Promotion of manganese chelate catalyzed polyphenylene ether oxide polymerization reactions

Claim 2

In a process for the preparation of a polyphenylene oxide resin which comprises the steps of: (a) oxidatively coupling a phenolic monomer to form a polyphenylene oxide resin in the presence of an organic solvent and a manganese chelate complex of the formula: (L).sub.x Mn wherein L is a ligand derived from an ω-hydroxyoxime by conventional means, Mn is the transition metal manganese and x is at least equal to about 0.5, the improvement which comprises enhancing the rate of reaction by adding to the reaction mixture an amount of a bis-secondary diamine of the formula: ##STR7## wherein R 1 is selected from the group consisting of: ##STR8## wherein R 4 is lower alkyl of from 1 to 10 carbon atoms; R 2 is methylene; and R 3 is selected from the group consisting of: ##STR9## wherein R 4 is the same as hereinabove defined; n is 0 or 1; m is 0 or a whole number from 1 to 10; and p is 0 or 1 with the proviso that the values of n and p are such that the compound always has two nitrogen atoms, said amount of said bis-secondary diamine being sufficient to increase the rate of reaction.

Claim 3

The process of claim 1 wherein the phenolic monomer is selected from compounds having the formula: ##STR10## wherein X is a substituent selected from the group consisting of hydrogen, chlorine, bromine and iodine, Q is a monovalent substituent selected from the group consisting of hydrocarbon radicals, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenol nucleus, hydrocarbonoxy and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenol nucleus; and Q' is as defined for Q, and in addition may be halogen and Q" are each as defined for Q' and in addition hydrogen, with the proviso that Q, Q' and Q" are all free of a tertiary carbon atom.

Claim 4

The process of claim 2 wherein the ligand of the manganese chelate complex is of the formula: ##STR11## wherein R a , R b , R c , and R d are selected from the group consisting of hydrogen, acyclic and cyclic organic radicals and n is a positive integer equal to 0 or 1.

Claim 5

The process of claim 3 wherein the oxidative coupling is carried out in the presence of between 0.1 and 3.0 mole percent of the bis-secondary diamine.

Claim 6

The process of claim 4 wherein the phenolic monomer is 2,6-xylenol.

Claim 7

The process of claim 5 wherein the manganese (II) chelate complex is manganese benzoin oxime.

Claim 8

The process of claim 3 wherein the bis-secondary diamine is N,N'-diethyl-1,6-hexanediamine.

Claim 9

The process of claim 3 wherein the bis-secondary diamine is 1,3-di-4-piperidylpropane.

Claim 10

The process of claim 3 wherein the bis-secondary diamine is piperazine.

Claim 11

In a process for the preparation of a polyphenylene oxide resin which comprises the steps of (a) oxidatively coupling a phenolic monomer in the presence of oxygen to form a polyphenylene oxide in the presence of an organic solvent and a manganese (II) chelate complex of the formula: ##STR12## wherein R a , R b , R c , and R d are selected from the group consisting of hydrogen, acyclic and cyclic organic radicals and n is a positive integer equal to 0 or 1; the improvement which comprises enhancing the rate of reaction by adding to the reaction mixture an amount of a bis-secondary diamine of the formula: ##STR13## wherein R 1 is selected from the group consisting of: ##STR14## wherein R 4 is lower alkyl of from 1 to 10 carbon atoms; R 2 is methylene and R 3 is selected from the group consisting of ##STR15## wherein R 4 is the same as hereinabove defined; n is 0 or 1; m is 0 or a whole number from 1 to 10; and p is 0 or 1 with the proviso that the values of n and p are such that the compound always has two nitrogen atoms, said amount being between 0.1 to 3.0 mole percent of the phenolic monomer.

Claim 12

In a process for the preparation of a polyphenylene oxide resin which comprises the steps of (a) oxidatively coupling a phenolic monomer in the presence of oxygen to form a polyphenylene oxide in the presence of an organic solvent and a manganese (II) chelate complex of the formula: ##STR12## wherein R a , R b , R c , and R d are selected from the group consisting of hydrogen, acyclic and cyclic organic radicals and n is a positive integer equal to 0 or 1; the improvement which comprises enhancing the rate of reaction by adding to the reaction mixture an amount of a bis-secondary diamine of the formula: ##STR13## wherein R 1 is selected from the group consisting of: ##STR14## wherein R 4 is lower alkyl of from 1 to 10 carbon atoms; R 2 is methylene and R 3 is selected from the group consisting of ##STR15## wherein R 4 is the same as hereinabove defined; n is 0 or 1; m is 0 or a whole number from 1 to 10; and p is 0 or 1 with the proviso that the values of n and p are such that the compound always has two nitrogen atoms, said amount being between 0.1 to 3.0 mole percent of the phenolic monomer.

Claim 13

The process of claim 10 wherein the phenolic monomer is 2,6-xylenol.

Claim 14

The process of claim 11 wherein the manganese (II) chelate complex is manganese benzoin oxime.

Claim 15

The process of claim 12 wherein the bis-secondary diamine is all added to the reaction mixture at one time.

Claim 16

The process of claim 13 wherein the bis-secondary diamine is N,N'-diethyl-1,6-hexanediamine.

Claim 17

The process of claim 13 wherein the bis-secondary diamine is 1,3-di-4-piperidinylpropane.

Claim 18

The process of claim 13 wherein the amount of bis-secondary diamine is 0.1 to 3.0 moles percent of the 2,6-xylenol.

Claim 19

In a process for the preparation of a polyphenylene oxide resin which comprises the steps of: (a) oxidatively coupling a phenolic monomer to form a polyphenylene oxide resin in the presence of an organic solvent and a manganese chelate complex of the formula: (L).sub.x Mn wherein L is a ligand of the formula ##STR16## wherein R a , R b , R c , and R d are selected from the group consisting of hydrogen, acyclic and cyclic organic radicals and n is a positive integer equal to 0 or 1; and wherein, Mn is the transition metal manganese and x is at least equal to about 0.5, the improvement which comprises enhancing the rate of reaction by adding to the reaction mixture an amount of a bis-secondary diamine of the formula ##STR17## wherein R 1 is selected from the group consisting of: ##STR18## wherein R 4 is a lower alkyl of from 1 to 10 carbon atoms; R 2 is methylene; and R 3 is selected from the group consisting of: ##STR19## wherein R 4 is the same as hereinabove defined; n is 0 or 1; m is 0 or a whole number from 1 to 10; and p is 0 or 1 with the proviso that the values of n and p are such that the compound always has two nitrogen atoms, said amount of said bis-secondary diamine being sufficient to increase the rate of reaction.

Claim 20

In a process for the preparation of a polyphenylene oxide resin which comprises the steps of: (a) oxidatively coupling a phenolic monomer to form a polyphenylene oxide resin in the presence of an organic solvent and a manganese chelate complex of the formula: (L).sub.x Mn wherein L is a ligand of the formula ##STR16## wherein R a , R b , R c , and R d are selected from the group consisting of hydrogen, acyclic and cyclic organic radicals and n is a positive integer equal to 0 or 1; and wherein, Mn is the transition metal manganese and x is at least equal to about 0.5, the improvement which comprises enhancing the rate of reaction by adding to the reaction mixture an amount of a bis-secondary diamine of the formula ##STR17## wherein R 1 is selected from the group consisting of: ##STR18## wherein R 4 is a lower alkyl of from 1 to 10 carbon atoms; R 2 is methylene; and R 3 is selected from the group consisting of: ##STR19## wherein R 4 is the same as hereinabove defined; n is 0 or 1; m is 0 or a whole number from 1 to 10; and p is 0 or 1 with the proviso that the values of n and p are such that the compound always has two nitrogen atoms, said amount of said bis-secondary diamine being sufficient to increase the rate of reaction.

Claim 21

The process of claim 17 wherein the phenolic monomer is selected from compounds having the formula ##STR20## wherein X is a substituent selected from the group consisting of hydrogen, chlorine, bromine and iodine, Q is a monovalent substituent selected from the group consisting of hydrocarbon radicals, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenol nucleus, hydrocarbonoxy and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenol nucleus; and Q' is defined for Q, and in addition may be halogen and Q" are each as defined for Q' and in addition hydrogen, with the proviso that Q, Q' and Q" are all free of a tertiary carbon atom.

Claim 22

The process of claim 18 wherein the oxidative coupling is carried out in the presence of between 0.1 and 3.0 mole percent of the bis-secondary diamine.

Claim 23

The process of claim 19 wherein the phenolic monomer is 2,6-xylenol.

Claim 24

The process of claim 20 wherein the manganese (II) chelate complex is manganese benzoin oxime.

Claim 25

The process of claim 17 wherein the bis-secondary diamine is all added to the reaction mixture at one time.

Claim 26

The process of claim 17 wherein the bis-secondary diamine is N,N'-diethyl-1,6-hexanediamine.

Claim 27

The process of claim 17 wherein the bis-secondary diamine is 1,3-di-4-piperidylpropane.

Claim 28

The process of claim 17 wherein the bis-secondary diamine is piperazine.