Bis(aniline) compounds containing multiple substituents with carbon-carbon triple-bonded groups
AssigneeThe United States of America as represented by the Secretary of the Air Force
InventorsLoon-Seng Tan, Zhenning Yu
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Abstract
The invention relates to bis(aniline) compounds containing multiple arylethynyl, alkylethynyl, ethynyl groups or their combinations, processes of making such compounds and materials comprising such compounds. Such, bis(aniline) compounds preferably comprise multiple phenylethynyl (PE) groups, i.e. 2-4 PE moieties. Such compounds are useful monomers for the preparation of polyimides, polyamides and poly(amide-imides) whose post-fabrication crosslinking chemistry (i.e. reaction temperature) can be controlled by the number of PE per repeat unit as well as finding utility in thermosetting matrix resins, 3D printable resins, and as high-carbon-content precursors to carbon-carbon composites.
Claims12
A process of making multiple-arylethynylated bis(aniline) compound comprising:
- a) oxidatively halogenating Structure 2 below to form Structure 3 below wherein R1 and R2 are each independently I or Br and X is oxygen or CH2;
- b) optionally, oxidatively iodinating chemical Structure 3 below one or two more times to form at least one of chemical Structures 4 through 5 below wherein R3 and R4 are each I:
- c) substituting the halogens on at least one of said chemical Structures 3 through chemical Structure 5 with a moiety comprising a carbon-carbon triple-bonded group, to form at least one of chemical Structures 6 through 8 below, wherein R5, R6, R7, and R8 are each ethynyl moieties,
- e) reducing the nitro moieties on at least one of said chemical Structures 6 through 8 to form at least one of chemical Structures 9, through chemical Structure 11 below:
- wherein R9, R10, R11, and R12 are moieties containing carbon-carbon triple bonded groups.
A process of making multiple-arylethynylated bis(aniline) compound comprising:
- a) oxidatively halogenating Structure 2 below to form Structure 3 below wherein R1 and R2 are each I and X is oxygen or CH2;
- b) optionally, oxidatively iodinating chemical Structure 3 below one or two more times to form at least one of chemical Structures 4 through 5 below wherein R3 and R4 are each I:
- c) substituting the halogens on at least one of said chemical Structures 3 through chemical Structure 5 with a moiety comprising acetylene or mono-substituted acetylene, to form at least one of chemical Structures 6 through 8 below, wherein each R5, R6, R7, and R8 is an arylethynyl moiety,
- e) reducing the nitro moeities on at least one of said chemical Structures 6 through 8 to form at least one of chemical Structures 9, through chemical Structure 11 below:
- wherein R9, R10, R11, and R12 are each an arylethynyl moiety.
The process of 9 wherein said oxidizing agent is selected from the group consisting of the sodium or potassium salt of bromate, iodate, perbromate or periodate and said reducing agent is selected from the group consisting sodium iodide, potassium iodide and mixtures thereof.
Dependencies are inferred from the claim text.