Controlling crosslinking density and processing parameters of phthalonitriles

Abstract

Disclosed is a composition having: a diphthalonitrile compound having at least two phthalonitrile groups; a reactive plasticizer; and an amine curing agent. Also disclosed is a composition having: a diphthalonitrile compound having at least two phthalonitrile groups; a nonreactive plasticizer; and an amine curing agent. Also disclosed is a method of: providing a composition having a phthalonitrile compound; heating the composition to a processing temperature until the composition has a viscosity of 30-40 Pa.Math.s at the processing temperature to form a partially cured composition; placing the partially cured composition into a material chamber of an extrusion machine; heating the partially cured composition and the material chamber to within 10 C. of the processing temperature; and extruding fiber from the extrusion machine.

Claims

1. A method comprising: providing a composition comprising a phthalonitrile compound; heating the composition to a processing temperature that causes the composition to have a viscosity of 30-40 Pa.Math.s at the processing temperature to form a partially cured composition; placing the partially cured composition into a material chamber of an extrusion machine; heating the partially cured composition and the material chamber to within 10 C. of the processing temperature; and extruding fiber from the extrusion machine.

2. The method of claim 1, wherein the processing temperature is from 220 to 250 C.

3. The method of claim 1, wherein the composition comprises: a diphthalonitrile compound having at least two phthalonitrile groups; a reactive plasticizer; and an amine curing agent.

4. The method of claim 3, wherein the composition further comprises: a nonreactive plasticizer.

5. The method of claim 1, wherein the composition comprises: a diphthalonitrile compound having at least two phthalonitrile groups; a nonreactive plasticizer; and an amine curing agent.

6. The fiber made by the method of claim 1.

Description

EXAMPLE 1

(1) General Synthetic Procedure of Oligomeric Phthalonitrile Based on Bisphenol A and 4,4-Dichlorobenzophenone in One Reaction Pot

(2) To a 250 mL, three-necked flask fitted with a thermometer, a Dean-Stark trap with condenser, and a nitrogen inlet were added bisphenol A, 4,4-dichlorobenzophenone, powdered anhydrous K.sub.2CO.sub.3 (2.2 eq based on bisphenol A), toluene, and dimethylsulfoxide (DMSO). Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content. The resulting mixture was degas sed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene. The mixture was refluxed at 165-175 C. under a nitrogen atmosphere for 6-18 hr or until no more water was observed being collected in the Dean-Stark trap. The toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate. The mixture was cooled to 50 C. At this time, 4-nitrophthalonitrile was added in one portion and the reaction mixture was heated at 80 C. for 6-8 hr. The mixture was allowed to cool to ambient temperature and poured into a 5% aqueous HCl solution resulting in the formation of a solid. The material was broken up and collected using a Bchner funnel. The white solid was washed with 200 mL portions of distilled water until neutral. The isolated solid was vacuum dried to yield the oligomeric phthalonitrile. The length and molecular weight of the PN is designated by the ratio of bisphenol A to 4,4-dichlorobenzophenone, e.g. 2:1 oligomeric phthalonitrile means 2 moles bisphenol A to 1 mole 4,4-dichlorobenzophenone.

EXAMPLE 2

(3) Formulation of 2:1 Oligomeric Phthalonitrile Based on Bisphenol A and 4,4-Dichlorobenzophenone with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile, 30 Mol %), Ferro Phosphate Plasticizer (10 wt %), and m-BAPS (5 Mol %) Heat Treated at 225 C.

(4) The 2:1 oligomeric phthalonitrile from Example 1 (5.0 g), 4-dodecyl phthalonitrile (0.127 g, 30 mol %), Ferro phosphate plasticizer (0.537 g, 10 wt %) and m-BAPS (0.256 g, 5 mol %) were stirred at 200 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 225 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 30 Pa.Math.s.

EXAMPLE 3

(5) Formulation of 2:1 Oligomeric Phthalonitrile Based on Bisphenol A and 4,4-Dichlorobenzophenone with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile, 30 Mol %) and m-BAPS (5 Mol %) Heat Treated at 225 C.

(6) The 2:1 oligomeric phthalonitrile from Example 1 (5.0 g), 4-dodecyl phthalonitrile (0.127 g, 30 mol %), and m-BAPS (0.256 g, 5 mol %) were stirred at 200 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 225 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 30 Pa.Math.s.

EXAMPLE 4

(7) Formulation of 5:4 Oligomeric Phthalonitrile Based on Bisphenol A and 4,4-Dichlorobenzophenone with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile, 30 Mol %), Ferro Phosphate Plasticizer (10 wt %), and p-BAPS (15 Mol %) Heat Treated at 200 C.

(8) The 5:4 oligomeric phthalonitrile prepared by the procedure of Example 1 (6.0 g), 4-dodecyl phthalonitrile (0.324 g, 30 mol %), Ferro phosphate plasticizer (0.600 g, 10 wt %), and p-BAPS (0.181 g, 15 mol %) were stirred at 225 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 200 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. of between 10 and 30 Pa.Math.s.

EXAMPLE 5

(9) Polymerization of Formulation of 5:4 Oligomeric Phthalonitrile Based on Bisphenol a and 4,4-Dichlorobenzophenone with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile, 30 Mol %), Ferro Phosphate Plasticizer (10 wt %), and p-BAPS (15 Mol %) Heat Treated to 375 C.

(10) The formulation (1.5 g) prepared by the procedure of Example 4 was placed in an Al planchet and cured to a solid thermoset by heating at 250 C. for 1 hr, at 300 C. for 2 hr, and at 375 C. for 2 hr. Gelation occurred to a solid thermoset during the 250 C. thermal treatment.

EXAMPLE 6

(11) Formulation of 8:7 Oligomeric Phthalonitrile Based on Bisphenol A and 4,4-Dichlorobenzophenone with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile; 30 Mol %), Ferro Phosphate Plasticizer (10 wt %), and p-BAPS (25 Mol %) Heat Treated at 200 C.

(12) The 8:7 oligomeric phthalonitrile prepared by the procedure of Example 1 (8.0 g), 4-dodecyl phthalonitrile (0.278 g, 30 mol %), Ferro phosphate plasticizer (0.800 g, 10 wt %), and p-BAPS (0.258 g, 25 mol %) were stirred at 225 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 200 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 30 Pa.Math.s.

EXAMPLE 7

(13) Formulation of 8:7 Oligomeric Phthalonitrile Based on Bisphenol A and 4,4-Dichlorobenzophenone with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile; 30 Mol %), Ferro Phosphate Plasticizer (10 wt %), and p-BAPS (30 Mol %) Heat Treated at 200 C.

(14) The 8:7 oligomeric phthalonitrile prepared by the procedure of Example 1 (10.6 g), 4-dodecyl phthalonitrile (0.376 g, 30 mol %), Ferro phosphate plasticizer (1.06 g, 10 wt %), and p-BAPS (0.410 g, 30 mol %) were stirred at 225 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 225 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. of between 10 and 30 Pa.Math.s.

EXAMPLE 8

(15) Formulation of 8:7 Oligomeric Phthalonitrile Based on Bisphenol A and 4,4-Dichlorobenzophenone with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile; 30 Mol %), Ferro Phosphate Plasticizer (10 wt %), and p-BAPS (15 Mol %) Heat Treated at 200 C.

(16) The 8:7 oligomeric phthalonitrile prepared by the procedure of Example 1 (8.0 g), 4-dodecyl phthalonitrile (0.278 g, 30 mol %), Ferro phosphate plasticizer (0.800 g, 10 wt %), and p-BAPS (0.155 g, 15 mol %) were stirred at 225 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 200 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 30 Pa.Math.s.

EXAMPLE 9

(17) Formulation of 11:10 Oligomeric Phthalonitrile Based on Bisphenol A and 4,4-Dichlorobenzophenone with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile; 30 Mol %), Ferro Phosphate Plasticizer (10 wt %), and p-BAPS (10 Mol %) Heat Treated at 200 C.

(18) The 11:10 oligomeric phthalonitrile prepared by the procedure of Example 1 (12.0 g), 4-dodecyl phthalonitrile (0.306 g, 30 mol %), Ferro phosphate plasticizer (1.2 g, 10 wt %), and p-BAPS (0.113 g, 10 mol %) were stirred at 225 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 200 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 50 Pa.Math.s.

EXAMPLE 10

(19) Formulation of 21:20 Oligomeric Phthalonitrile Based on Bisphenol A and 4,4-Dichlorobenzophenone with Trioctyl Trimellitate Plasticizer (20 wt %) and m-BAPS (50 Mol %) Heat Treated at 250 C.

(20) The 21:20 oligomeric phthalonitrile prepared by the procedure of Example 1 (12.0 g), trioctyl trimellitate plasticizer (2.4 g, 20 wt %), and m-BAPS (0.300 g, 50 mol %) were stirred at 250 C. for 5 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 250 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 50 Pa.Math.s.

EXAMPLE 11

(21) Formulation of 11:10 Oligomeric Phthalonitrile Based on Bisphenol A and 4,4-Dichlorobenzophenone with Trioctyl Trimellitate Plasticizer (20 wt %) and m-BAPS (5 Mol %) Heat Treated at 250 C.

(22) The 11:10 oligomeric phthalonitrile prepared by the procedure of Example 1 (12.0 g), trioctyl trimellitate plasticizer (2.4 g, 20 wt %), and m-BAPS (0.113 g, 5 mol %) were stirred at 250 C. for 5 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 250 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 50 Pa.Math.s.

EXAMPLE 12

(23) Polymerization of Formulation of 11:10 Oligomeric Phthalonitrile Based on Bisphenol a and 4,4-Dichlorobenzophenone with Trioctyl Trimellitate Plasticizer (20 wt %) and m-BAPS (5 Mol %) Heat Treated to 300 C.

(24) The formulation (1.3 g) prepared by the procedure of Example 11 was heated at 250 C. for 2 hr, at 300 C. for 2 hr, and at 400 C. for 2 hr. Gelation occurred to a solid thermoset during the 250 C. thermal treatment.

EXAMPLE 13

(25) Preparation of Phthalonitrile Resin for General Melt Extrusion into Fiber

(26) Approximately 1 g of phthalonitrile composition prepared as in Example 10 is powdered and tested for viscosity in a rotational rheometer using a 25 mm diameter top rotor at a gap setting of 250 microns, at a single temperature in the range of 220 to 250 C. as desired. The measurement is in oscillation mode, with maximum strain of 3%. The resulting curve of viscosity vs. time is used to determine the time needed to cure the material to a measured viscosity of 30 to 40 Pa.Math.s. The required amount of material prepared as in Example 10 is then heated in a convection oven at the same temperature as the viscosity measurement to a time equivalent to that determined from the viscosity curve, plus an additional amount of time that must be determined empirically to account for oven and sample heating uniformity and heat-up time. A second check of the viscosity of the partially cured material is then performed to insure a resulting value of 30 to 40 Pa.Math.s.

EXAMPLE 14

(27) General Process for Melt Extrusion of Phthalonitrile Resin into Fiber Using a Piston Type Extruder or a Capillary Rheometer

(28) Partially cured material prepared as in Example 13 in an amount appropriate for the capacity of the extruder barrel is ground to a coarse powder. The barrel must be preheated to the extrusion temperature, which is generally the temperature at which viscosity is measured from Example 13. The piston should also be heated to the same temperature. The amount of material to be extruded should be chosen not only based on the capacity of the extruder, but also on the residence time of material in the barrel for a given piston rate. Typically, the amount of time necessary for the material to advance to a viscosity value that is twice its starting value should be taken as the upper limit of the residence time. This time is directly given by the viscosity data obtained in Example 13. The material is then added to the barrel, and is allowed to thermally equilibrate for a few minutes. This time depends on the size of the extruder, and must be empirically determined. The material is then extruded at the desired rate. Mechanical drawing and winding of the resulting fiber can take place at least up to 100 m/min when using a 250 micron orifice. Fiber thickness is determined by the relative rates of both extrusion and draw winding. Following extrusion the barrel should be purged with an inert thermoplastic such as polypropylene, or otherwise cleaned, unless a second charge is to be immediately added.

EXAMPLE 15

(29) General Process for Melt Extrusion of Phthalonitrile Resin into Fiber Using a Screw Driven Extruder with or without a Melt Pump

(30) Partially cured material prepared as in Example 13 in an amount appropriate for the capacity of the extruder is ground to coarse powder. The extruder must be preheated to the extrusion temperature, which is generally the temperature at which viscosity is measured from Example 13. The amount of material to be extruded should be chosen not only based on the capacity of the extruder, but also on the residence time of material in the extruder chamber for a given feed rate. Typically, the amount of time necessary for the material to advance to a viscosity value that is twice its starting value should be taken as the upper limit of the residence time. This time is directly given by the viscosity data obtained in example 13. The material is then added to the extruder feed and is allowed to thermally equilibrate for several minutes. This process is greatly aided by the drive action of the extruder, which melts and equilibrates the material quickly. The material is then extruded at the desired rate. Mechanical winding of the resulting fiber can take place at least up to 100 m/min for an individual fiber when using a 250 micron orifice, or 200 m/min when the material is extruded as a multifilament fiber tow. Following extrusion the extruder should be purged with an inert thermoplastic such as polypropylene, or otherwise cleaned, unless a second charge is to be immediately added.

EXAMPLE 16

(31) Formulation of 5:4 Oligomeric Phthalonitrile Based on Bisphenol A and 4,4-Dichlorobenzophenone with Trioctyl Trimellitate Plasticizer (15 wt %) and m-BAPS (5 Mol %) Heat Treated at 250 C.

(32) The 5:4 oligomeric phthalonitrile prepared by the procedure of Example 1 (10.0 g), trioctyl trimellitate plasticizer (1.5 g, 15 wt %), and m-BAPS (0.100 g, 5 mol %) were stirred at 250 C. for 5 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 250 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 50 Pa.Math.s.

EXAMPLE 17

(33) Polymerization of Formulation of 5:4 Oligomeric Phthalonitrile Based on Bisphenol a and 4,4-Dichlorobenzophenone with Trioctyl Trimellitate Plasticizer (15 wt %) and m-BAPS (5 Mol %) Heat Treated at 400 C.

(34) The formulation (1.6 g) prepared by the procedure of Example 16 was heated at 250 C. for 2 hr, at 300 C. for 2 hr, and at 400 C. for 2 hr. Gelation occurred to a solid thermoset during the 250 C. thermal treatment.

EXAMPLE 18

(35) Formulation of 26:25 Oligomeric Phthalonitrile Based on Bisphenol A and 4,4-Dichlorobenzophenone with Trioctyl Trimellitate Plasticizer (20 wt %) and m-BAPS (75 Mol %) Heat Treated at 225 C.

(36) The 26:25 oligomeric phthalonitrile prepared by the procedure of Example 1 (12.0 g), trioctyl trimellitate plasticizer (2.4 g, 20 wt %), and m-BAPS (0.300 g, 75 mol %) were stirred at 250 C. for 5 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 225 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 50 Pa.Math.s.

EXAMPLE 19

(37) Formulation of 26:25 Oligomeric Phthalonitrile Based on Bisphenol A and 4,4-Dichlorobenzophenone with Trioctyl Trimellitate Plasticizer (30 wt %) and m-BAPS (75 Mol %) Heat Treated at 240 C.

(38) The 26:25 oligomeric phthalonitrile prepared by the procedure of Example 1 (12.0 g), trioctyl trimellitate plasticizer (3.6 g, 30 wt %), and m-BAPS (0.300 g, 75 mol %) were stirred at 250 C. for 5 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 240 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 50 Pa.Math.s.

EXAMPLE 20

(39) General Synthesis of Oligomeric Phthalonitrile Based on Bisphenol A and 1,4-Dibromobenzene in One Reaction Pot

(40) To a 250 mL, three-necked flask fitted with a thermometer, a Dean-Stark trap with condenser, and a nitrogen inlet were added bisphenol A, 1,4-dibromobenzene, powdered anhydrous K.sub.2CO.sub.3 (1.2 eq based on bisphenol A), (PPH.sub.3).sub.3CuBr, toluene, and dimethylsulfoxide (DMSO). Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content. The resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene. The mixture was refluxed at 160-170 C. under a nitrogen atmosphere for 6-18 hr or until no more water was observed being collected in the Dean-Stark trap. The toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl dipotassium salt and high conversion, in general, to the intermediate. The mixture was cooled to 50 C. At this time, 4-nitrophthalonitrile was added in one portion and the reaction mixture was heated at 80 C. for 6-8 hr. The mixture was allowed to cool to ambient temperature and poured into a 5% aqueous HCl solution resulting in the formation of a solid. The material was broken up and collected using a Bchner funnel. The white solid was washed with 200 mL portions of distilled water until neutral. The isolated solid was vacuum dried to yield the oligomeric phthalonitrile. The length of the PN will be designated by the ratio of bisphenol A to 1,4-dibromobenzene, e.g. 2:1 oligomeric phthalonitrile means 2 moles bisphenol A to 1 mole 1,4-dibromobenzene.

EXAMPLE 21

(41) Formulation of 11:10 Oligomeric Phthalonitrile Based on Bisphenol A and 1,4-Dibromobenzene with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile; 30 Mol %), Ferro Phosphate Plasticizer (10 wt %), and m-BAPS (5 Mol %) Heat Treated at 225 C.

(42) The 11:10 oligomeric phthalonitrile prepared by the procedure of Example 20 (11.0 g), 4-dodecyl phthalonitrile (0.368 g, 30 mol %), Ferro phosphate plasticizer (1.10 g, 10 wt %), and m-BAPS (0.068 g, 5 mol %) were stirred at 200 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 225 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 30 Pa.Math.s.

EXAMPLE 22

(43) Polymerization of Formulation of 11:10 Oligomeric Phthalonitrile Based on Bisphenol a and 1,4-Dibromobenzene with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile; 30 Mol %), Ferro Phosphate Plasticizer (10 wt %), and m-BAPS (5 Mol %) Heat Treated at 375 C.

(44) The formulation (2.0 g) prepared by the procedure of Example 21 was heated at 250 C. for 2 hr, at 300 C. for 3 hr, at 350 C. for 2 hr, and finally at 400 C. for 3 hr. Gelation to a solid thermoset occurred during the 250 C. thermal treatment.

EXAMPLE 23

(45) Formulation of 41:40 Oligomeric Phthalonitrile Based on Bisphenol A and 1,4-Dibromobenzene with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile; 30 Mol %), Ferro Phosphate Plasticizer (10 wt %), and m-BAPS (50 Mol %) Heat Treated at 250 C.

(46) The 41:40 oligomeric phthalonitrile prepared by the procedure of Example 20 (12.0 g), 4-dodecyl phthalonitrile (0.111 g, 30 mol %), Ferro phosphate plasticizer (1.20 g, 10 wt %), and m-BAPS (0.206 g, 50 mol %) were stirred at 200 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 250 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 30 Pa.Math.s.

EXAMPLE 24

(47) Formulation of 11:10 Oligomeric Phthalonitrile Based on Bisphenol A and 1,4-Dibromobenzene with a Ferro Phosphate Plasticizer (10 wt %) and m-BAPS (5 Mol %) Heat Treated at 225 C.

(48) The 11:10 oligomeric phthalonitrile prepared by the procedure of Example 20 (12.0 g), Ferro phosphate plasticizer (1.20 g, 10 wt %), and m-BAPS (0.074 g, 5 mol %) were stirred at 200 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 225 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 30 Pa.Math.s.

EXAMPLE 25

(49) Polymerization of Formulation of 11:10 Oligomeric Phthalonitrile Based on Bisphenol a and 1,4-Dibromobenzene with a Ferro Phosphate Plasticizer (10 wt %) and m-BAPS (5 Mol %) Heat Treated at 225 C.

(50) The formulation (1.5 g) prepared by the procedure of Example 24 was heated at 250 C. for 2 hr, at 300 C. for 2 hr, at 350 C., and finally at 400 C. for 2 hr. Gelation to a solid thermoset occurred during the 250 C. thermal treatment.

EXAMPLE 26

(51) Formulation of 21:20 Oligomeric Phthalonitrile Based on Bisphenol A and 1,4-Dibromobenzene with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile; 30 Mol %), Ferro Phosphate Plasticizer (10 wt %), and m-BAPS (40 Mol %) Heat Treated at 250 C.

(52) The 21:20 oligomeric phthalonitrile prepared by the procedure of Example 20 (12.0 g), 4-dodecyl phthalonitrile (0.215 g, 30 mol %), Ferro phosphate plasticizer (1.20 g, 10 wt %), and m-BAPS (0.318 g, 40 mol %) were stirred at 200 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace and heated at 250 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 50 Pa.Math.s.

EXAMPLE 27

(53) Formulation of 2:1 Oligomeric Phthalonitrile Based on Bisphenol A and 1,4-Dibromobenzene with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile; 30 Mol %), Ferro Phosphate Plasticizer (10 wt %), and m-BAPS (5 Mol %) Heat Treated at 225 C.

(54) The 2:1 oligomeric phthalonitrile from prepared by the procedure of Example 20 (12.0 g), 4-dodecyl phthalonitrile (1.79 g, 30 mol %), Ferro phosphate plasticizer (1.20 g, 10 wt %), and m-BAPS (0.331 g, 5 mol %) were stirred at 200 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 225 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 30 Pa.Math.s.

EXAMPLE 28

(55) Formulation of 2:1 Oligomeric Phthalonitrile Based on Bisphenol A and 1,4-Dibromobenzene with a Ferro Phosphate Plasticizer (10 wt %) and m-BAPS (5 Mol %) Heat Treated at 250 C.

(56) The 2:1 oligomeric phthalonitrile prepared by the procedure of Example 20 (12.0 g), Ferro phosphate plasticizer (1.20 g, 10 wt %), and m-BAPS (0.331 g, 5 mol %) were stirred at 200 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 225 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 50 Pa.Math.s.

EXAMPLE 29

(57) Polymerization of Formulation of 2:1 Oligomeric Phthalonitrile Based on Bisphenol A and 1,4-Dibromobenzene with a Ferro Phosphate Plasticizer (10 wt %) and m-BAPS (5 Mol %) Heat Treated at 250 C.

(58) The formulation (1.6 g) prepared by the procedure of Example 28 was heated at 250 C. for 2 hr, at 300 C. for 2 hr, at 350 C., and finally at 400 C. for 2 hr. Gelation to a solid thermoset occurred during the 250 C. thermal treatment.

EXAMPLE 30

(59) Formulation of 21:20 Oligomeric Phthalonitrile Based on Bisphenol A and 1,4-Dibromobenzene with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile; 30 Mol %), Trioctyl Trimellitate (10 wt %), and m-BAPS (40 Mol %) Heat Treated at 225 C.

(60) The 21:20 oligomeric phthalonitrile prepared by the procedure of Example 20 (12.0 g), 4-dodecyl phthalonitrile (0.215 g, 30 mol %), trioctyl trimellitate (1.20 g, 10 wt %), and m-BAPS (0.318 g, 40 mol %) were stirred at 200 C. for 2 minutes to form a homogeneous solution. The mixture was cooled, placed in a furnace, and heated at 225 C. for various times in order to obtain a mixture with an initial viscosity at 225 C. between 10 and 50 Pa.Math.s.

EXAMPLE 31

(61) Polymerization of Formulation of 21:20 Oligomeric Phthalonitrile Based on Bisphenol A and 1,4-Dibromobenzene with a Mono Phthalonitrile (4-Dodecyl Phthalonitrile; 30 Mol %), Trioctyl Trimellitate (10 wt %), and m-BAPS (40 Mol %) Heat Treated at 225 C.

(62) The formulation (1.7 g) prepared by the procedure of Example 30 was heated at 250 C. for 2 hr, at 300 C. for 2 hr, at 350 C., and finally at 400 C. for 2 hr. Gelation to a solid thermoset occurred during the 250 C. thermal treatment.

(63) Obviously, many modifications and variations are possible in light of the above teachings. It is therefore to be understood that the claimed subject matter may be practiced otherwise than as specifically described. Any reference to claim elements in the singular, e.g., using the articles a, an, the, or said is not construed as limiting the element to the singular.