Oligomers, acetylene terminated synthesis

The idea of synthesizing imide oligomers which carry acetylenic terminations appeared attractive because homopolymerization through acetylenic endgroups occurs without any volatile evolution and provides materials with good properties. Landis et. al (8,9) published the synthesis of such acetylene terminated imide oligomers from benzophenone tetracarboxylic anhydride, aromatic diamine and 3-ethynylaniline via the classical route. As usual, the amide acid is formed as an intermediate which, after chemical cyclodehydration, provides the polymide. Since ethynyl-terminated polyimide is used as a matrix resin for fiber composites, processing is possible via the amide acid, which is soluble in acetone, or via the fully imidized prepolymer, which is soluble in NMP. The chemical structure of the fully imidized ethynyl-terminated polyimide is provided in Fig. 44. 

The key to acetylene terminated polyimides is the availability of the end-capper which carries the acetylene group. Hergenrother (130) published a series of ATI resins based on 4-ethynylphthalic anhydride as endcapping agent. This approach first requires the synthesis of an amine-terminated amide acid prepolymer, by reacting 1 mole of tetracarboxylic dianhydride with 2 moles of diamine, which subsequently is endcapped with 4-ethynylphthalic anhydride. The imide oligomer is finally obtained via chemical cyclodehydration. The properties of the ATI resin prepared via this route are not too different from those prepared from 3-ethynylaniline as an endcapper. When l,3-bis(3-aminophenox)benzene was used as diamine, the prepolymer is completely soluble in DMAc or NMP at room temperature, whereas 4,4 -methylene dianiline and 4,4 -oxydianiline based ATIs were only partially soluble. The chemical structure of ATIs based on 4-ethynylphthalic anhydride endcapper is shown in Fig. 45. 

The Michael addition reaction of dimercaptodiphenylether with N-(3-ethynyl phenyl) maleimide allowed the synthesis of ethynyl-terminated imido-thioether as shown in Fig. 50 (139). This acetylene terminated imidothioether was blended with acetylene terminated polyarylene ether oligomers of different molecular weights and tested as composite resins (140). Blends of functionalized thermoplastics such as the acetylene terminated polyarylene ethers with brittle high-Tg imide resins are finding increased attention for tough high-Tg composites. 

SYNTHESIS AND PROPERTIES OF ACETYLENE TERMINATED ARYL-ETHER OLIGOMERS... 

A substantial effort in this laboratory has been directed toward the synthesis and characterization of acetylene terminated oligomers for use as addition-curable, moisture-resistant, thermoset systems. Early work on the acetylene-terminated phenylquinoxalines demonstrated the moisture insensitivity of the product generated from the thermal cure. Studies of various difunctional acetylene-terminated monomers has demonstrated that the polymerization is a free radical propogation of the acetylene moiety to a linear conjugated polyene. 

A series of acetylene-terminated, aryl-ether thermoset systems were prepared by an Ullmann ether synthesis involving the condensation of various salts of aromatic bis—diols with m—dibromobenzene. The bromo end-capped oligomers were converted to the acetylene-terminated systems by the catalytically-induced, bromo-displacement reaction with 2-methyl-3-but3m-2-ol, followed by base hydrolysis. 

The initial synthesis of acetylenic terminated phenylquinoxaline oligomers was reported in 1975. An alternate synthesis reported in 1976 involved endcapping o-diamino-termi-nated phenylquinoxaline oligomers with 4-(4-ethynylphenoxy)benzil to yield acetylene-terminated phenylquinoxaline oligomers (ATPQs) as shown in the representative scheme in Eq. (4) ... 

As mentioned in the introduction, the synthesis of telechelics is important to preparative polymer chemistry because of their use as macromonomer precursors (and therefore graft copolymer and network precursors), as precursors to block copolymers, and as the basis of reaction injection molding. Some general reviews on telechelics include those of A they and Heitz. In addition, the synthesis, reactions and properties of acetylene-terminated oligomers were recently reviewed.An extensive discussion of this class of reactive polymers is the subject of a recent book. ... 

The most convenient method of preparing the flexible (low Tg) system is to employ the Ullmann ether reaction of dibromobenzene and aromatic bis-diols followed by catalytic replacement of the bromine atoms by terminal acetylene groups. A host of commercially available bis-diols have been used in the synthesis with both meta and para dibromobenzene. Low Tg arylether oligomers have been prepared containing sulfone, sulfide, carbonyl, isopropyl and perfluoroisopropyl groups in the backbone (9). 

Efficiency of the deprotection and coupling reactions are critical to the success of any iterative solid-phase synthesis. Shown in Scheme 1 is a triad of reactions for phenylacetylene oligomer synthesis trimethylsilyl deprotection,28 29 triazene unmasking of an iodobenzene,30 and the Sonogashira coupling of a terminal acetylene with an aryl iodide.31-33 Representative procedures for each step in this sequence are included at the end of this chapter. 

A comparative study of phenylacetylene oligomer synthesis on a solid support14 with solution-phase approaches has been undertaken.37 Results from syntheses featuring a free and bound terminal acetylene are shown in Scheme 5. (For clarity, substituted arene units are symbolized as a filled circle throughout the rest of this chapter.)... 

In 1868, Berthelot discovered the method of synthesis of benzene by the cyclotrimerization of three molecules of acetylene. Applied to telechelic oligomers terminated by acetylenic groups, this method could provide the most thermally stable networks. This concept was applied in 1974 to synthesize the new thermosetting resins displayed in Fig. 9.19." " " They are prepared by reacting BTDA 18 with 3,3 -(l,3-phenylenedioxy)bisbenzeneamine... 

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