Phenylene ether oligomer composition

1. A phenylene ether oligomer composition comprising,

a phenylene ether oligomer having an external amine content of greater than 0 to less than or equal to 1.3 weight percent; and

wherein the phenylene ether oligomer composition has a residual solvent in an amount of 10 to 10,000 parts per million by weight, based on the weight of the phenylene ether oligomer composition;

wherein the external amine has a formula

wherein:

Z 1 is halogen, unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;

each occurrence of Z 2 is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;

each occurrence of R 1 is independently hydrogen or unsubstituted or substituted C 1 -C 12 hydrocarbyl; and

each occurrence of R 2 is independently an unsubstituted or substituted C 1 -C 12 hydrocarbyl;

wherein the phenylene ether oligomer composition has

an intrinsic viscosity of 0.03 to 0.13 deciliter per gram;

a glass transition temperature of 135 to 175° C.; or

a combination thereof.

2. The phenylene ether oligomer composition of claim 1 , wherein phenylene ether oligomer comprises phenylene ether repeating units having the structure

wherein:

each Z 1 is independently halogen, unsubstituted or substituted C 1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and

each Z 2 is independently hydrogen, halogen, unsubstituted or substituted C 1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atom.

3. The phenylene ether oligomer composition of claim 2 wherein each Z 1 is independently methyl, allyl, substituted or unsubstituted phenyl, substituted or unsubstituted C 3-12 cycloalkyl, substituted or unsubstituted C 7-12 bicycloalkyl, or substituted or unsubstituted C 7-12 bicycloalkenyl; and each Z 2 is independently hydrogen or methyl.

4. The phenylene ether oligomer composition of claim 2 , wherein one occurrence of Z 1 is methyl; and the other occurrence of Z 1 is methyl, allyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted —CH 2 -adamantyl, substituted or unsubstituted —(CH 2 ) 2 -bicyclo[2.2.1]heptenyl, or substituted or unsubstituted C 1-3 alkyl(C 3-12 bicycloalkenyl) different from the substituted or unsubstituted —(CH 2 ) 2 -bicyclo[2.2.1]heptenyl.

5. The phenylene ether oligomer composition of claim 1 , wherein the phenylene oligomer comprises a bifunctional phenylene ether oligomer having the structure

wherein

Q 1 and Q 2 are each independently halogen, unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;

Q 3 and Q 4 are independently hydrogen, halogen, unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;

x and y are each independently 0 to 30, provided that the sum of x and y is at least 2,

L has the structure

wherein

each occurrence of R 3 and R 4 and R 5 and R 6 is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12 primary or secondary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;

z is 0 or 1; and

Y has a structure

wherein:

each occurrence of R 7 is independently hydrogen or C 1-12 hydrocarbyl, and

each occurrence of R 8 and R 9 is independently hydrogen, C 1-12 hydrocarbyl, or C 1-6 hydrocarbylene, wherein R 8 and R 9 collectively form a C 4-12 alkylene group.

6. The phenylene ether oligomer composition of claim 2 , wherein at least one occurrence of Z 1 is methyl and wherein the phenylene oligomer comprises

a bridging fragment of the formula

a branching fragment of the formula

or a combination thereof.

7. The phenylene ether oligomer composition of claim 1 , wherein the phenylene ether composition has:

an intrinsic viscosity of 0.075 to 0.095 deciliter per gram;

a glass transition temperature of 135 to 150° C.; or

a combination thereof.

8. The phenylene ether oligomer composition of claim 1 , wherein

the phenylene ether oligomer has an amine end group content of less than or equal to 0.1 weight percent; and

the phenylene ether composition has:

an intrinsic viscosity of 0.125 to 0.13 deciliter per gram;

a glass transition temperature of 150 to 175° C.; or

a combination thereof.

9. A phenylene ether oligomer composition comprising,

a phenylene ether oligomer having an external amine content of greater than 0 to less than or equal to 1.3 weight percent;

and

a residual solvent in an amount of 10 to 10000 parts per million by weight, based on the weight of the phenylene ether oligomer composition;

wherein the phenylene ether oligomer composition has a zero shear melt viscosity of 20,000 to 100,000 centipoise at 200° C. and an intrinsic viscosity of 0.03 to 0.13 deciliter per gram.

10. The phenylene ether oligomer composition of claim 9 , wherein phenylene ether oligomer is monofunctional or bifunctional.

11. The phenylene ether oligomer composition of claim 9 , wherein phenylene ether oligomer comprises phenylene ether repeating units having the structure

wherein:

each Z 1 is independently halogen, unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and

each Z 2 is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atom.

12. The phenylene ether oligomer composition of claim 11 , wherein each Z 1 is independently methyl, allyl, substituted or unsubstituted phenyl, substituted or unsubstituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 7 -C 12 bicycloalkyl, or substituted or unsubstituted C 7 -C 12 bicycloalkenyl; and each Z 2 is independently hydrogen or methyl.

13. The phenylene ether oligomer composition of claim 11 , wherein one occurrence of Z 1 of the first monohydric phenol is methyl; and the other occurrence of Z 1 of the first monohydric phenol comprises methyl, allyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted —CH 2 -adamantyl, substituted or unsubstituted —(CH 2 ) 2 -bicyclo[2.2.1]heptenyl, or substituted or unsubstituted C 1-3 alkyl(C 3-12 bicycloalkenyl) different from the substituted or unsubstituted —(CH 2 ) 2 -bicyclo[2.2.1]heptenyl.

14. The phenylene ether oligomer composition of claim 9 , wherein the external amine has a formula

wherein:

Z 1 is halogen, unsubstituted or substituted C 1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;

each occurrence of Z 2 is independently hydrogen, halogen, unsubstituted or substituted C 1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;

each occurrence of R 1 is independently hydrogen or unsubstituted or substituted C 1-12 hydrocarbyl; and

each occurrence of R 2 is independently an unsubstituted or substituted C 1-12 hydrocarbyl.

15. The phenylene ether oligomer composition of claim 9 , wherein the phenylene oligomer comprises a bifunctional phenylene ether oligomer having the structure

wherein

Q 1 and Q 2 are each independently halogen, unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;

Q 3 and Q 4 are independently hydrogen, halogen, unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;

x and y are each independently 0 to 30, provided that the sum of x and y is at least 2,

L has the structure

wherein

each occurrence of R 3 and R 4 and R 5 and R 6 is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12 primary or secondary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;

z is 0 or 1; and

Y has a structure

wherein:

each occurrence of R 7 is independently hydrogen or C 1-12 hydrocarbyl, and

each occurrence of R 8 and R 9 is independently hydrogen, C 1-12 hydrocarbyl, or C 1-6 hydrocarbylene, wherein R 8 and R 9 collectively form a C 4-12 alkylene group.

16. The phenylene ether oligomer composition of claim 11 , wherein at least one occurrence of Z 1 is methyl and wherein the phenylene oligomer comprises

a bridging fragment of the formula

a branching fragment of the formula

or a combination thereof.

17. The phenylene ether oligomer composition of claim 9 , wherein

the phenylene ether oligomer has an amine end group content of 0 to 1.3 weight percent; and

the residual solvent is in an amount of 10 to 9000 parts per million by weight, based on the weight of the phenylene ether oligomer composition; and

the phenylene ether composition has:

a number average molecular weight of 750 to 4,000 grams per mole, and a weight average molecular weight of 1,500 to 9,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards;

a glass transition temperature of 135 to 150° C.;

or a combination thereof.

18. The phenylene ether oligomer composition of claim 1 , wherein

the phenylene ether oligomer has the external amine content of greater than 0 to less than or equal to 0.1 weight percent; and

the phenylene ether composition has:

a number average molecular weight of 750 to 4,000 grams per mole, and a weight average molecular weight of 1,500 to 9,000 grams per mole, as determined by gel permeation chromatography using polystyrene standards.