Branching of polymer chains

Branching of polymer chains might be introduced by intermolecular reactions... 

Now let us consider the probability that a section of polymer chain is capped at both ends by potential branch points ... 

Crystallinity and Density. Crystallinity and density of HDPE resins are derivative parameters both depend primarily on the extent of short-chain branching in polymer chains and, to a lesser degree, on molecular weight. The density range for HDPE resins is between 0.960 and 0.941 g/cm. In spite of the fact that UHMWPE is a completely nonbranched ethylene homopolymer, due to its very high molecular weight, it crystallines poorly and has a density of 0.93 g/cm. ... 

Physical Properties. LLDPE is a sernicrystaUine plastic whose chains contain long blocks of ethylene units that crystallize in the same fashion as paraffin waxes or HDPE. The degree of LLDPE crystallinity depends primarily on the a-olefin content in the copolymer (the branching degree of a resin) and is usually below 40—45%. The principal crystalline form of LLDPE is orthorhombic (the same as in HDPE) the cell parameters of nonbranched PE are a = 0.740 nm, b = 0.493 nm, and c (the direction of polymer chains) = 0.2534 nm. Introduction of branching into PE molecules expands the cell slightly thus a increases to 0.77 nm and b to around 0.50 nm. 

Thermal, Thermooxidative, and Photooxidative Degradation. Polymers of a-olefins have at least one tertiary C-H bond in each monomer unit of polymer chains. As a result, these polymers are susceptible to both thermal and thermooxidative degradation. Reactivity in degradation reactions is especially significant in the case of polyolefins with branched alkyl side groups. For example, thermal decomposition of... 

The formation of the microstructure involves the folding of linear segments of polymer chains in an orderly manner to form a crystalline lamellae, which tends to organize into a spherulite structure. The SCB hinder the formation of spherulite. However, the volume of spherulite/axialites increases if the branched segments participate in their formation [59]. Heterogeneity due to MW and SCB leads to segregation of PE molecules on solidification [59-65], The low MW species are accumulated in the peripheral parts of the spherulite/axialites [63]. The low-MW segregated material is brittle due to a low concentration of interlamellar tie chains [65] and... 

Keywords. Statistical chemistry of polymers, Chain and step polymerizations, Linear and branched polymers... 

Viscosity measurement or rheology. Viscosity is an important property of many fluids, particularly consumer products. Pancake syrup that does not appear thick or a runny shampoo has little consumer appeal. Viscosity is also an important measurement for liquid polymers. It is a measure of polymer chain length and branching. On the other hand, viscosity does not have the sensitivity to detect small amounts of impurities in pure substance. 

The tube model gives a direct indication of why one might expect the strange observations on star melts described above. Because the branch points themselves in a high molecular weight star-polymer melt are extremely dilute, the physics of local entanglements is expected to be identical to the linear case each segment of polymer chain behaves as if it were in a tube of diameter a. However, in... 

It is evident that due to polymeric specificity of LC polymers most of the information on their molecular parameters, i.e. molecular mass, conformational state, polymeric chain flexibility and mobility, optical anisotropy and others, may be obtained from studies of dilute solutions of these compounds. However, taking into account that this branch of polymer science has already been reviewed 134>172-176> we will here confine our treatment only to the initial steps of LC phase formation in polymer solutions. 

Co-polymerization of pentaerythritol and two other monomers—an unsaturated acid and benzene 1,3-dicarboxylic acid—gives a network of polymer chains branching out from the quaternary carbon atom at the centre of pentaerythritol. The reaction is simply ester formation by a carbonyl substitution reaction at high temperature (> 200°C). Ester formation between acids and alcohols is an equilibrium reaction but at high temperatures water is lost as steam and the equilibrium is driven over to the right. 

It is not necessary to have quite such a highly branched cross-linking agent to make a network of polymer chains. A triply branched compound is the basis for one of the strongest polymers known— one that we take for granted every time we use the kitchen. It is made by a very simple reaction. 

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