Polyethylene short-chain

Figure 2 Short chain branching distribution in polyethylenes. Source Ref. 31.

Copolymerization e.g., of 1-butene or 1-hexene with ethylene, gives short-chain branching-, e.g., the branches contain three or five carbon atoms. The random location of the side-chains lowers the crystallinity and density. Long-chain branching refers to branches that are similar in length to the polymer backbone and this type occurs in polyethylene manufactured using the... 

These monomers are biodegradeable and used for the production of bioplastics. PHAs produced from the process are usually composed of 100-30,000 monomers and exist in a short chain. Naturally, the properties of PHAs are similar to thermoplastics that are obtained from petrochemical industry such as polypropylene (PP) and polyethylene (PE) as shown in Table 1 (Evan and Sikdar, 1990). 

The predominating type of nonlinearity in polyethylene appears to consist of short chain branches three or four chain atoms in length formed by intramolecular chain transfer as follows ... 

There are numerous variations on the basic linear structure of polymers. Returning to our example of polyethylene, we find short chain branches and long chain branches, as shown in Figs. 1.2 and 1.3, respectively. The number and type of these branches strongly influences the way that the molecules pack in the solid state, and hence affect the physical properties. Long... 

Figure 1.2 Polyethylene molecule with a short chain (butyl) branch...

At the opposite end of the polyethylene spectrum are the so-called ultra low density products with a high concentration of short chain branching that inhibits crystallization. These materials are soft, flexible, and transparent we encounter these materials in applications such as medical tubing, meat packaging films, and ice bags. 

We can incorporate short chain branches into polymers by copolymerizing two or more comonomers. When we apply this method to addition copolymers, the branch is derived from a monomer that contains a terminal vinyl group that can be incorporated into the growing chain. The most common family of this type is the linear low density polyethylenes, which incorporate 1-butene, 1-hexene, or 1-octene to yield ethyl, butyl, or hexyl branches, respectively. Other common examples include ethylene-vinyl acetate and ethylene-acrylic acid copolymers. Figure 5.10 shows examples of these branches. 

An example of a backbiting reaction that creates the short chain branches is shown in Fig. 18.5. In this example the growing end of a polyethylene chain turns back on itself and abstracts a hydrogen atom from the carbon atom located four bonds away from the chain end, as shown in Fig. 18.5 a). Chain growth proceeds from the newly formed unpaired electron, leaving a pendant butyl group, as shown in Fig. 18.5 b). There are many variants of backbiting, which create a variety of short chain branches. 

We can also incorporate branches by copolymerizing ethylene with vinyl esters and vinyl acids. In addition to their ester or acid side groups, these copolymers also contain the long and short chain branches, which are characteristic of low density polyethylene. 

How do long and short chain branching influence the crystallinity of polyethylene ... 

Favorable rheological properties are an essential requirement for the commercialization of polyolefins like polyethylene. The ease of processability of the polymer melt, obtained through modifications in the microstructural features, is as important as the end use mechanical properties of these polymers. Presence of long-chain as well as short-chain branching, LCB and SCB, respectively, more or less dictates the rheological behavior of most commercial... 

Despite this tremendous versatility, there is still a fundamental limitation for these random copolymers melting point and modulus (stiffness) are inextricably coupled to the density (or percentage short-chain branching from LAO comonomer) as shown in Fig. 1. The same method employed to lower modulus (incorporation of comonomer) results in a thinning of the polyethylene crystals, concomitant with a lowering of the melting point, according to a relationship established by Flory [8],... 

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