Acetylenic chain extenders

Polymerization by Gycloaddition. Bisimides and oligoimides capped with reactive unsaturations such as maleimide, acetylene, and xylylene groups, can be chain-extended by a cycloaddition reaction with proper bisdienes. 

About 1970, research was initiated under Air Force funding on acetylene-terminated imide oligomers (ATI) which could be thermally chain extended through the acetylenic end-groups (33, 34). This effort resulted in the development of HR-600 (Eq. 9) and subsequent commercialization by Gulf Oil Chemicals Company in the form of Ther-mid -600. Neat resin properties of HR-600 are presented in Table IV while preliminary composite properties are given in Table V. 

We at NASA reopened the question of learning to chain extend these fluoroether systems In consort with scientists at PCR Inc. The objective was to prepare long-chain difunctional polyperfluoroethers and investigate chain extension mechanisms, as well as to convert these materials to stable cross-linked polymers for sealant applications. The nitrile, acetylene, and isocyanate groups were considered. Each of these is capable of both trimerization reactions and dipolar cycloadditions. From this base line, one could then evoke both chain extension and cross-linking with a variety of reaction schemes. 

A method for preparing alkenyl triflates from lactones and one for preparing a,P-unsaturated aldonic acids by chain extending D-glyceraldehyde derivatives are covered in Chapter 16, and the preparation of sugar vinyltin derivatives from sugar acetylenes is mentioned in Chapter 17. 

In this contribution, in order to illustrate tlie importance of shake-up bands for extended systems, we simulate and compare on correlated grounds the ionization spectra of polyethylene and poly acetylene, the most simplest systems one can consider to represent insulating or semi-conducting polymers. Conclusions for the infinite stereoregular chains are drawn by exU apolation of the trends observed with the first terms of the related n-alkane or acene series, CnH2n+2 and CnHn+2. respectively, with n=2, 4, 6 and 8. Our simulations are also compared to X-ray photoionization spectra (7) recorded on gas phase samples of ethylene, butadiene and hexatriene, which provide a clear experimental manisfestation of the construction of correlation bands (8-12). 

The electronic properties of germanium have led to an interest in incorporating the element into extended polymeric chains due to the intrinsic properties of the polymers themselves or in their use as precursors for material synth-esis. Catalytic co-polymerization of the germylene Ge[N(SiMe3)2]2 with various substituted acetylenes leads to... 

The reaction sequence in steps two and three is known as the Corey-Fuchs method to create an alkyne from an aldehyde 10 Reaction of triphenylphosphane with carbontetrabromide gives phenylphosphane-dibromomethylene. This reagent then transforms aldehyde 19 into the corresponding dibromoalkene 20 thereby extending the chain by one carbon. Reaction of the bromo compound with two equivalents of n-butyllithium in THF at -78 °C results in the rapid formation of the acetylenic lithio derivative which forms the terminal acetylene 21 upon aqueous work-up. 

The helical conformation of polyacetylene derivatives bearing chiral side chains was first pointed out by Ciardelli in 197 4 24 and later extended and more clearly demonstrated by Grubbs in 199 1 25 and by Yashima and Okamoto in 1994.26a For poly(phenyl-acetylene) derivatives bearing no chiral side groups, Yashima and Okamoto showed that a helical conformation can be induced by interaction with added chiral small molecules.260 Apart from optical activity, a helical conformation of cis-cisoidal poly(phenyl-acetylene) in the solid state was pointed out by Simionescu and Percec.27... 

This synthesis has been adapted to make the natural (5 -isomer of 114, reducing the initially formed aldehyde to (S)-114 with baker s yeast. [This same synthesis has been adapted to make (S)-callosobruchic acid (115), see below]. Julia s synthesis of a-geraniol (73) was also extended to make 114 by hydro-boration. Hydroboration of 73 with diisopinocampheylborane (made from (- )-a-pinene [(-)-116]) gave only a small ee however. A synthesis of ( )-114 started with the reaction of 2-methylpropiolactone and the ethylene acetal of 3-oxobutylmagnesium bromide. The methyl ester of the acid 117 thus prepared was chain-lengthened by reaction with acetylene and rearrangement with a vanadium catalyst of the ynol thereby obtained. The aldehyde 118 was then reduced with lithium aluminum hydride to 114. ... 

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