Imide oligomer, ethynyl

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 ethynyl terminated imide oligomers are very attractive because their cured polymers are thermally stable (131). However, improvements are required in processability. An interesting approach to this problem was the synthesis and use of ethynyl-terminated isoimide (132). If the cyclodehydration of the amide acid intermediate is performed chemically with dicyclohexylcarbodiimide, isoimide is formed in almost quantitative yield. (Fig. 46). It is claimed that the isoimide provides better flow and solubility compared with the corresponding imide. At elevated temperatures, during cure, the isoimide rearranges into the... 

Hanky and St. Clair evaluated [81] a series of imide oligomers end-capped with ethynyl groups. Polyamic acid 50 and polyimide 51 in Fig. 27 were prepared from BTDA 70, 3,3 -sulphonylbisbenzeneamine 49 and 3-ethynylbenzeneamine 45 with a degree of polycondensation n varying between 1 and 3. 

Thermid 600 Ethynyl-terminated imide oligomers 48 (Fig. 19) Solid powder... 

Two types of reactive groups, ethynyl and nor-bomene (Nadic), have been placed on the ends of imide oligomers in an attempt to develop more processable high temperature PI adhesives. The thermal reaction of the ethynyl groups occurs without the evolution of volatiles, whereas the thermal reaction of the nor-bomene group may involve the release of a small amount of cyclopentadiene from the reverse Diels-Alder reaction (depending on con-... 

The ethynyl terminated imide oligomer work was initially reported in 1974. Neat resin and composite " properties for cured acetylene terminated imide oligomers have been reported. These materials were initially designated HR-600 and later Thermid -600 (60). The ethynyl terminated imide oligomer in structure 8 is representative of this class... 

Cured ethynyl-terminated ester oligomers prepared from the reaction of hydroxy-termi nated ester oligomers with 4-ethynyl benzoyl chloride exhibited higher Tgs and better solvent resistance than comparable unendcapped polymers (50). Biphenylene end-caps have been placed on imide (40, 51), quinoline (52, 53) and quinoxaline (53) oligomers. High temperatures (> 316°C"J are required to cure... 

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. 

The ethynyl monomer is reacted with an oligomeric imide terminated in anhydride groups to yield the ethynyl terminated oligomers as it is shown in Scheme (68). 

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