The United States of America As Represented by the Administrator of the

The United States of America As Represented by the United States

The United States of America As Represented by the Administrator

John A Mikroyannidis

Demetrius A Kourtides

James M Beggs

1-[(Diorganooxyphosphonyl)methyl]-2,4- and -2,6-dinitro- and diamino benzenes are prepared by nitrating an (organophosphonyl)methyl benzene to produce the dinitro compounds which are then reduced to the diamino compounds. The organo groups (alkyl, haloalkyl, aryl) on the phosphorus may be removed to give the free acids, (HO).sub.2 P(.dbd.O)--. The diamino compounds may be polymerized with dianhydrides or diacyl halides to produce fire and flame resistant polymers which are useful in the manufacture of aircraft structures.

1-[(Diorganooxyphosphonyl)methyl]-2,4- and -2,6-dinitro-benzenes

1-[(Diorganooxyphosphonyl)-methyl]-2,4- and -2,6-diamido benzenes

The subject invention pertains to a novel class of fire- and heat-resistant bisimide resins prepared by thermal polymerization of maleimido or citraconimido substituded 1-[(dialkoxyphosphonyl)-methyl]-2-4 and -2,6-diaminobenzenes. Typical polymer presursors have the chemical structure: ##STR1## wherein R is alkyl, substituted alkyl or aryl, and R.sup.1 is hydrogen or lower alkyl. The polymer precursors are prepared by reacting 1-[(diorganooxyphosphonyl)methyl]-2-4 and -2,6-diaminobenzenes with maleic anhydride or citraconic anhydride in a mole ratio 1:2. Chains extension of the monomers is achieved by reacting the mono-N-maleimido derivatives of 1-[(diorganooxyphosphonyl)methyl]-2,4 and -2,6-diaminobenzenes with aryl tetracarboxylic dianhydrides, such as benzophenone tetracarboxylic diandydride, or aryl diisocyanates, such as methylenebis(4-phenylisocyanate), in a mole ratio 2:1. The polymerization of the monomers is studied by differential scanning calorimetry (DSC) and the thermal stability of the polymers is ascertained by thermogravimetric analysis (TGA).

Fire and heat resistant laminating resin based on maleimido and

1-[(Diorganooxyphosphonyl)methyl]-2,4- and -2,6-dinitro- and diamino benzenes are prepared by nitrating an (organophosphonyl)methyl benzene to produce The dinitro compounds which are then reduced to the diamino compounds. The organo groups (alkyl, haloalkyl, aryl) on the phosphorus may be removed to give the free acids, (HO).sub.2 P(.dbd.O)--. The diamino compounds may be polymerized with dianhydrides or diacyl halides to produce fire and flame resistant polymers which are useful in the manufacture of aircraft structures.

1-[(diorganooxyphosphonyl)methyl]-2,4,- and -2,6-diamino benzines and

The subject invention pertains to a novel class of fire- and heat-resistant bisimide resins prepared by thermal polymerization of maleimido or citraconimido substituted 1-[(dialkoxyphosphonyl)methyl]-2-4 and -2,6-diaminobenzenes. Typical polymer precursors have the chemical structure: ##STR1## wherein R is alkyl, substituted alkyl or aryl, and R.sup.1 is hydrogen or lower alkyl. The polymer precursors are prepared by reacting 1-[(diorganooxyphosphony)methyl]-2-4- and -2,6-diaminobenzenes with maleic anhydride or citraconic anhydride in a mole ratio 1:2. Chain extension of the monomers is achieved by reacting the mono-N-maleimido derivatives of 1-[(diorganooxyphosphonyl)methyl]-2,4 and -2,6-diaminobenzenes with aryl tetracarboxylic dianhydrides, such as benzophenone tetracarboxylic dianhydride, or aryl diisocyanates, such as methylenebis(4-phenylisocyanate), in a mole ratio 2:1. The polymerization of the monomers is studied by differential scanning calorimetry (DSC) and the thermal stability of the polymers is ascertained by thermogravimetric analysis (TGA).

Fire and heat resistant laminating resins based on maleimido and

The subject invention pertains to a novel class of fire- and heat-resistant bisimide resins prepared by thermal polymerization of maleimido or citraconimido substituted 1-[(dialkoxyphosphonyl)methyl]-2-4 and -2,6-diaminobenzenes. Typical polymer precursors have the chemical structure: ##STR1## wherein R is alkyl, substituted alkyl or aryl, and R.sup.1 is hydrogen or lower alkyl. The polymer precursors are prepared by reacting 1-[(diorganooxyphosphonyl)methyl]-2-4- and -2,6-diaminobenzenes with maleic anhydride or citraconic anhydride in a mole ratio 1:2. Chain extension of the monomers is achieved by reacting the mono-N-maleimido derivatives of 1-[(diorganooxyphosphonyl)methyl]-2,4 and -2,6-diaminobenzenes with aryl tetracarboxylic dianhydrides, such as benzophenone tetracarboxylic dianhydride, or aryl diisocyanates, such as methylenebis(4-phenylisocyanate), in a mole ratio 2:1. The polymerization of the monomers is studied by differential scanning calorimetry (DSC) and the thermal stability of the polymers is ascertained by thermogravimetric analysis (TGA).

1-[(Diorganooxyphosphonyl)methyl]2,4- and -2,6-diamino benzenes are reacted with polyacylhalides and optionally comonomers to produce polyamides which have desirable heat and fire resistance properties. These polymers are used to form fibers and fabrics where fire and flame resistance properties are important, e.g., aircraft equipment and structures.

Fire resistant polyamide based on 1-[(diorganooxyphosphonyl)methyl]-2,4-

Compounds having the general formula 1 ##STR1## wherein X and Y are functional groups, preferably amino groups, are polymerized with, for example, polyfunctional epoxides to provide heat and fire resistant polymers useful for making flame and fire resistant polymer structures such as for aircraft secondary structures. The groups R in 1 are preferably alkyl and lower halo (e.g., chloro) alkyl.

Polymer of phosphonylmethyl-2,4-and -2,6-diamino benzene and

Phosphorus-containing polyimides and copolyimides are synthesized in a two-step polycondensation reaction from 1-[(diorganooxyphosphonyl)methyl]-2,4- and -2,6-diaminobenzenes and tetracarboxylic anhydride. The diorgano position of the diorganooxyphosphonyl group includes alkyl, such as ethyl, substituted alkyl, such as 2-chloroethyl, and aryl such as phenyl. The tetracarboxylic anhydrides include compounds such as pyromellitic dianhydride and benzophenone tetracarboxylic dianhydride. The glass transition temperature (Tg) of the polyimides is reduced by incorporation of the (dialkoxyphosphonyl)methyl groups. Both the molecular weight and the thermal stability of the polymers are reduced with increasing concentration of the phosphorus moieties. The phosphorus-containing copolyimides show a considerably higher degree of fire-resistance as compared to that of the corresponding common polyimides, and can be used in matrix composites in very thermally stable high temperature graphite composites for aircraft applications.

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Patras, Greece

John A Mikroyannidis