Dynamic mechanical and dielectric properties of phosphonylated polypentenamers and their hydrogenated derivatives

Abstract

Dynamic mechanical and dielectric properties of substituted polypentenamers with phosphonate side groups and their hydrogenated derivatives have been studied. Methyl esters, acids, and salts were investigated at two concentrations, 6.5 and 11.1 mole percent. In the unhydrogenated derivatives, one principal relaxation, labeled (3, is observed mechanically in the temperature range from-160 to 100°C. This (3 relaxation arises from micro-Brownian segmental motion accompanying the glass transition. Its temperature is substantially affected by the substituent concentration while its breadth is affected by the chemical nature of the substituent. An extended "rubbery plateau" region exists in the acid and salt derivatives. The dielectric results generally reinforce the mechanical assignments. In the hydrogenated derivatives, three relaxations labeled a, (3, and 'Y in order of decreasing temperature occur mechanically in this temperature range. The temperatures at which the a and (3 relaxations occur depend greatly on the chemical nature of the substituents, the substituent concentration, and the thermal history of the sample; while the 'Y relaxation appears to be independent of these variables. Suggested assignments for the relaxations observed in these polymers, based on the duiil glass transition theory of Boyer for semicrystalline polymers, have been proposed. The dielectric results are consistent with the proposed assignments.

Structural Properties of Ionomers

“…These reactions can be carried out in solution or via reactive milling in an extruder. During the last decade, a novel ionic elastomer was developed based on a polypentenamer backbone (15)(16)(17)(18)(19)(20)(21). The starting poly pentenamer was prepared via ring-opening polymerization of cyclo pentane.…”

Structure and Properties of Ionomers

“…The concept of neutralizing the acid side groups to produce materials containing "ionic crosslinks" was apparently largely due to Brown (1957). In the 1960s, DuPont introduced an ionomer which was the zinc or sodium salt of an ethylene-methacrylic acid copolymer (Rees andVaughan, 1965a, 1965b) and which was marketed under the trade name of Surlyn. The Surlyn resins have since become increasingly important in the areas of packaging and coatings.…”

“…The dynamic mechanical properties of ethylene ionomers have been investigated by many workers (Rees and Vaughan, 1965a;Otocka and K wei, 1968aOtocka and K wei, , 1968bOtocka and K wei, , 1969Longworth and Vaughan, 1968;Read, 1967, 1968a;McKenna, Kajiyama, and MacKnight, 1968). In general the response for both the parent acid copolymers and their salts resembles that of low-density polyethylene.…”

“…This is interpreted to mean that the concentration of ionic material is growing in the hydrocarbon phase at the expense of the ion-rich phase, or more simply that the clusters are breaking up at high temperatures. Several studies of the dielectric properties of ethylene-methacrylic acid copolymers and their salts have been conducted (MacKnight and Emerson, 1971;Read et al, 1969;Phillips and MacKnight, 1970). In general, the same features observed mechanically occur also in the dielectric experiments.…”

“…A number of different backbones and pendant acid groups have been prepared and described. In the case of the backbone these include polybutadiene (Brown, 1957), polystyrene (Longworth et al, 1958), polyethylene (Rees et al, 1965), polyoxymethylene (Wissbrun, 1963), and polypentenamer (Sanui et al, 1974;Rahrig et al, 1978;Azuma and MacKnight, 1978;Tanaka and MacKnight, 1978). Acid groups have included carboxylic, sulfonic, thioglycolic, phosphonic, and others.…”