Bisphthalonitrile

Bisphthalonitrile monomers were cured neat, with nucleophilic and redox co-reactants, or in combination with a reactive diluent. Dynamic mechanical measurements on the resulting polymers from -150 to +300°C turn up several differences attributable to differences in network structure. Rheovibron results were supplemented with solvent extraction, differential scanning calorimetry (DSC), vapor pressure osmometry, and infrared spectroscopy to characterize the state of cure. 

Ether-linked bisphthalonitriles were synthesized by Mr. T. R. Price of the Naval Research Lab. A number of monomers containing various aliphatic and aromatic "linking groups" between the phthalonitrile functions are available three representative aromatic monomers were selected for this study... 

A number of reactions have been proposed to explain the viscosity increase and gelation which occur when bisphthalonitriles are heated. Possible products include phthalocyanine, triazine rings, and isoindoline chains (7), depending on the reaction conditions and co-reactants used. 

Figure 5. Hypothesized network structure in amine-cured bisphthalonitrile polymers.

Moreover, vinyl-bridged Pc adducts with ferrocene derivatives have been described [78,79], Upon reaction of 3,4-dicyanobenzylphosphonate with formylfer-rocene under Wittig-Horner conditions with the corresponding ferrocene-containing mono- or bisphthalonitriles have been obtained, which were then subjected to statistical cyclotetramerization with 4-tert-butylphthalonitrile in the presence of the appropriate metal salt. Furthermore, a double bond has also been employed as spacer between the Pc and ruthenium(trisbipyridine) [47],... 

The key starting compound is the mono nitro derivative of calix[4]arene 4, which was obtained via a single-step reaction with 10 equivalents of 63% HNO3 in a mixture of dichloromethane and glacial acetic acid in less than 5 min in 94% yield according to the literature method. Compound 4 converted to bisphthalonitrile derivative 5 by the given method in 59% yield. Ball-type ZnPc 6 was prepared from 5 and zinc acetate in 1-pentanol in the presence of DBU. Hexanuclear ball-type ZnPc 8 was obtained by the reaction of 6 with 7 in a mixture of NaOH, MeOH, THF, and activated zinc powder with a yield of 55%. 

Isopropylidendioxydiphenyl was used as a bridged compound in order to obtain ball-type Pc. Mixing the bisphthalonitril derivative 44 with zinc or cobalt salt in the solid phase and heating the mixtures in a sealed tube at 250° C for 10 min gave the Pcs 45 and 46 with the yields of 9.39 and 8.27%, respectively, Fig. 12 [49],... 

Not all reactions in the solid phase convert bisphthalonitrile derivatives into ball-type Pcs. One example of such reactions is the conversion of the bisphthalonitrile derivative of phenolphthalein into ball-type Pc [50], As can be seen in Fig. 13, when a solid mixture of bisphthalonitrile 48 and metal salt was heated in a sealed tube at 320° C for 5 min, only mono Pcs 49 and 50 were formed. Further reaction of 49 or 50 with an excess of the corresponding metal salt in a refluxing solvent for 24 h resulted in the formation of ball-type Pcs 51 or 52. 

Sumner, M. J., Sankarapandian, M., McGrath, J. E., Riffle, J. S., and Sorathia, U. Flame retardant novolac-bisphthalonitrile structural thermosets, Polymer 2002, 43, 5069. 

Polymerization of Bisphthalonitriles Metal Free Phthalocyanine Formation... 

Low molecular weight phthalocyanines are prepared by cyclotetramerization of unsubstituted or substituted phthalic acid derivatives such as phthalonitrile in the presence of suitable metals. If bifunetional tetracarbonitriles are employed, polymeric phthalocyanines 56 and 57 are obtained [equations (22) and (23)] 1,2,4,5-tetracyano-benzene, oxyalkyleneoxy-, oxyaryleneoxy- [239-242], tetrathio- or dioxadithia-bridged [243], bisphthalonitriles and tetracarboxylic acid derivatives such as 1,2,4,5-benzenetetra-carboxylic acid dianhydride [244-246]. The reactions of the carbonitriles were carried out in bulk in the presence of a metal at T= 200-400 °C. Dark-blue till black-coloured polymers insoluble in any organic solvent were obtained. Recently the synthesis of the... 

Zou Xingqiang, Xu Mingzhen, Jia Kun, and Liu Xiaobo. Copolymerizing behavior and processability of allyl-functional bisphthalonitrile/bismaleimide system. Polym. Compos. (2015) doi 10.1002/pc. 

Melt polymerizable bisimido-bisphthalonitrile polymer precursors were synthesized by the reaction of 4-aminophthalonitrile (4-APN) with 6FDA. The synthesized monomer showed a melting point at about 270 °C, which upon melt polymerization gave thermally - stable tough polymers. [84]. 6FDA based Pis can be prepared via one-step synthesis using gamma radiation fi om a cobalt-60 source [85]. 

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