Homopolymers branched

Two other forms of copolymers that can be prepared under certain conditions are called block copolymers and graft copolymers. Block copolymers are those in which different blocks of identical monomer units alternate with each other graft copolymers are those in which homopolymer branches of one monomer unit are "grafted" onto a homopolymer chain of another monomer unit. 

Graft copolymer (Section 31.3) A copolymer in which homopolymer branches of one monomer unit are grafted onto a homopolymer chain of another monomer unit. 

An-type star corresponds to a star with n similar homopolymer branches (n>2)... 

The polymer molecule will be associated with the designated operation by subscripts 1, 2, etc. Thus Pi indicates polymerization of mi. The operation G is specified by both subscripts, the order of the subscripts indicating the backbone and the branch side chain. (Identical subscripts could, of course, be used to indicate homopolymer branching.)... 

Gi2> distance between the star center and the center of mass of the i homopolymer branch in a symmetric star homopolymer with the same number of branches as the miktoarm star... 

Figure 1.3 Different types of configuration of homopolymers branching...

During the polymeriza tion process the normal head-to-tad free-radical reaction of vinyl chloride deviates from the normal path and results in sites of lower chemical stabiUty or defect sites along some of the polymer chains. These defect sites are small in number and are formed by autoxidation, chain termination, or chain-branching reactions. Heat stabilizer technology has grown from efforts to either chemically prevent or repair these defect sites. Partial stmctures (3—6) are typical of the defect sites found in PVC homopolymers (2—5). 

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. ... 

The number of branches in HDPE resins is low, at most 5 to 10 branches per 1000 carbon atoms in the chain. Even ethylene homopolymers produced with some transition-metal based catalysts are slightly branched they contain 0.5—3 branches per 1000 carbon atoms. Most of these branches are short, methyl, ethyl, and -butyl (6—8), and their presence is often related to traces of a-olefins in ethylene. The branching degree is one of the important stmctural features of HDPE. Along with molecular weight, it influences most physical and mechanical properties of HDPE resins. 

The chemical iadustry manufactures a large variety of semicrystalline ethylene copolymers containing small amounts of a-olefins. These copolymers are produced ia catalytic polymerisation reactions and have densities lower than those of ethylene homopolymers known as high density polyethylene (HDPE). Ethylene copolymers produced ia catalytic polymerisation reactions are usually described as linear ethylene polymers, to distiaguish them from ethylene polymers containing long branches which are produced ia radical polymerisation reactions at high pressures (see Olefin POLYMERS, LOWDENSITY polyethylene). 

As shown in Table 3, the glass-transition temperatures of the amorphous straight-chain alkyl vinyl ether homopolymers decrease with increasing length of the side chain. Also, the melting points of the semicrystalline poly(alkyl vinyl ether)s increase with increasing side-chain branching. 

The distinctions between these homopolymers arise from the different ways in which the monomer units are hooked together in polyacetal chains. Starch (qv), plant nutrient material, is composed of two polysaccharides a-amylose and amylopectin. cx-Amylose is linear because of exclusive a (1 — 4) linkages, whereas amylopectin is branched because of the presence of a (1 — 6) as well as a (1 — 4) links. The terms linear and branched refer only to primary stmcture. 

Short chain branching is negligible with Ziegler and Phillips homopolymers although it is possible to introduce deliberately up to about seven ethyl side chains per 1000 carbon atoms in the Ziegler polymers. 

Polyethylene s simplicity of structure has made it one of the most thoroughly studied polymeric materials. With an estimated demand of close to 109 billion pounds in 2000 of the homopolymer and various copolymers of polyethylene,24 it is by far the world s highest volume synthetic macromolecule. Therefore, it is still pertinent to study its structure-property relationships, thermal behavior, morphology, and effects of adding branches and functional groups to the polymer backbone. 

Graft copolymers are those in which a homopolymer backbone has a number of branches, which are themselves homopolymers of another monomer, grafted on ... 

Relationships between dilute solution viscosity and MW have been determined for many hyperbranched systems and the Mark-Houwink constant typically varies between 0.5 and 0.2, depending on the DB. In contrast, the exponent is typically in the region of 0.6-0.8 for linear homopolymers in a good solvent with a random coil conformation. The contraction factors [84], g=< g >branched/ <-Rg >iinear. =[ l]branched/[ l]iinear. are another Way of cxprcssing the compact structure of branched polymers. Experimentally, g is computed from the intrinsic viscosity ratio at constant MW. The contraction factor can be expressed as the averaged value over the MWD or as a continuous fraction of MW. 

For illustration consider SEC chromatograms obtained for two polymers on the same chromatographic system. One sample is a linear homopolymer while the other is a branched polymer with the same chemical composition. In the latter sample assume that the polymer components of different molecular weight have uniform branching characteristics so that all have similar molecular size/weight relationships. 

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