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US3965069A Expired / Lapsed US ⏱️ 0.0 years remaining

Polyphenylene oxide is prepared using a mixture of manganese chelates as a catalyst

Assignee: General Electric Co
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Filing: 1974-12-20
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Granted: 1976-06-22
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Expires: 1994-12-20
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Abstract

Abstract A process for the preparation of polyphenylene oxide employing a mixture comprising a manganese(II) oxime chelate Type (A) and a manganese chelate Type (B) as a catalyst is described. The catalyzed process can be effectively carried out in the presence as well as the absence of an amine. The process is economical and useful in the production of polyphenylene oxide resins.

Inventors

  • 👤 Walter K. Olander

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-25 08:03
CPC Classifications
C; C08; C08G; C08G65/00; C08G65/34; C08G65/38; C08G65/44

Claims Analysis

Total Claims: 22
Claim 1
Independent Claim 301 words
A process of forming self-condensation products of a phenol having the structural formula: ##SPC4## where X is a substituent selected from the group consisting of hydrogen, chlorine, bromine, and iodine; R' is a monovalent constituent selected from the group consisting of hydrogen, hydrocarbon radicals, halohydrocarbon radicals having at least two carbon atoms between the halogen atoms and phenol nucleus, hydrocarbonoxy radicals, and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atoms and phenol nucleus, R" and R'" being the same as R' and, in addition, halogen under reaction conditions which comprise contacting said phenol with oxygen in the presence of a basic reaction medium and a mixture of Type (A) and Type (B) manganese chelate complexes selected from Type (A) complexes of the formulas: Type (A): (L.sup.1).sub.x Mn, where L 1 is a ligand derived from an ortho-hydroxyareneoxime of the general formula ##EQU12## wherein R a is independently selected from the group consisting of hydrogen and lower alkyl radicals having from 1-5 carbon atoms, Ar is at least a divalent arene radical having at least one -OH radical and at least one ##EQU13## radical attached directly to ortho-positioned arene ring carbon atoms, and an ω-hydroxyoxime of the formula ##EQU14## wherein each R b , R c , R d and R e is independently selected from the group consisting of hydrogen, acyclic and cyclic organic radicals, and n is a positive integer equal to 0 or 1, Mn is the transition metal manganese(II), and x is a positive number at least equal to about 0.5, and selected from Type (B) complexes of the formula: Type (B): (L.sup.2).sub.x Mn, wherein L 2 is a ligand other than an L 1 ligand, Mn is the transition metal manganese, and x is a positive number at least equal to about 0.5.
Claim 2
Dependent Claim 301 words
A process of forming self-condensation products of a phenol having the structural formula: ##SPC4## where X is a substituent selected from the group consisting of hydrogen, chlorine, bromine, and iodine; R' is a monovalent constituent selected from the group consisting of hydrogen, hydrocarbon radicals, halohydrocarbon radicals having at least two carbon atoms between the halogen atoms and phenol nucleus, hydrocarbonoxy radicals, and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atoms and phenol nucleus, R" and R'" being the same as R' and, in addition, halogen under reaction conditions which comprise contacting said phenol with oxygen in the presence of a basic reaction medium and a mixture of Type (A) and Type (B) manganese chelate complexes selected from Type (A) complexes of the formulas: Type (A): (L.sup.1).sub.x Mn, where L 1 is a ligand derived from an ortho-hydroxyareneoxime of the general formula ##EQU12## wherein R a is independently selected from the group consisting of hydrogen and lower alkyl radicals having from 1-5 carbon atoms, Ar is at least a divalent arene radical having at least one -OH radical and at least one ##EQU13## radical attached directly to ortho-positioned arene ring carbon atoms, and an ω-hydroxyoxime of the formula ##EQU14## wherein each R b , R c , R d and R e is independently selected from the group consisting of hydrogen, acyclic and cyclic organic radicals, and n is a positive integer equal to 0 or 1, Mn is the transition metal manganese(II), and x is a positive number at least equal to about 0.5, and selected from Type (B) complexes of the formula: Type (B): (L.sup.2).sub.x Mn, wherein L 2 is a ligand other than an L 1 ligand, Mn is the transition metal manganese, and x is a positive number at least equal to about 0.5.
Claim 3
Dependent Claim 254 words
A process of forming self-condensation products of a phenol having the structural formula: ##SPC5## where X is a substituent selected from the group consisting of hydrogen, chlorine, bromine, and iodine; R' is a monovalent constituent selected from the group consisting of hydrogen, hydrocarbon radicals, halohydrocarbon radicals having at least two carbon atoms between the halogen atoms and phenol nucleus, hydrocarbonoxy radicals, and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atoms and phenol nucleus, R" and R'" being the same as R' and, in addition, halogen under reaction conditions which comprise contacting said phenol with oxygen in the presence of a basic reaction medium and a mixture of Type (A) and Type (B) manganese chelate complexes selected from Type (A) complexes of the formulas: Type (A): (L.sup.1).sub.x Mn, where L 1 is a ligand derived from an ortho-hydroxyareneoxime of the general formula ##EQU15## wherein R a is independently selected from the group consisting of hydrogen and lower alkyl radicals having from 1-5 carbon atoms, Ar is a mono- or dicyclic arene radical having one -OH radical and one ##EQU16## radical attached directly to orthopositioned arene ring carbon atoms, and an ω-hydroxyoxime of the formula ##EQU17## wherein each R b , R c , R d and R e is independently selected from the group consisting of hydrogen, acyclic and cyclic organic radicals, and n is a positive integer equal to 0 or 1, Mn is the transition metal manganese(II), and x is a positive number at least equal to about 1.0.
Claim 4
Dependent Claim 254 words
A process of forming self-condensation products of a phenol having the structural formula: ##SPC5## where X is a substituent selected from the group consisting of hydrogen, chlorine, bromine, and iodine; R' is a monovalent constituent selected from the group consisting of hydrogen, hydrocarbon radicals, halohydrocarbon radicals having at least two carbon atoms between the halogen atoms and phenol nucleus, hydrocarbonoxy radicals, and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atoms and phenol nucleus, R" and R'" being the same as R' and, in addition, halogen under reaction conditions which comprise contacting said phenol with oxygen in the presence of a basic reaction medium and a mixture of Type (A) and Type (B) manganese chelate complexes selected from Type (A) complexes of the formulas: Type (A): (L.sup.1).sub.x Mn, where L 1 is a ligand derived from an ortho-hydroxyareneoxime of the general formula ##EQU15## wherein R a is independently selected from the group consisting of hydrogen and lower alkyl radicals having from 1-5 carbon atoms, Ar is a mono- or dicyclic arene radical having one -OH radical and one ##EQU16## radical attached directly to orthopositioned arene ring carbon atoms, and an ω-hydroxyoxime of the formula ##EQU17## wherein each R b , R c , R d and R e is independently selected from the group consisting of hydrogen, acyclic and cyclic organic radicals, and n is a positive integer equal to 0 or 1, Mn is the transition metal manganese(II), and x is a positive number at least equal to about 1.0.
Claim 5
Dependent Claim 14 words
The process of claim 2, wherein n is a positive integer equal to 1.
Claim 6
Dependent Claim 14 words
The process of claim 2, wherein n is a positive integer equal to 0.
Claim 7
Dependent Claim 17 words
The process of claim 2, wherein x is a positive number at least equal to about 2.
Claim 8
Dependent Claim 18 words
The process of claim 2, wherein the Ar radical contains from about 6 to about 30 carbon atoms.
Claim 9
Dependent Claim 16 words
The process of claim 1, wherein the Ar radical is selected from mono- and polycyclic radicals.
Claim 10
Dependent Claim 13 words
The process of claim 1, wherein the Ar radical is mono- or dicyclic.
Claim 11
Dependent Claim 38 words
The process of claim 6, wherein independently R b , R c , R d , and R e is selected from hydrogen and acyclic or cyclic organic radicals containing from about 1 to about 30 carbon atoms.
Claim 12
Dependent Claim 36 words
The process of claim 9, wherein R b , R c , R d and R e are selected from hydrogen and acyclic or cyclic organic radicals containing from about 1 to about 15 carbon atoms.
Claim 13
Dependent Claim 20 words
The process of claim 10, wherein independently at least one of R b and R e is an aromatic radical.
Claim 14
Dependent Claim 25 words
The process of claim 2, wherein the contacting is carried out at a temperature within the range of from about 0° to about 60° C.
Claim 15
Dependent Claim 15 words
The process of claim 2, wherein the contacting is carried out at superatmospheric oxygen pressure.
Claim 16
Dependent Claim 25 words
The process of claim 2, wherein the phenol is 2,6-xylenol, the Type (A) chelate is Mn(II) bis(salicylaldoxime) and the Type (B) chelate is Mn(II) bis(salicylaldehyde)ethylenediimine.
Claim 17
Dependent Claim 25 words
The process of claim 2, wherein the phenol is 2,6-xylenol, the Type (A) chelate is Mn(II) bis(salicylaldoxime) and the Type (B) chelate is Mn(II) bis(acetylacetone).
Claim 18
Dependent Claim 18 words
The process of claim 2, wherein the contacting is carried out in the presence of a primary amine.
Claim 19
Dependent Claim 85 words
The process of claim 16, wherein the primary amine is of the formula: R.sup.1 --NH.sub.2).sub.y wherein R 1 is selected from mono- or polyvalent aliphatic and aromatic radicals, or combinations thereof, y is a positive integer equal to at least 1, subject to the proviso that (a) at least three carbon atoms separate any amino (--NH 2 ) group from any other amino (--NH 2 ) group, and (b) at least two carbon atoms separate any amino group (--NH 2 ) from any other nucleophile.
Claim 20
Dependent Claim 21 words
The process of claim 17, wherein the amine is an aromatic amine containing from about 7 to about 30 carbon atoms.
Claim 21
Dependent Claim 21 words
The process of claim 17, wherein the amine is an aliphatic amine containing from about 1 to about 30 carbon atoms.
Claim 22
Dependent Claim 24 words
The process of claim 16, wherein the mole ratio of phenol to amine is within the range of from about 100:0.05 to about 100:1.5.

References Cited (Backward Citations)

US3444133A Cited
US3793246A Cited
US3825521A Cited
US3784575A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1979-06-22 1979-12-22 1980-06-22 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1983-06-22 1983-12-22 1984-06-22 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1987-06-22 1987-12-22 1988-06-22 $7700.00 Window Closed / Lapsed

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