Isocyanate Reactions with Difunctional Polyisobutylenes

Abstract

The reactions of isocyanates with carboxy terminated polyisobutylenes, CTPIB, and with hydroxy terminated polyisobutylenes, HTPIB, have been studied in detail. In the case of HTPIB specific emphasis has been given to an hydroxy-ester functionality prepared by the base catalyzed reaction of CTPIB with propylene oxide. Isocyanate reactions with polymeric carboxyl groups were studied to observe if conditions could be established to remove quickly the undesirable carbon dioxide by-product. A potential advantage of this reaction would be the formation of a more stable amide link compared with that of a urethane linkage. In capping reactions with CTPIB and diisocyanates (where NCO group concentrations are in excess), the course of the reaction essentially follows second order kinetics with respect to carboxyl utilization. Bulk reactions, run under vacuum, facilitated the removal of CO2 and markedly increased the rate of reaction. Even so, the reaction required relatively high concentrations of tertiary amine catalysts suggesting a dual role for the base. Aromatic diisocyanates with chlorine substitution were several fold more reactive with CTPIB than was toluene diisocyanate, and gave indications of a better selectivity. Sulfonyl isocyanates possess still greater reactivity. The selectivity of the isocyanate reaction with polymeric COOH is poor when using common diisocyanates such as TDI. The predominant extension of prepolymers is far less probably than in the case of hydroxyl based systems. However, tough, dense, and flexible networks can be formed from initial products of 2000 number average molecular weight. The reactivity of the secondary hydroxyl ester terminal functionality of polyisobutylene, 2° HTPIB, with diisocyanates was comparable to that of commercial polyether or polyester diols which are largely primary hydroxyl. This comparable activity is explained by the fact that in bulk reactions the hydrocarbon backbone of 2° HTPIB provides a reaction medium with a lower dielectric constant and thus a more advantageous environment. In capping reactions followed by IR monitoring of OH consumption, reaction rates also followed second order kinetics with respect to OH consumption when the NCO concentration was in excess. In contrast to isocyanate-polymeric COOH systems, the reaction with HTPIB required no catalysts for extensive consumption of OH groups at moderate temperatures. The HTPIB-toluene diisocyanate reaction was far more selective, and this resulted in a greater potential for extension with the prepolymer. The physical properties of extended and crosslinked networks reflected this selectivity. For a given molecular weight level, networks with HTPIB-diisocyanate prepolymers were more extensible and had higher strengths than did CTPIB based counter parts. Fractionation of original starting materials into narrower molecular weight ranges with slightly improved degrees of functionality improved tensile strengths and extensibilities of subsequent HTPIB based networks. Interesting blocked polymer networks were formed with HTPIB and polyether diols (for example polytetramethyleneglycol). These two liquids which were immiscible, in the molecular weight range of Mn−2000, formed transparent elastic networks of high strength after mutual capping with TDI and subsequent extension and crosslinking by a combination of aromatic diamines and low molecular weight aliphatic diols.

Polyisobutylene‐based polyurethanes with unprecedented properties and how they came about

“…Among early developments, the contribution by Zapp et al must also be mentioned 12. These authors prepared polyisobutylene‐based polyurethanes by the use of sec‐ OH‐telechelic polyisobutylenes, HOCH(CH 3 )CH 2 ‐PIB‐CH 2 CH(CH 3 )OH, in combination with a conventional diisocyanate (toluyl diisocyanate).…”

Hydroxy-telechelic poly(ethylene-co-isobutylene) as a soft segment for thermoplastic polyurethanes

“…1 PIB-based thermoplastic polyurethane (PU) elastomers represent a particularly interesting class of biomaterials and have attracted much attention. 5 Kennedy et al reported the synthesis of PIB-based PUs by the use of well-defined hydroxy-telechelic PIB (HO-PIB-OH), diisocyanates and chain extenders; 6 those materials exhibited excellent chemical and thermal stability. 4 As early as in 1970, Zapp et al prepared PIB-based PUs utilizing sec-hydroxy-telechelic PIB.…”

Isocyanates, Organic

“…The anhydrides subsequently evolve carbon dioxide to yield amines at elevated temperatures (70)(71)(72). The aromatic amines are further converted into amides by reaction with excess anhydride.…”