Aryl ether ketone oligomers

Macrocyclic aryl ether ketone oligomers containing the 1,2-dibenzoyl-... 

Hedrick et al. reported imide aryl ether ketone segmented block copolymers.228 The block copolymers were prepared via a two-step process. Both a bisphenol-A-based amorphous block and a semicrystalline block were prepared from a soluble and amorphous ketimine precursor. The blocks of poly(arylene ether ether ketone) oligomers with Mn range of 6000-12,000 g/mol were coreacted with 4,4,-oxydianiline (ODA) and pyromellitic dianhydride (PMDA) diethyl ester diacyl chloride in NMP in the presence of A - me thy 1 morphi 1 i nc. Clear films with high moduli by solution casting and followed by curing were obtained. Multiphase morphologies were observed in both cases. 

Table 2 contains the characteristics of the amic ester-aryl ether copolymers including coblock type, composition, and intrinsic viscosity. Three series of copolymers were prepared in which the aryl ether phenylquinoxaline [44], aryl ether benzoxazole [47], or aryl ether ether ketone oligomers [57-59] were co-re-acted with various compositions of ODA and PMDA diethyl ester diacyl chloride samples (2a-k). The aryl ether compositions varied from approximately 20 to 50 wt% (denoted 2a-d) so as to vary the structure of the microphase-separated morphology of the copolymer. The composition of aryl ether coblock in the copolymers, as determined by NMR, was similar to that calculated from the charge of the aryl ether coblock (Table 2). The viscosity measurements, also shown in Table 2, were high and comparable to that of a high molecular weight poly(amic ethyl ester) homopolymer. In some cases, a chloroform solvent rinse was required to remove aryl ether homopolymer contamination. It should also be pointed out that both the powder and solution forms of the poly(amic ethyl ester) copolymers are stable and do not undergo transamidization reactions or viscosity loss with time, unlike their poly(amic acid) analogs.

Macrocyclic aromatic carbonates, arylates, etherimides, ether-ketones and ethersulfones have all been prepared in yields of 50-90%. For example, macrocyclic aromatic carbonate oligomers of a variety of bisphenols have been prepared in 70-90% yields by a kinetically... 

As seen in the preparation of cyclic arylate oligomers, the spirobiindane moiety conveys a propensity to form cyclics. Celia, Fukuyama, et al have prepared a number of aromatic ether and thioether imides, sulfones, and ketones in cases where the spirobiindane has been built into the structure of one of the monomers.22 Using bisphenol 1 as a synthetic precursor to dianhydride 2 or diamine 3 has enabled the preparation of a variety of ether polyimide structures via subsequent reaction with various amines or dianhydrides (Table 6). 

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