3-OXO-2-ALKYLISOINDOLINE DIPHTHALONITRILE MONOMERS, METHODS OF MANUFACTURE, THERMOSETTING COMPOSITIONS COMPRISING THE SAME, AND USES THEREOF

1 . A thermosetting composition, comprising a 4,4′-(((3-oxo-2-hydrocarbylisoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy)) diphthalonitrile compound of formula (1)

wherein

R is a C 1-12 hydrocarbyl;

each occurrence of R 2 and R 3 is independently a hydrogen, a halogen, or a C 1-25 hydrocarbyl; and

p and q are each independently 0 to 4.

2 . The thermosetting composition of claim 1 , wherein the 4,4′-(((3-oxo-2-hydrocarbylisoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy)) diphthalonitrile compound is of formula (1a)

wherein

R is a C 1-6 alkyl or a C 6-12 aryl;

each occurrence of R 2 is independently a hydrogen or C 1-6 alkyl; and

p is independently 0 or 1.

3 . The thermosetting composition of claim 1 , wherein the 4,4′-(((3-oxo-2-hydrocarbylisoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy)) diphthalonitrile compound is of formula (1b)

4 . The thermosetting composition of claim 1 , further comprising a curing agent.

5 . The thermosetting composition of claim 4 , wherein the curing agent is a diamine, a triamine, a higher amine, an acid salt of an amine, an organic acid having a pKa in water of less than 4, or a combination thereof.

6 . The thermosetting composition of claim 4 , wherein the curing agent is an amine-containing phosphazene, an aromatic diamine, an aromatic diamine/metal salt complex, an aromatic ether amine, an amine salt of p-toluene sulfonic acid, an organic acid having a pKa in water of less than 3, or a combination thereof.

7 . The thermosetting composition of claim 4 , wherein the curing agent is o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 2,4-bis(β-amino-t-butyl)toluene, bis(p-β-amino-t-butyl)ether, bis(p-β-methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene, 1,2-bis(3-aminopropoxy)ethane, benzidine, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4′-bis(3-aminophenoxy)biphenyl, 4,4′-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, or a combination thereof.

8 . The thermosetting composition of claim 1 , further comprising a comonomer.

9 . The thermosetting composition of claim 8 , wherein the comonomer is a diphthalonitrile different from the compound of formula (1).

10 . The thermosetting composition of claim 1 , further comprising an additive, wherein the additive is a particulate filler, fibrous filler, antioxidant, heat stabilizer, light stabilizer, ultraviolet light stabilizer, ultraviolet light-absorbing compound, near infrared light-absorbing compound, infrared light-absorbing compound, plasticizer, lubricant, release agent, antistatic agent, anti-fog agent, antimicrobial agent, colorant, surface effect additive, radiation stabilizer, flame retardant, anti-drip agent, fragrance, a polymer different from the thermoset polymer, or a combination thereof.

11 . A method for the manufacture of a 4,4′-(((3-oxo-2-hydrocarbylisoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy)) diphthalonitrile compound of formula (1),

the method comprising:

reacting a 3,3-bis(4-hydroxyaryl)-2-hydrocarbylisoindolin-1-one of formula (2)

with 4-nitrophthalonitrile under conditions effective to provide the 4,4′-(((3-oxo-2-hydrocarbylisoindoline-1,1-diyl)bis(4,1-arylene))bis(oxy)) diphthalonitrile compound (1),

wherein

R is a C 1-12 hydrocarbyl;

each occurrence of R 2 and R 3 is independently a hydrogen, a halogen, or a C 1-25 hydrocarbyl; and

p and q are each independently 0 to 4.

12 . The method of claim 11 , wherein the 3,3-bis(4-hydroxyaryl)-2-hydrocarbylisoindolin-1-one is of formula (2a)

wherein

R is a C 1-6 alkyl;

each occurrence of R 2 is independently a hydrogen or C 1-6 alkyl; and

p is 0 or 1.

13 . The method of claim 11 , wherein the 3,3-bis(4-hydroxyaryl)-2-alkylisoindolin-1-one is of formula (2b)

14 . The method of claim 11 , wherein the reacting is in a solvent in the presence of an inorganic base.

15 . The method of claim 14 , wherein the solvent is an alkyl pyrrolidone solvent, an aromatic solvent, a halogenated aromatic solvent, or a combination thereof.

16 . The method of claim 14 , wherein the inorganic base is lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, or a combination thereof.

17 . The method of claim 11 , further comprising:

contacting an inorganic base and a 3,3-bis(4-hydroxyaryl)-2-arylisoindolin-1-one of formula (2) to provide a metal salt precursor; and

reacting the metal salt precursor with 4-nitrophthalonitrile.

18 . A thermoset polymer composition comprising a crosslinked product of the thermosetting composition of claim 1 .

19 . An article comprising the thermoset polymer composition of claim 18 , wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a component, a prepreg, a casing, or a combination thereof.

20 . The article of claim 19 , wherein the article is an electronic substrate, an electronic housing, a microelectronic device, a printed electronic component, a tooling, a geothermal tool, an oil rig component, a flame retardant component, a sizing resin, a resin infusion molded component, a resin transfer molded component, or a combination thereof.