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Linear low density polyethylene (LLDPE) is a substantially linear polymer (polyethylene), with significant numbers of short branches, commonly made by copolymerization of ethylene with longer-chain olefins. Linear low-density polyethylene differs structurally from conventional low-density polyethylene because of thee absence of long chain branching. The linearity of LLDPE results from the different manufacturing provesses of LLDPE and LDPE. LLDPE is typically produced, at lower temperatures and pressures, by copolymerization of ethylene and such higher alpha olefins as butene, hexene or octene. The copolymerization process produces a LLDPE polymer that has a narrower molecular weight distribution than conventional LDPE and in combination with the linear structure, significantly different rheological properties.

The production of LLDPE is initiated by transition metal catalysts, particularly Ziegler or Philips type of catalyst. The actual polymerization process can be done in either solution phase or gas phase reactors. Usually, octene is the copolymer in solution phase while butene and hexene are copolymerized with ethylene in a gas phase reactor. The LLDPE resin produced in a gas phase reactor is in granular form and may be sold as granules or processed into pellets. LLDPE has higher tensile strength and higher impact and puncture resistance than LDPE. It is very flexible and elongates under stress. It can be used to make thinner films, with better environmental stress cracking resistance. It has good resistance to chemicals and to ultraviolet radiation. It has good electrical properties. However it is not as easy to process as LDPE, has lower gloss, and narrower range for heat sealing.

LDPE and LLDPE have unique rheological or melt flow properties. LLDPE is less shear sensitive because of its narrower molecular weight distribution and shorter chain branching. During a shearing process, such as extrusion, LLDPE remains more viscous, therefore harder to process than a 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 because of chain entanglement. This phenomena 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 downgaged easily while maintaining high strength and toughness. The rheological properties of LLDPE are summarized as "stiff in shear" and "soft in extension."

LLDPE has penetrated almost all traditional markets for polyethylene, it is used for plastic bags and sheets (where it allows using lower thickness than comparable LDPE), plastic wrap, stretch wrap, pouches, toys, lids, pipes, buckets and containers, covering of cables, geomembranes, and mainly for flexible tubing.

LLDPE manufactured using metallocene catalysts is labeled mLLDPE.

• Modern Plastic Mid-October Encyclopedia Issue, page 56 and 61

• [1] Example of LLDPE Physical Properties

• Low density polyethylene
• High density polyethylene
• Ultra high molecular weight polyethylene