US3972851A
Expired / Lapsed
US
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Preparation of polyphenylene oxide using a manganese(II) ortho-hydroxyarene-oxime chelate reaction promoter
Assignee: General Electric Co
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Filing: 1974-07-24
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Granted: 1976-08-03
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Expires: 1994-07-24
Abstract
Abstract A process for the preparation of polyphenylene oxide employing a manganese (II) ortho-hydroxyareneoxime chelate catalyst is described. The process can be effectively carried out both in the absence as well as in the presence of amines. 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
2026-11-01 12:02
CPC Classifications
C; C08; C08G; C08G65/00; C08G65/34; C08G65/38; C08G65/44
Claims Analysis
Total Claims: 19
Claim 1
Independent Claim
190 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 a basic reaction medium and in the presence of a manganese chelate complex of the formula: (L).sub.x Mn, wherein L is an ortho-hydroxyareneoxime ligand of the formula: ##EQU9##wherein independently R a is selected from the group consisting of hydrogen and lower alkyl radicals having from one to five carbon atoms, Ar is at least a divalent arene radical having at least --OH radical and at least one ##EQU10##radical attached directly to an ortho positioned arene ring carbon atom, and x is a positive number at least equal to about 1.
Claim 2
Dependent Claim
190 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 a basic reaction medium and in the presence of a manganese chelate complex of the formula: (L).sub.x Mn, wherein L is an ortho-hydroxyareneoxime ligand of the formula: ##EQU9##wherein independently R a is selected from the group consisting of hydrogen and lower alkyl radicals having from one to five carbon atoms, Ar is at least a divalent arene radical having at least --OH radical and at least one ##EQU10##radical attached directly to an ortho positioned arene ring carbon atom, and x is a positive number at least equal to about 1.
Claim 3
Dependent Claim
21 words
The process of claim 1, wherein R a is selected from lower alkyl radicals having from one to two carbon atoms.
Claim 4
Dependent Claim
30 words
The process of claim 1, wherein said arene radical is selected from the group consisting of monocyclic and polycyclic organic radicals having from about 6 to about 30 carbon atoms.
Claim 5
Dependent Claim
18 words
The process of claim 1 where said contacting is carried out in the presence of a primary amine.
Claim 6
Dependent Claim
80 words
The process of claim 1, wherein said amine has the formula R.sup.2 --NH.sub.2).sub.y, wherein R 2 is selected from mono- and polyvalent aliphatic and aromatic radicals, y is a positive integer at least equal to 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 7
Dependent Claim
15 words
The process of claim 5, wherein said y is at least equal to about 2.
Claim 8
Dependent Claim
26 words
A process in accordance with claim 6, wherein said amine is selected from the group consisting of polyamino substituted mono- and polycyclic aliphatic and aromatic compounds.
Claim 9
Dependent Claim
19 words
The process of claim 1, wherein said contacting is carried out in the presence of an alkali metal base.
Claim 10
Dependent Claim
25 words
The process of claim 1, wherein said contacting is carried out at a temperature within the range of from about 0° to about 50° C.
Claim 11
Dependent Claim
16 words
The process of claim 1, wherein said range is from about 20° to about 30° C.
Claim 12
Dependent Claim
15 words
The process of claim 1, wherein said contacting is carried out at superatmospheric oxygen pressure.
Claim 13
Dependent Claim
11 words
The process of claim 1, wherein said a phenol is 2,6-dimethylphenol.
Claim 14
Dependent Claim
89 words
The process of claim 1, wherein said complex is of the formula ##EQU11##wherein R a is independently selected from the group consisting of hydrogen and lower alkyl radicals having from 1 to 5 carbon atoms, Ar is at least a divalent arene radical having at least one --OH radical and at least one ##EQU12##radical attached directly to ortho positioned arene ring carbon atoms, and R b is selected from the group consisting of hydrogen, or alkyl, cycloalkyl, aryl, amino, monoalkylamino, dialkylamino, halide, hydroxy, alkoxy, alkanoate radicals and combinations thereof.
Claim 15
Dependent Claim
13 words
The process of claim 1, wherein said complex is of the formula: ##EQU13##
Claim 16
Dependent Claim
16 words
The process of claim 1, wherein said complex is a Mn(II) bis(salicylaldoxime) chelate of the formula:
Claim 17
Dependent Claim
16 words
The process of claim 1, wherein said complex is a Mn(II) bis(2-hydroxy-5-bromophenylaldoxime) chelate of the formula:
Claim 18
Dependent Claim
17 words
The process of claim 1, wherein said complex is a Mn(II) bis(2-hydroxy-5-methoxyphenylaldoxime) chelate of the formula: ##EQU14##
Claim 19
Dependent Claim
16 words
The process of claim 1, wherein said complex is a Mn(II) bis(2-hydroxy-acetophenoneoxime) chelate of the formula:
References Cited (Backward Citations)
US3444133A
Cited
US3825521A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1979-08-03 | 1980-02-02 | 1980-08-03 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1983-08-03 | 1984-02-02 | 1984-08-03 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1987-08-03 | 1988-02-02 | 1988-08-03 | $7700.00 | Window Closed / Lapsed |