Branching branched polymer

In terms of their architecture, polymers can be classified as linear, branched and cross-linked polymers (Table 1.2). In the linear polymers, the structural imits are arranged in a linear sequence. Branched polymers may have short and long branches. Branched polymers include comblike and star polymers. Extensive branching may lead to a dendritic structure. 

The simplest case of structure-property relationships are qualitative rules of thumb. For example, the statement that branched polymers are generally more biodegradable than straight-chain polymers is a qualitative structure-property relationship. 

An area of great interest in the polymer chemistry field is structure-activity relationships. In the simplest form, these can be qualitative descriptions, such as the observation that branched polymers are more biodegradable than straight-chain polymers. Computational simulations are more often directed toward the quantitative prediction of properties, such as the tensile strength of the bulk material. 

We must be careful in assessing the experimental results on the viscosity of branched polymers. If we compare two polymers of identical molecular weight, one branched and the other unbranched, it is possible that the branched one would show lower viscosity. Two considerations enter the picture here. First, since the side chains contribute to the molecular weight, the backbone chain... 

We noted above that the presence of monomer with a functionality greater than 2 results in branched polymer chains. This in turn produces a three-dimensional network of polymer under certain circumstances. The solubility and mechanical behavior of such materials depend critically on whether the extent of polymerization is above or below the threshold for the formation of this network. The threshold is described as the gel point, since the reaction mixture sets up or gels at this point. We have previously introduced the term thermosetting to describe these cross-linked polymeric materials. Because their mechanical properties are largely unaffected by temperature variations-in contrast to thermoplastic materials which become more fluid on heating-step-growth polymers that exceed the gel point are widely used as engineering materials. 

StmcturaHy, arabinogalactan is a complex, highly branched polymer of arabinose and galactose in a 1 6 ratio (67). It is composed of one fraction with an average molecular weight of 16,000, and one of 100,000 (68). 

The polymerization of ethyleneimine (16,354—357) is started by a catalyticaHy active reagent (H or a Lewis acid), which converts the ethyleneimine into a highly electrophilic initiator molecule. The initiator then reacts with nitrogen nucleophiles, such as the ethyleneimine monomer and the subsequendy formed oligomers, to produce a branched polymer, which contains primary, secondary, and tertiary nitrogen atoms in random ratios. Termination takes place by intramolecular macrocycle formation. 

Secondary bonds are considerably weaker than the primary covalent bonds. When a linear or branched polymer is heated, the dissociation energies of the secondary bonds are exceeded long before the primary covalent bonds are broken, freeing up the individual chains to flow under stress. When the material is cooled, the secondary bonds reform. Thus, linear and branched polymers are generally thermoplastic. On the other hand, cross-links contain primary covalent bonds like those that bond the atoms in the main chains. When a cross-linked polymer is heated sufficiently, these primary covalent bonds fail randomly, and the material degrades. Therefore, cross-linked polymers are thermosets. There are a few exceptions such as cellulose and polyacrylonitrile. Though linear, these polymers are not thermoplastic because the extensive secondary bonds make up for in quantity what they lack in quahty. 

Similarly, polymers dissolve when a solvent penetrates the mass and replaces the interchain secondary bonds with chain-solvent secondary bonds, separating the individual chains. This cannot happen when the chains are held together by primary covalent cross-links. Thus, linear and branched polymers dissolve in appropriate solvents, whereas cross-linked polymers are insoluble, although they may be swelled considerably by absorbed solvent. 

Chain transfer to monomer and to other small molecules leads to lower molecular weight products, but when polymerisation occurs ia the relative absence of monomer and other transfer agents, such as solvents, chain transfer to polymer becomes more important. As a result, toward the end of batch-suspension or batch-emulsion polymerisation reactions, branched polymer chains tend to form. In suspension and emulsion processes where monomer is fed continuously, the products tend to be more branched than when polymerisations are carried out ia the presence of a plentiful supply of monomer. 

High pressure (60—350 MPa) free-radical polymerization using oxygen, peroxide, or other strong oxidizers as initiators at temperatures of up to 350°C to produce low density polyethylene (LDPE), a highly branched polymer, with densities from 0.91 to 0.94 g/cm. ... 

If a polymer molecule has a sufficiently regular structure it may be capable of some degree of crystallisation. The factors affecting regularity will be discussed in the next chapter but it may be said that crystallisation is limited to certain linear or slightly branched polymers with a high structural regularity. Well-known examples of crystalline polymers are polyethylene, acetal resins and polytetrafluoroethylene. 

With the availability of the higher density polymers the value of the melt flow index as a measure of molecular weight diminishes. For example, it has been found that with two polymers of the same weight average molecular weight (4.2 X 10 ), the branched polymer (density = 0.92 g/cm ) had only 1/50 the viscosity of the more or less unbranched polymer (density = 0.96 g/cm ). This is due to long chain branches as explained above. 

Commercial polyfvinyl alcohol) (e.g. Gelvatol, Elvanol, Mowiol and Rhodo-viol) is available in a number of grades which differ in molecular weight and in the residual acetate content. Because alcoholysis will cause scission of branched polymers at the points where branching has proceeded via the acetate group, polyfvinyl alcohol) polymer will have a lower molecular weight than the poly (vinyl acetate) from which it is made. 

By incorporation of some trihalide to give a branched polymer such as Thiokol ST (about 2% of 1,2,3-trichloropropane is used in this instance). The resultant vulcanisates have lower cold flow and compression set than obtained with Thiokol A. 

Structurally viscous grades are based on branched polymers (branching being effected by the use of tri- or higher functional phenols). These polymers exhibit a sharp decrease in viscosity with increasing shear rate which makes them particularly suitable for extrusion and blow moulding and also, it is claimed, in reducing drip in case of fire. 

Whilst conventional polycarbonate based on bis-phenol A is essentially linear, branched polymers have recently been introduced. These materials have flow properties and a melt stability that makes them particularly suitable for large (20 litre) water and milk containers. Branched polymers have also been used in the manufacture of twin-walled sheet for the building industry. 

The first commercial grades were introduced by Phillips Petroleum in 1968 under the trade name Ryton. These were of two types, a thermoplastic branched polymer of very high viscosity which was processed by PTFE-type processes and an initially linear polymer which could be processed by compression moulding, including laminating with glass fibre, and which was subsequently oxidatively cross-linked. 

It has been shown" that branched polymers have lower melting points and viscosities than linear polymers of the same molecular weight. The viscosity of the silicone fluids is much less affected by temperature than with the corresponding paraffins (see Figure 29.2). 

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