Thermosetting monomers and compositions containing phosphorus and cyanato groups

1. A thermosetting monomer comprising at least two of an aryl-cyanato group and at least two of a phosphorus group, where the thermosetting monomer is represented by a compound of Formula (I):

wherein m is an integer from 1 to 20;

wherein n is an integer from 0 to 20 with the proviso that when n is 0 then m is an integer from 2 to 20;

wherein X is selected from the group consisting of sulfur, oxygen, and a lone electron pair;

wherein each R 1 and R 2 is independently a hydrogen, an aliphatic moiety having 1 to 20 carbon atoms, or aromatic hydrocarbon moiety having 6 to 20 carbon atoms, where the aliphatic moiety and the aromatic hydrocarbon moiety can be joined to form a cyclic structure;

wherein R 3 is selected from the group consisting of a hydrogen, an aliphatic moiety having 1 to 20 carbon atoms, an aromatic hydrocarbon moiety having 6 to 20 carbon atoms, R 4 R 5 P(═X)CH 2 —, and ROCH 2 —, where R is an aliphatic moiety having 1 to 20 carbon atoms; and

wherein each R 4 and R 5 is inde endentl an aliphatic moiety havin 1 to 20 carbon atoms, an aromatic hydrocarbon moiety having 6 to 20 carbon atoms, where the aliphatic moiety and the aromatic hydrocarbon moiety can be joined to form a cyclic structure, RX—, or wherein R 4 and R 5 together are Ar 2 X—; and

wherein each Ar 1 and Ar 2 is independently a benzene, a naphthalene, or a biphenyl.

2. The thermosetting monomer of claim 1 , wherein for the compound of Formula (I) X is oxygen, n is 1, m is 1, each R 1 and R 2 is a methyl group, R 3 is R 4 R 5 P(═X)CH 2 —, and R 4 and R 5 together are Ar 2 X, wherein Ar 2 is biphenyl such that R 4 R 5 P(═X)— is represented by a compound of Formula (II):

3. The thermosetting monomer of claim 1 , wherein for the compound of Formula (I) X is oxygen, n is 0, m is 2 or 3, R 3 is R 4 R 5 P(═X)CH 2 —, and R 4 and R 5 together are Ar 2 X, wherein Ar 2 is biphenyl such that R 4 R 5 P(═X)— is represented by a compound of Formula (II):

4. The thermosetting monomer of claim 1 , where Ar 1 is benzene.

5. A composition, comprising:

a formulation component selected from the group consisting of an epoxy resin, bismaleimide-triazine resin, a maleimide resin, a cyanate ester resin and combinations thereof; and

a thermosetting monomer comprising at least two of an aryl-cyanato group and at least two of a phosphorus group, where the thermosetting monomer is represented by a compound of Formula (I):

wherein m is an integer from 1 to 20;

wherein n is an integer from 0 to 20 with the proviso that when n is 0 then m is an integer from 2 to 20;

wherein X is selected from the group consisting of sulfur, oxygen, and a lone electron pair;

wherein each R 1 and R 2 is independently a hydrogen, an aliphatic moiety having 1 to 20 carbon atoms, or aromatic hydrocarbon moiety having 6 to 20 carbon atoms, where the aliphatic moiety and the aromatic hydrocarbon moiety can be joined to form a cyclic structure;

wherein R 3 is selected from the group consisting of a hydrogen, an aliphatic moiety having 1 to 20 carbon atoms, an aromatic hydrocarbon moiety having 6 to 20 carbon atoms, R 4 R 5 P(═X)CH 2 —, and ROCH 2 —, where R is an aliphatic moiety having 1 to 20 carbon atoms; and

wherein each R 4 and R 5 is independently an aliphatic moiety having 1 to 20 carbon atoms, an aromatic hydrocarbon moiety having 6 to 20 carbon atoms, where the aliphatic moiety and the aromatic hydrocarbon moiety can be joined to form a cyclic structure, RX—, or wherein R 4 and R 5 together are Ar 2 X—; and

wherein each Ar 1 and Ar 2 is independently a benzene, a naphthalene, or a biphenyl.

6. The composition of claim 5 , where the maleimide resin is bismaleimide of 4,4′-diaminodiphenylmethane.

7. The composition of claim 5 , where the composition has a phosphorus content of 0.1 to 3.5 weight percent.

8. The composition of claim 5 , where the composition has an onset to cure temperature of 180.2° C. and a cure enthalpy of 232.1 joules per gram of the composition.

9. The composition of claim 8 , where the composition is fully cured after a single exotherm at 237.4° C.

10. A process for making a thermosetting monomer, comprising:

condensing an etherified resole with (H—P(═X)R 4 R 5 ) to form a reaction product, wherein each R 4 and R 5 is independently an aliphatic moiety having 1 to 20 carbon atoms, an aromatic hydrocarbon moiety having 6 to 20 carbon atoms, where the aliphatic moiety and the aromatic hydrocarbon moiety can be joined to form a cyclic structure, RX—, or wherein R 4 and R 5 together are Ar 2 X—; wherein X is sulfur, oxygen, or a lone electron pair; and wherein Ar 2 is benzene, naphthalene, or biphenyl; and

converting the reaction product to the thermosetting monomer with a cyanogen halide and a base, where the thermosetting monomer is represented by a compound of Formula (I):

wherein m is an integer from 1 to 20;

wherein n is an integer from 0 to 20 with the proviso that when n is 0 then m is an integer from 2 to 20;

wherein X is selected from the group consisting of sulfur, oxygen, and a lone electron pair;

wherein each R 1 and R 2 is independently a hydrogen, an aliphatic moiety having 1 to 20 carbon atoms or aromatic hydrocarbon moiety having 6 to 20 carbon atoms, where the aliphatic moiety and the aromatic hydrocarbon moiety can be joined to form a cyclic structure;

wherein R 3 is selected from the group consisting of a hydrogen, an aliphatic moiety having 1 to 20 carbon atoms, an aromatic hydrocarbon moiety having 6 to 20 carbon atoms, R 4 R 5 P(═X)CH 2 —, and ROCH 2 —, where R is an aliphatic moiety having 1 to 20 carbon atoms; and

wherein each R 4 and R 5 is independently an alphatic moirty having 1 to 20 carbon atoms, an aromatic hydrocarbon moiety having 6 to 20 carbon atoms, where the aliphatic moiety and the aromatic hydrocarbon moiety can be joined to form a cyclic structure, RX—, or wherein R 4 and R 5 together are Ar 2 X—; and

wherein each Ar 1 and Ar 2 is independently a benezene, a naphthalene, or a biphenyl.

11. The process of claim 10 , wherein R 4 and R 5 together are Ar 2 X—, X is oxygen and Ar 2 is biphenyl to give 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide.

12. The process of claim 10 , wherein the etherified resole is a butyl ether bisphenol-A resole, the cyanogen halide is cyanogen bromide, and the base is triethylamine.