*
Ultra-high-molecular-weight polyethylene
Ultra-high-molecular-weight polyethylene (UHMWPE, UHMW) is a subset of the thermoplastic polyethylene. Also known as high-modulus polyethylene, (HMPE), it has extremely long chains, with a molecular mass usually between 3.5 and 7.5 million amu. T ...
(UHMWPE)
*
Stretch wrap
Stretch wrap or stretch film is a highly stretchable plastic film that is wrapped around items. The elastic recovery keeps the items tightly bound. In contrast, shrink wrap is applied loosely around an item and shrinks tightly with heat. While ...
*
Plastic recycling
Plastic recycling is the reprocessing of plastic waste into new products. When performed correctly, this can reduce dependence on landfill, conserve resources and protect the environment from plastic pollution and greenhouse gas emissions.
A ...
References
*Modern Plastic Mid-October Encyclopedia Issue, ''page 56 and 61''
External links
*
Example of LLDPE Physical Properties
{{Packaging
Polyolefins
Plastics
Packaging materials