CONTAINING BOTH TRIAZINE AND OXAZOLINE GROUPS AND

FOR PREPARING EPOXY RESINS FROM THE OLIGOMERS

The present invention provides processes for preparing hydroxyaromatic oligomers containing both triazine and oxazoline groups, and for preparing epoxy resins from said oligomers.

Epoxy resins containing triazine groups are known from Japan Kokai Tokkyo Koho 81 26,925 dated March 16, 1981. However, the preparation of said resins involves the use of the difficult-to-obtain intermediate 2,4,6-trichloro-l,3,5-triazine. Furthermore, coupling of 2,4,6-trichloro-l,3,5-triazine with a diphenol through the chloride groups is difficult and leads to a relatively uncontrollable product mix.

The hydroxyaromatic oligomers prepared by the process of the present invention contain both triazine and oxazoline groups. The oligomers are prepared by co-oligomerization of a mixed cyanate of a polyphenol with an epoxy resin. In the process, the polyphenol, such as 4 ₇ 4'-isopropylidenediphenol (Bisphenol A) is reacted with less than a stoichiometric equivalent of a

cyanogen halide in the presence of an alkaline agent, such as triethylamine. This provides a mixture of monocyanate, dicyanate and, optionally, unreacted polyphenol. Co-oligomerization of this mixture with the desired amount of an epoxy resin, such as the diglycidyl ether of Bisphenol A, provides hydroxyaromatic oligomers containing both triazine and oxazoline groups. Epoxidation of the oligomers and unreacted polyphenol, if any, using methods well known in the art provides the epoxy resin compositions of this invention.

Although included within the scope of this invention, oligomers prepared from co-oligomerization of the mixed cyanate of a diphenol with an epoxy resin wherein the mole ratio of epoxy groups to cyanate groups is less than 1:10, respectively, are generally insoluble in solvent(s) and/or reactant(s) useful in epoxidation reactions but are useful as thermoset resins. Oligomers prepared from co-oligomerization of the mixed cyanate of a diphenol with an epoxy resin wherein the mole ratios of epoxy groups to cyanate groups are 1:10 to 1:40 are most preferred precursors ^• to the epoxy resins of the present invention.

Unreacted polyphenol, which is preferably present as a component of the oligomers, is converted to the corresponding polyglycidyl ether during the epoxidation of the hydroxyaromatic oligomers. This improves overall processability of the epoxy resin. If desired, extra polyphenol can be added prior to epoxidation to increase the polyphenol polyglycidyl ether content of the finished epoxy resin product.

Likewise, extra polycyanate may be added to the cyanate mixture prior to co-oligomerization with an epoxy resin.

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The present invention pertains to a process for preparing hydroxyaromatic oligomers containing both triazine and oxazoline groups characterized by

(I) reacting (A) at least one material having an average of more than one aromatic hydroxyl group per molecule with (B) at least 0.01 but not more than 0.95, preferably from 0.05 to 0.55, moles of cyanogen halide or mixture of cyanogen halides per aromatic hydroxyl group in the presence of (C) a suitable base in a quantity of from 0.01 to 1.1, preferably from 0.05 to 0.6, moles per aromatic hydroxyl group at a temperature and time sufficient to essentially complete the reaction and thereafter recovering the resultant cyanate mixture;

(II) co-oligomerizing the product resulting from (I) with an epoxy resin wherein the mole ratio of epoxy groups to cyanate groups is from 1:1 to 1:100, preferably from 1:10 to 1:40 in the presence of a suitable co-oligomerization catalyst at a temperature and time to essentially complete the co-oligomerization reaction.

Another aspect of the present invention pertains to a process for preparing epoxy resin containing both triazine and oxazoline groups by epoxidizing a hydroxyaromatic material in a conventional manner by reaction with an epihalohydrin with subsequent dehydro- halogenation with a basic-acting material and finally recovering the resultant glycidyl ether product, characterized in that the hydroxyaromatic material is the resultant co-oligomerization product from step (II) of the process described hereinbefore.

Suitable materials having an average of more than one aromatic hydroxyl group per molecule which can be employed in the present invention include, for example, those represented by the formulas

wherein A is a divalent hydrocarbon group having from 1 to 12, preferably from 1 to 6

0 0 0 0

II II II II carbon atoms, -S-, -S-S-, -S-, -S-, -C-, -O-C-O-, -O-, tr

0

the like; each A' is a divalent

hydrocarbon group having from 1 to 3, preferably 1, carbon atoms; each R is independently hydrogen, halogen, preferably chlorine or bromine, a hydrocarbyl group having from 1 to 6 carbon atoms or a hydroxyl group; each R ¹ is independently hydrogen or a hydrocarbyl

group having from 1 to 6 carbon atoms or a halogen, preferably chlorine or bromine; m has a value from zero to 2; m ^» has a value from 1 to 100; n has a value of zero or 1 and n ¹ has a value from 1.01 to 6.

Particularly suitable aromatic hydroxyl-contain- ing compounds include, for example, o-, m- and p-dihydroxy- benzene, 2-tert butyl hydroquinone, 2,4-dimethyl resorcinol, 2,5-di-tert butyl hydroquinone, tetramethyl hydroquinone, 2,4,6-trimethyl resorcinol, 4-chlororesorcinol, 4-tert butyl pyrocatechol, l,l-bis(4-hydroxyphenyl)ethane;

2,2-bis(4-hydroxyphenyl)propane; 2,2-bis(4-hydroxyphenyl)- pentane; bis(4,4'-dihydroxyphenyl)methane; 4,4'-dihydroxy- diphenyl, 2,2*-dihydroxydiphenyl, 3,3* ,5,5'-tetramethyl- 4,4'-dihydroxydiphenyl, 3,3• ,5,5•-tetrachloro-4,4 ^• -dihy- droxydiphenyl, 3,3' ,5,5'-tetrachloro-2,2'-dihydroxy¬ diphenyl, 2,2' ,6,6•-tetrachloro-4,4'-dihydroxydiphenyl, 4,4'-bis((3-hydroxy)phenoxy)-diphenyl, 4,4'-bis((4-hy- droxy)phenoxy)-diphenyl, 2,2'-dihydroxy-1,1*-binaphthyl, and other dihydroxydiphenyls; 4,4'-dihydroxydiphenyl ether, 3,3* ,5,5'-tetramethyl-4,4 ^» -dihydroxydiphenyl ether, 3,3' ,5,5•-tetrachloro-4,4'-hydroxydiphenyl ether, 4,4'-bis(p-hydroxyphenoxy)-diphenyl ether, 4,4'-bis(p-hydroxyphenyl isopropyl)-diphenyl ether, 4,4'-bis(p-hydroxyphenoxy)-benzene, 4,4'-bis(p-hydroxy- phenoxy)-diphenyl ether, 4,4'-bis(4(4-hydroxyphenoxy)- phenyl sulfone)-diphenyl ether, and other dihydroxy¬ diphenyl ethers; 4,4'-dihydroxydiphenyl sulfone, 3,3',- 5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfone, 3,3'5,5'- tetrachloro-4,4 ^• -dihydroxydiphenyl sulfone, 4,4'-bis(p- hydroxyphenyl isopropyl)-diphenyl sulfone, 4,4'-bis((4- hydroxy)-phenoxy)-diphenyl sulfone, 4,4'-bis( (3-hydroxy)- phenoxy)-diphenyl sulfone, 4,4'-bis(4-(4-hydroxyphenyl- isopropyl)-phenoxy)-diphenyl sulfone, 4,4'-bis(4(4-hy- droxy)diphenoxy)-diphenyl sulfone, and other diphenyl

sulfones; 4,4'-dihydroxydiphenyl methane, 4,4'-bis(p-hydroxyphenyl)-diphenyl methane, 2,2'-bis(p-hydroxyphenyl)-propane, 3,3' ,5,5'-tetramethyl- -2,2'-bis(p-hydroxyphenyl)-propane, 3,3',5,5,'- -tetrachloro-2,2'-bis(p-hydroxyphenyl)-propane,

1,1-bis(p-hydroxyphenyl)-cyclohexane, bis-(2-hydroxy- -1-naphthyl)-methane, 1,2-bis(p-hydroxyphenyl)-1,1,2,2- -tetramethyl ethane, 4,4'-dihydroxybenzophenone, 4,4'-bis(4-hydroxy)phenoxy-benzophenone, 1,4-bis- (p-hydroxyphenyl isopropyl)-benzene, phloroglucinol, pyrogallol, 2,2' ,5,5'-tetrahydroxy-diphenyl sulfone, other dihydroxydiphenyl alkanes, and mixtures thereof.

Suitable cyanogen halides which can be employed herein include, for example, cyanogen chloride, cyanogen bromide, and mixtures thereof.

If desired, the method reported in Organic Syntheses, Vol. 61, page 35-37 (1983), published by John Wiley & Sons, may be used to generate the required amount of cyanogen halide in situ, although this is less preferred than using neat cyanogen halide.

Suitable basic-acting materials which can be employed herein as component (I-C) include both inorganic bases and tertiary amines, such as, for example, sodium hydroxide, potassium hydroxide, triethylamine, and mixtures -thereof. The tertiary amines are most preferred as the base material.

Suitable epoxy resins for co-oligomerization with the cyanate mixture include, for example, those represented by the formulas

wherein A, R' and n are as hereinbefore defined, and m ² has an average value of

Suitable co-oligomerization catalysts which can be employed herein include, for example, metal salts of carboxylic acids, such as, lead octoate, zinc stearate, zinc acetylacetonate, at concentrations of 0.001 to 5 percent. Most preferred catalysts are cobalt naphthenate, cobalt octoate, or mixtures thereof.

Although the co-oligomerization of the cyanate mixture with an epoxy resin provides both triazine and oxazoline functionality in the oligomer product, it is felt that other reactions may also be occurring. For example, unreacted phenolic groups may react with cyanate groups to form iminocarbonate linkages which may in turn react with remaining epoxide groups.

The epoxidation step can be accomplished by employing the known methods described in Handbook of Epoxy Resins by Lee and Neville, McGraw-Hill, 1967. This usually includes reacting the product from step (II) with an epihalohydrin followed by dehydrohalo- genation with a basic-acting material such as an alkali metal hydroxide and finally recovering the resultant glycidyl ether product.

Suitable curing agents and/or catalysts for the epoxy resins are described in the aforementioned Handbook of Epoxy Resins.

The step (I) reaction is usually conducted at a temperature of from -40°C to 60°C, preferably from -20°C to 25°C for from 10 minutes (600 s) to 120 minutes (7200 s), preferably from 10 minutes (600 s) to 60 minutes (3600 s).

If desired, the reaction of step (I) can be conducted in the presence of an inert solvent reaction medium. Suitable such solvents include, for example, water, chlorinated hydrocarbons, ketones, and mixtures thereof. Acetone, chloroform, and methylene chloride are most preferred as solvents.

The reaction of step (II) is usually conducted at a temperature of from 70°C to 350°C, preferably from 70°C to 200°C for a period of from 15 minutes (900 s) to 120 minutes (7200 s), preferably from 30 minutes (1800 s) to 75 minutes (4500 s). The reaction is preferably performed in the presence of a suitable co-oligomerization catalyst..

The epoxy resins of the present invention can be used to prepare, castings, coatings, laminates, or encapsulations, and are especially suited for use in high temperature environments and where high mechanical strength is required.

The following examples are illustrative of the invention, but are not to be construed as to limit¬ ing the scope thereof in any manner.

EXAMPLE 1 ^A * Preparation of Diphenol Cyanate Mixture

Cyanogen bromide (0.55 moles, 58.26 grams) was added to a reactor containing stirred acetone (175 milliliters) under a nitrogen atmosphere. The cyanogen bromide-acetone solution was cooled to -3°C, then Bisphenol A (1.00 mole, 228.30 grams) dissolved in chilled acetone (650 milliliters) was added to the reactor. The stirred solution was allowed to equilibrate

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at -3°C, then triethyla ine (0.50 mole, 50.60 grams) was added to the reactor over a thirty minute (1800 s) period so as to maintain the reaction temperature at -5 to 0°C. After completion of the triethylamine addition, the reactor was maintained at 0 to 7°C for an additional 20 minutes (1200 s), followed by addition of the reaction product to chilled water (1 gallon, 3078 ml) with agitation. After 15 minutes (900 s), the water and product mixture was multiply extracted with methylene chloride (400 milliliters total). The combined methylene chloride extracts were washed 5 percent hydrochloric acid (500 milliliters), then water (800 milliliters), and then dried over anhydrous sodium sulfate. The dry methylene chloride extract was filtered and solvent removed by rotary evaporation under vacuum. The diphenol cyanate mixture was recovered (234.12 grams) as a white-colored solid at room temperature (25°C). Infrared spectrophotometric analysis demonstrated the presence of the cyanate functionality as well as unreacted hydroxyl functionality. Liquid chromatographic analysis demonstrated the presence of 67.2 area percent Bisphenol

A, 29.9 area percent Bisphenol A monocyanate, and 2.9 area percent Bisphenol A dicyanate.

B. Co-oligomerization of Diphenol Cyanate Mixture and an Epoxy Resin

A portion of the diphenol cyanate mixture

(230.3 grams) from A above, an epoxy resin (10.79 grams) and 6.0 percent cobalt naphthenate (0.10 percent by weight, 0.24 gram) were thoroughly mixed and placed in a glass tray. The epoxy resin had an epoxide equivalent weight (EEW) of 337.8 and was prepared by reaction of Bisphenol A diglycidyl ether, EEW = 183,

(0.40 mole, 146.4 grams) with Bisphenol A (0.20 mole,

45.66 grams) and benzyl trimethylammonium chloride

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catalyst 60 percent aqueous, (0.19 gram) at 120°C for 50 minutes (3000 s). The tray was then placed in a forced-air, convection-type oven and maintained for 1.25 hours (4500 s) at 177°C. The hydroxyaromatic co-oligomerization product containing triazine and oxazoline groups was recovered in quantitative yield as a transparent, light amber-colored, brittle solid at room temperature (25°C). Infrared spectrophotometric analysis demonstrated complete disappearance of the cyanate functionality, appearance of the triazine functionality, appearance of the oxazoline functionality and the presence of unreacted hydroxyl functionality.

Portions of the hydroxyaromatic co-oligomer¬ ization product containing triazine and oxazoline groups were analyzed by gel permeation chromatography using polystyrene standards. The weight average molecular weight was 7937 and the polydispersity ratio is 4.24. The polydispersity ratio is defined as the ratio of the weight average to number average molecular weights.

C. Epoxidation of Hydroxyaromatic Co-oligomerization Product Containing Triazine and Oxazoline Groups

A portion of the hydroxyaromatic co-oligomeriz¬ ation product containing triazine and oxazoline groups (215.0 grams), epichlorohydrin (7.602 moles, 703.41 grams), isopropanol (35 percent by weight of epichloro¬ hydrin used, 378.76 grams), and water (8 percent by weight of epichlorohydrin used, 61.16 grams) were added to a reactor and stirred under a nitrogen atmosphere at 50°C until a solution was formed. At that time, dropwise addition of a sodium hydroxide (2.74 moles, 109.47 grams) solution in water (437.88 grams) commenced and was completed over the next 45 minutes (2700 s).

During this sodium hydroxide addition, the reaction temperature was allowed to increase to 60°C and was then held at this temperature. Fifteen minutes (900 s) after the addition of sodium hydroxide solution, a second solution of sodium hydroxide (1.22 mole 48.65 grams) in water (194.61 grams) was added dropwise to the reactor over the next 20 minutes (1200 s). Fifteen minutes (900 s) later, the reactor was cooled to 40°C, then an initial water wash (400 milliliters) was added to the reactor. The reactor contents were transferred to a separatory funnel containing additional epichloro¬ hydrin (200 milliliters). The water wash layer was separated and discarded while the organic layer was added back into the separatory funnel along with a second water wash (200 milliliters). The organic layer was separated then added back into the separatory funnel along with a third water wash (800 milliliters) and additional epichlorohydrin (200 milliliters). The recovered organic layer was stripped of solvents by rotary evaporation at 100°C for 30 minutes (1800 s) under vacuum. The epoxy resin was recovered (301.91 grams) as a transparent, light amber-colored liquid at room temperature (25°C). Infrared spectrophotometric analysis demonstrated substantially complete disappear- ance of hydroxyl functionality, appearance of epoxide functionality and presence of both triazine and oxazoline functionalities. Epoxide titration revealed the presence of 20.82 percent by weight epoxide.

A portion of the epoxy resin described above (285.0 grams) was heated to 75°C, then methylenedianiline (68.31 grams) was added and thoroughly mixed in. This, solution was used to prepare a clear, unfilled one-eighth

inch (3.175 mm) casting for heat distortion temperature (264 psi, 1820 kPa), tensile and flexural strength, flexural modulus, percent elongation, average Barcol hardness (934-1 scale) and unnotched Izod impact strength determinations. The casting was cured for 2 hours

(7200 s) at 75°C, followed by post-curing for 2 hours (7200 s) at 125°C, 2 hours (7200 s) at 175°C, then 2 hours (7200 s) at 200°C. Mechanical properties of tensile (8) and flexural (5) test pieces were determined using an Instron machine with standard test methods

(ASTM D638 and D790). Heat distortion temperature of clear casting test pieces (2) was determined using an Aminco Plastic Deflection Tester (American Instrument Co.) with standard test methods (ASTM D648). Nine 2.5 x 0.5 x 0.125 inch (63.5 x 12.7 x 3.125 mm) test pieces were prepared from the clear, unfilled casting and tested for unnotched Izod impact using a TMI Impact Tester No. 43-1 with standard test methods (ASTM D256). The results are reported in Table I.

TABLE I

Average Barcol Hardness 40

Heat Distortion Temperature (°F/°C) 296/147

Tensile Strength, psi 12,593

, MPa 87 Elongation (%) 5.36

Flexural Strength, psi 23,081

, MPa 159

Flexural Modulus, psi 512,000

, MPa 3528 Izod Impact Strength, unnotched, ft-lb/in 8.35

, J/m 446

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WIPO i >

A sample (9.56 milligrams) of the clear, unfilled casting prepared above was analyzed by thermo- gravimetric analysis (TGA) using a nitrogen flow rate of 80 cubic centimeters per minute and a rate of temper- ature increase of 10°C per minute. The weight of the sample as a function of temperature is reported in Table IV.

COMPARATIVE EXPERIMENT A

A. Preparation of Diphenol Cyanate Mixture Cyanogen bromide (0.55 moles, 58.26 grams) was added to a reactor containing stirred acetone (175 milliliters) under a nitrogen atmosphere. The cyanogen bromide-acetone solution was cooled to -5 ^β C, then Bisphenol A (1.00 mole, 228.30 grams) dissolved in chilled acetone (650 milliliters) was added to the reactor. The stirred solution was allowed to equili¬ brate at -5°C, then triethylamine (0.50 mole, 50.60 grams) was added to the reactor over a 25 minute (1500 s) period and so as to maintain the reaction temperature at -2 to -5°C. After completion of the triethylamine addition, the reactor was maintained at -2 to 0°C for an additional 20 minutes (1200 s), followed by addition of the reaction product to chilled water (1 gallon, 3078 ml) with agitation. After 15 minutes (900 s), the water and product mixture was multiply extracted with methylene chloride. The combined methylene chloride extracts were sequentially washed with dilute hydrochloric acid (5 percent), water, hydrochloric acid, water and then dried over anhydrous magnesium sulfate. The dry methylene chloride extract was filtered and solvent _. removed by rotary evaporation under vacuum. The diphenol cyanate mixture was recovered (229.7 grams) as a white- colored solid at room temperature (25°C). Infrared

spectrophotometric analysis demonstrated the presence of the cyanate functionality as well as unreacted hydroxyl functionality. Liquid chromatographic analysis demonstrated the presence of 55.82 area percent Bisphenol A, 37.89 area percent Bisphenol A monocyanate, and 6.29 area percent Bisphenol A dicyanate.

B. Trimerization of Diphenol Cyanate Mixture

The diphenol cyanate mixture (229.7 grams) and 6.0 percent cobalt naphthenate (0.10 percent by weight, 0.23 gram) were thoroughly mixed and placed in a glass tray. The tray was then placed in a forced-air, convection-type oven and maintained for 1.25 hour at 177°C. The hydroxyaromatic oligomers containing triazine groups were recovered in quantitative yield as a trans- parent, brittle solid at room temperature (25°C). The oligomers had a greenish-colored cast due to the catalyst. At the 177°C temperature, the oligomers were still totally fluid. Infrared spectrophotometric analysis demonstrated complete disappearance of the cyanate functionality, appearance of the triazine functionality, and the presence of unreacted hydroxyl functionality.

Portions of the hydroxyaromatic co-oligomer¬ ization product containing triazine and oxazoline groups were analyzed by gel permeation chromatography using polystyrene standards. The average molecular weight was 3748 and the polydispersity ratio is 1.40.

C. Epoxidation of Hydroxyaromatic Oligomers Containing Triazine Groups

A portion of the hydroxyaromatic oligomers containing triazine groups (215.00 grams), epichlorohydrin

(6.865 moles, 635.22 grams), isopropanol (35 percent by

weight of epichlorohydrin used, 342.04 grams), and water (8 percent by weight of epichlorohydrin used, 55.24 grams) were added to a reactor and stirred under a nitrogen atmosphere at 60°C until a solution was formed. At this time, the reactor was cooled to 50°C and dropwise addition of a sodium hydroxide (2.4714 moles, 98.86 grams) solution in water (395.42 grams) commenced and was completed over the next 45 minutes (2700 s). During this sodium hydroxide addition, the reaction temperature was allowed to increase to 60°C and was then held at this temperature. Fifteen minutes (900 s) after the addition of sodium hydroxide solution, a second solution of sodium hydroxide (1.0984 mole, 43.94 grams) in water (175.76 grams) was added dropwise to the reactor over the next 20 minutes (1200 s).

Fifteen minutes (900 s) later, the reactor was cooled to 40°C then an initial water wash (400 grams) was added to the reactor. The reactor contents were transferred to a separatory funnel containing additional epichlorohydrin (200 grams). The water wash layer was separated and discarded while the organic layer was added back into the separatory funnel along with a second water wash (200 grams). The organic layer was separated then added back into the separatory funnel along with a third water wash (200 grams). The water wash layer was separated and discarded while the organic layer was added back into the separatory funnel with a final wash (1000 grams). Epichlorohydrin (200 grams) was added to the separatory funnel, then the water wash layer was separated and discarded. The recovered organic layer was stripped of solvents by rotary evaporation at 100°C for 30 minutes (1800 s) under vacuum. The epoxy resin was recovered (272.4 grams) as a transparent, light yellow-colored liquid at room

temperature (25°C). Infrared spectrophotometric analysis demonstrated substantially complete disappearance of hydroxyl functionality, appearance of epoxide func¬ tionality and presence of triazine functionality. 5 Epoxide titration revealed the presence of 21.55 percent by weight epoxide.

A portion of the epoxy resin prepared above (265.0 grams) was heated to 75°C, then methylene- dianiline (65.74 grams) was added and thoroughly mixed 10 in. This solution was used to prepare a clear, unfilled, one-eighth inch (3.175 mm) casting using the method of Example 1. Mechanical property testing was completed using the method of Example 1 and the results are reported in Table II.

1.5 TABLE II

Average Barcol Hardness 42

Heat Distortion Temperature (°F/°C) 307/152.75

Tensile Strength, psi 10,694

, MPa 73.73 0 Elongation (%) 3.69

Flexural Strength, psi 21,709

, MPa 149.68

Flexural Modulus, psi 519,000

, MPa 3578.4 5 Izod Impact Strength, unnotched, ft-lb/in 8.24

, J/m 440

A sample (14.98 milligrams) of the clear, unfilled casting prepared above was analyzed by thermogravimetric analysis (TGA) using the method of 0 Example 1. The results are reported in Table III.

TABLE III

Percent of Original Weight

Comparative

Temperature (°C) Example 1 Experiment A

200 99.5 99.6

250 99.2 99.2

300 98.8 98.9

350 98.2 97.0

400 95.0 66.8

450 43.2 31.4

500 20.8 24.8

EXAMPLE 2

A. Preparation of Diphenol Cyanate Mixture

Cyanogen bromide (0.55 moles, 58.26 grams) was added to a reactor, containing stirred acetone (175 milliliters) under a nitrogen atmosphere. The cyanogen bromide-acetone solution was cooled to -4°C, then Bisphenol A (1.00 mole, 228.30 grams) dissolved in chilled acetone (650 milliliters) was added to the reactor. The stirred solution was allowed to equilibrate at -4°C, then triethylamine (0.50 mole, 50.60 grams) was added to the reactor over a 25 minute (1500 s) period and so as to maintain the reaction temperature at -2 to -5°C. After completion of the triethylamine addition, the reactor was maintained at -3 to -5°C for an additional 20 minutes (1200 s), followed by addition of the reaction product to chilled water (1 gallon, 13.78 1) with agitation. After 15 minutes (900 s), the water and product mixture was multiply extracted with methylene chloride (400 milliliters total). The combined

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methylene chloride extracts were washed with 5 percent hydrochloric acid (500 milliliters), then water (800 milliliters), and then dried over anhydrous sodium sulfate. The dry methylene chloride extract was filtered and solvent removed by rotary evaporation under vacuum. The diphenol cyanate mixture was recovered (229.8 grams) as a white-colored solid at room temperature (25°C). Infrared spectrophotometric analysis demonstrated the presence of the cyanate functionality as well as unreacted hydroxyl functionality. Liquid chromatographic analysis demonstrated the presence of 55.5 area percent Bisphenol A, 37.7 area percent Bisphenol A monocyanate, and 6.8 area percent Bisphenol A dicyanate.

B. Co-όiigomerization of Diphenol Cyanate Mixture and an Epoxy Resin

A portion of the diphenol cyanate mixture

(229.0 grams), an epoxy resin (153.29 grams) and 6.0 percent cobalt naphthenate (0.10 percent by weight,

0.38 gram) were thoroughly mixed and placed in a glass tray. The epoxy resin used was identical to that described in Example 1-B. The tray was then placed in a forced-air, convection-type oven and maintained for 1.25 hours (4500 s) at 177°C. The hydroxyaromatic co-oligomerization product containing triazine and oxazoline groups was recovered in quantitative yield as a tan-colored, rigid, opaque solid at room temperature (25°C). The product behaved as a rubbery solid at the 177°C temperature. A lack of solubility in organic solvents precluded further analysis of the product.