Dynamic mechanical properties of poly(vinyl alkyl ethers)

Abstract

SynopsisThe temperature dependence of the dynamic mechanical properties of dicumyl peroxide/sulfur vulcanizates of seven members of the poly(viny1 alkyl ether) series of elastomers has been determined. The relative position of the curves, relating the dynamic resilience to the dynamic modulus of these polymers, was generally in the order of their glass transformation temperatures ( Tg). The dynamic mechanical property data on poly(viny1 n-pentyl ether) and poly(viny1 a-ethylhexyl ether), which have the same To, fall on a common curve characteristic of the temperature of measurement. The dynamic resilience versus dynamic modulus curves are displaced towards higher dynamic resilience and usually lower dynamic modulus values as the temperature of measurement is increased. Poly(viny1 isobutyl ether) and poly(viny1 ethyl ether) show a larger temperature coefficient of resilience than do the other poly(viny1 dkyl ethers), which also include the n-butyl, n-hexyl, and n-octyl members. Apparently, the To is a major factor in correlating the dynamic mechanical behavior of this homologous series of elastomers. The size and shape of the alkyl group appear to be reflected primarily in their effect on the T,. Poly(viny1 isobutyl ether) wm the only member of the series showing any anomalies in dynamic mechanical properties that might be ascribed to structure. Because the dynamic resilience of various poly(viny1 alkyl ether) vulcanizates, possessing the same concentration of chemical crosslinks, correlate better with their degree of polymerization than with their molecular weight it appears that the dynamic resilience depends more on the length of the free chain ends than it does on their mass or volume.

Cationic cyclopolymerization of divinyl ethers with norbornane‐, norbornene‐, or adamantane‐containing substituents: Synthesis of cyclopoly(divinyl ether)s with bulky rigid side chains leading to high glass transition temperature

“…Vinyl ethers are representatives of cationically polymerizable monomers and manufactured in industry mainly by addition of alcohols to acetylene originally developed by Reppe . Poly(vinyl ether)s with linear alkyl side chains are usually sticky liquid or gum‐like polymers at room temperature because of low glass transition temperature [examples of T g of poly(alkyl vinyl ether)s: alkyl: methyl, −34 °C; ethyl, −42 °C; n ‐butyl, −55 °C; n ‐octyl; −80 °C], so that the application of poly(vinyl ether)s for rubber materials or elastomers were intensively studied …”

“…7 Poly(vinyl ether)s with linear alkyl side chains are usually sticky liquid or gum-like polymers at room temperature because of low glass transition temperature [examples of T g of poly(alkyl vinyl ether)s: 8,9 alkyl: methyl, 234 C; ethyl, 242 C; n-butyl, 255 C; n-octyl; 280 C], so that the application of poly(vinyl ether)s for rubber materials or elastomers were intensively studied. [10][11][12][13] In contrast, the polymers of vinyl ethers with an aliphatic polycyclic substituent are a new class of poly(vinyl ether)s with high T g 's well above room temperature. [14][15][16][17][18][19][20] For example, we reported that the polymer of vinyl ether with a tricyclodecane unit (8-vinyloxytricyclo[5.2.1.0 2,6 ]decane; TCDVE) exhibited high T g (e.g., 100 C) and high thermal stability [e.g., thermal decomposition temperatures (T d ) 5 350 C].…”

“…We herein report that divinyl ethers 1-3 undergo cyclopolymerization to give highly cyclized polymers with high T g and high thermal stability. Figure 3(A); 13 C NMR (in toluene-d 8 ): d (ppm) 24.6 (ACH 2 ACH 2 ACH ACH 2 ACA), 28.8 (ACH 2 ACH 2 ACHACA), 37.3 (ACHACH 2 ACA), 37.9 (ACH 2 ACACH 2 A), 38.5 (ACHACH 2 ACA), 41.4 (ACHACA), 45.1 (ACHACH 2 ACHACACH 2 AOA), 69.14, 70.75 (AOACH 2 ACA), 86.16, 86.17 (CH 2 @CHAOA), 152.3, 152.5 (CH 2 @CHAOA). 13 C NMR (in toluene-d 8 ): d (ppm) 28.3, 29.5 (ACHACH 2 ACHACH 2 ACHAC) (ACH 2 ACHACH 2 ACHACA), 32.9 (ACHA CH 2 ACHACA), 39.7 (ACACHA), 42.3 (ACH 2 ACACH 2 A), 67.8 (AOACH 2 A), 86.0 (CH 2 @CHAOA), 152.6 (CH 2 @ CHAOA).…”

Synthesis of ABA‐triblock and star‐diblock copolymers with poly(2‐adamantyl vinyl ether) and poly(n‐butyl vinyl ether) segments: New thermoplastic elastomers composed solely of poly(vinyl ether) backbones

“…Such low T g s, conversely, provide poly(vinyl ether)s with a potential to be applicable for rubber materials. The Goodyear group reported an extensive study of vinyl ether‐based rubbers with crosslinking chains 9–12. Because of inherent lack of unsaturated double bonds of poly(alky vinyl ether)s, however, the vulcanization processes of the vinyl ether polymers in the presence of peroxide and/or sulfur seemed to involve complicated mechanisms and the formation of volatile products mainly coming from side‐chain scission 11.…”

“…Because of inherent lack of unsaturated double bonds of poly(alky vinyl ether)s, however, the vulcanization processes of the vinyl ether polymers in the presence of peroxide and/or sulfur seemed to involve complicated mechanisms and the formation of volatile products mainly coming from side‐chain scission 11. Nevertheless, the poly(alkyl vinyl ether) vulcanizates exhibited good mechanical properties as elastomeric polymers 12…”