Backbone, polymer

Since the monomers are specified to be vinyl monomers, each contributes two carbon atoms to the polymer backbone, with the associated extended length of 0.252 nm per repeat unit. Therefore the total extended length of the empirical formula unit is... 

For a carbon-carbon bond located along a polymer backbone, the preceding molecular representation must be modified to Fig. 1.8c. The chain segments on either side of the bond of interest are substituents for which the amount of steric hindrance follows a slightly different pattern than for the unsubstituted ethane. Using the same convention for [Pg.58]

Complications arising from other types of isomerism. Positional and geometrical isomerism, also described in Sec. 1.6, will be excluded for simplicity. In actual polymers these are not always so easily ignored. Polymerization of 1,2-disubstituted ethylenes. Since these introduce two different asymmetric carbons into the polymer backbone (second substituent Y), they have the potential to display ditacticity. Our attention to these is limited to the illustration of some terminology which is derived from carbohydrate nomenclature (structures [IX]-[XII]) ... 

Properly end-capped acetal resins, substantially free of ionic impurities, are relatively thermally stable. However, the methylene groups in the polymer backbone are sites for peroxidation or hydroperoxidation reactions which ultimately lead to scission and depolymerisation. Thus antioxidants (qv), especially hindered phenols, are included in most commercially available acetal resins for optimal thermal oxidative stabiUty. 

Numerous diamines and aromatic dianhydrides have been investigated. WhoUy aromatic Pis have been stmctiirally modified by incorporating various functional groups, such as ether, carbonyl, sulfide, sulfone, methylene, isopropjlidene, perfluoroisopropyUdene, bipyridyls, sdoxane, methyl phosphine oxide, or various combinations of these, into the polymer backbone to achieve improved properties. The chemistry and apphcations of Pis have been described in several review articles (4). 

Solid Polymer E,kctroljte. The electrolyte in soHd polymer electrolyte (SPE) units is Nafion, a soHd polymer developed by Du Pont, which has sulfonic acid groups attached to the polymer backbone. Electrodes are deposited on each side of the polymer sheet. H" ions produced at the anode move across the polymer to the cathode, and produce hydrogen. The OH ions at the anode produce oxygen. These units have relatively low internal resistances and can operate at higher temperatures than conventional alkaline electrolysis units. SPE units are now offered commercially. 

The resihency and dyeabihty of poly(vinyl alcohol) fibers is improved by a process incorporating -hydroxybenzaldehyde to provide a site for the formation of a stable Mannich base. Hydroxyl groups on the fiber are converted to acetal groups by -hydroxybenzaldehyde. Subsequent reaction with formaldehyde and ammonia or an alkylamine is rapid and forms a stable Mannich base that is attached to the polymer backbone (94). 

Other common radical-initiated polymer processes include curing of resins, eg, unsaturated polyester—styrene blends curing of mbber grafting of vinyl monomers onto polymer backbones and telomerizations. 

If a modest number of cross-links between the polymer backbone are introduced, the polymer Hquid crystal takes on elastomeric properties. The useflilness of these materials probably Hes in the coupling of mechanical and optical effects. 

Reactive groups can be introduced into the polymer backbone by the choice of an appropriate functional monomer. Commercially available examples of such monomers ate as follows ... 

Mechanical Properties Related to Polymer Structure. Methacrylates are harder polymers of higher tensile strength and lower elongation than thek acrylate counterparts because substitution of the methyl group for the a-hydrogen on the main chain restricts the freedom of rotation and motion of the polymer backbone. This is demonstrated in Table 3. 

Such copolymers of oxygen have been prepared from styrene, a-methylstyrene, indene, ketenes, butadiene, isoprene, l,l-diphen5iethylene, methyl methacrjiate, methyl acrylate, acrylonitrile, and vinyl chloride (44,66,109). 1,3-Dienes, such as butadiene, yield randomly distributed 1,2- and 1,4-copolymers. Oxygen pressure and olefin stmcture are important factors in these reactions for example, other products, eg, carbonyl compounds, epoxides, etc, can form at low oxygen pressures. Polymers possessing dialkyl peroxide moieties in the polymer backbone have also been prepared by base-catalyzed condensations of di(hydroxy-/ f2 -alkyl) peroxides with dibasic acid chlorides or bis(chloroformates) (110). 

The substantial decrease of polyacrylamide solution viscosity in mildly saline waters can be uti1i2ed to increase injection rates. A quaternary ammonium salt polymer can be added to the polyacrylamide solution to function as a salt and reduce solution viscosity (144). If the cationic charge is in the polymer backbone and substantially shielded from the polyacrylamide by steric hindrance, formation of an insoluble interpolymer complex can be delayed long enough to complete polyacrylamide injection. Upon contacting formation surfaces, the quaternary ammonium salt polymer is adsorbed reducing... 

The most innovative photohalogenation technology developed in the latter twentieth century is that for purposes of photochlorination of poly(vinyl chloride) (PVC). More highly chlorinated products of improved thermal stabiUty, fire resistance, and rigidity are obtained. In production, the stepwise chlorination may be effected in Hquid chlorine which serves both as solvent for the polymer and reagent (46). A soHd-state process has also been devised in which a bed of microparticulate PVC is fluidized with CI2 gas and simultaneously irradiated (47). In both cases the reaction proceeds, counterintuitively, to introduce Cl exclusively at unchlorinated carbon atoms on the polymer backbone. 

Polyamides, often also lefeiied to as nylons, are liigli polymers which contain the amide repeat linkage in the polymer backbone. They are generally characterized as tough, translucent, semicrystalline polymers that ate moderately low cost and easily manipulated commercially by melt processing. 

The aromatic sulfone polymers are a group of high performance plastics, many of which have relatively closely related stmctures and similar properties (see Polymers containing sulfur, polysulfones). Chemically, all are polyethersulfones, ie, they have both aryl ether (ArOAr) and aryl sulfone (ArS02Ar) linkages in the polymer backbone. The simplest polyethersulfone (5) consists of aromatic rings linked alternately by ether and sulfone groups. 

Degradation of polyolefins such as polyethylene, polypropylene, polybutylene, and polybutadiene promoted by metals and other oxidants occurs via an oxidation and a photo-oxidative mechanism, the two being difficult to separate in environmental degradation. The general mechanism common to all these reactions is that shown in equation 9. The reactant radical may be produced by any suitable mechanism from the interaction of air or oxygen with polyolefins (42) to form peroxides, which are subsequentiy decomposed by ultraviolet radiation. These reaction intermediates abstract more hydrogen atoms from the polymer backbone, which is ultimately converted into a polymer with ketone functionahties and degraded by the Norrish mechanisms (eq. 

During this early period, a very ingenious free-radical route to polyesters was used to introduce weak linkages into the backbones of hydrocarbon polymers and render them susceptible to bio degradabihty (128—131). Copolymerization of ketene acetals with vinyl monomers incorporates an ester linkage into the polymer backbone by rearrangement of the ketene acetal radical as illustrated in equation 13. The ester is a potential site for biological attack. The chemistry has been demonstrated with ethylene (128—131), acryhc acid (132), and styrene (133). 

Polymers. The molecular weights of polymers used in high energy electron radiation-curable coating systems are ca 1,000—25,000 and the polymers usually contain acryUc, methacrylic, or fumaric vinyl unsaturation along or attached to the polymer backbone (4,48). Aromatic or aUphatic diisocyanates react with glycols or alcohol-terrninated polyether or polyester to form either isocyanate or hydroxyl functional polyurethane intermediates. The isocyanate functional polyurethane intermediates react with hydroxyl functional polyurethane and with acryUc or methacrylic acids to form reactive p olyurethanes. 

Table 6. Performance Characteristics of Thermally Curable Polymer Backbone Systems...

Fig. 7. Photodimerization of light-sensitive functional groups attached to polymer backbone stmctuies (a) polymer containing photosensitive cinnamic...

Ethylene—Propylene Rubber. Ethylene and propjiene copolymerize to produce a wide range of elastomeric and thermoplastic products. Often a third monomer such dicyclopentadiene, hexadiene, or ethylene norbomene is incorporated at 2—12% into the polymer backbone and leads to the designation ethylene—propylene—diene monomer (EPDM) mbber (see Elastomers, synthetic-ethylene-propylene-diene rubber). The third monomer introduces sites of unsaturation that allow vulcanization by conventional sulfur cures. At high levels of third monomer it is possible to achieve cure rates that are equivalent to conventional mbbers such as SBR and PBD. Ethylene—propylene mbber (EPR) requires peroxide vulcanization. 

High heat ABS resins are produced by adding a third monomer to the styrene and acrylonitrile to stiffen the polymer backbone, thus raising the T. Two monomers used commercially for this purpose are a-methylstyrene (85) and /V-pheny1ma1eimide (86). 

Attaching the ketone groups to the polymer backbone is more efficient on a chain scission/ketone basis because some of the light energy that the pendent ketone absorbs leads direcdy to chain scission via the Norrish type II mechanism, as well as photooxidation via the Norrish type I mechanism (see... 

---