Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acids and salts thereof
Reexamination Certificate
1998-12-30
2001-05-22
Killos, Paul J. (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acids and salts thereof
C562S538000, C562S540000
Reexamination Certificate
active
06235931
ABSTRACT:
FIELD OF INVENTION
This invention relates to process for oxidizing polyoxyalkylene alcohols and/or glycols to their corresponding carboxylic acids in the presence of a free radical nitroxide and an NO
x
generating compound.
BACKGROUND OF THE INVENTION
The oxidation of polyoxyalkylene alcohols and glycols to their corresponding carboxylates in the presence of a free radical nitroxide and an NO
x
generating compound is described in various patents to Shell Oil Company by Herbert Fried. For example, U.S. Pat. No. 5,256,819 describes the oxidation of polyoxyalkylene glycols to their carboxylates in high yields (greater than about 98%) and high selectivities by using a free radical nitroxide, an NO
x
generating source, and an additional source of oxygen such as oxygen gas, in the presence of a solvent such as dichloromethane, triglyme, monoglyme, diglyme, tertiary amyl alcohol, acetonitrile, and the like. The results from the examples demonstrate degrees of conversion to the carboxylate in excess of 99%, with selectivities in excess of 99%.
SUMMARY OF THE INVENTION
We have discovered that it is not desirable to use highly converted carboxylate compositions of polyoxyalkylene alcohols and glycols as reagents in the manufacture of water borne epoxy resin compositions, and we have further discovered that it is desirable to only partially convert polyoxyalklyene alcohols and glycols to their corresponding carboxylates.
The carboxylates of the polyoxyalkylene alcohols and glycols are useful as reactive surfactants to provide stable dispersions of epoxy resin in water. In the manufacture of epoxy resin surfactants, however, we have found that carboxylate compositions made by high conversion of polyoxyalkylene alcohols and glycols to their corresponding carboxylates, upon reaction with primary amine compounds and epoxy resin compounds, results in an epoxy resin surfactant composition which is too viscous due to chain growth from the dicarboxylate-diamine reaction and a dispersion whose stability is not optimal due to the formation of a large number tertiary amine groups which autocatalyze further epoxy-hydroxyl reactions, and a partial loss in surfactancy due to the tendency of chain scission during the oxidation reaction as the degree of conversion rises above 95%.
Accordingly, there is provided a process for preparing a polycarboxylic acid composition comprising reacting a polyoxyalkylene polyol composition with a stable free radical nitroxide in the presence of an NO
x
generating compound under conditions sufficient to convert from 60% to no more than 95% of the polyoxyalkylene polyol composition.
There is also provided a process for preparing a polycarboxylic acid composition comprising reacting a polyoxyalkylene polyol composition with a stable free radical nitroxide in the presence of NO
x
and water as a solvent, under conditions sufficient to convert from 60% to no more than 95% of the polyoxyalkylene polyol composition.
There is further provided a process for preparing a polycarboxylic acid composition comprising reacting a polyoxyalkylene polyol composition with a stable free radical nitroxide having the formula:
wherein R
7
, R
8
, R
9
, R
10
are each independently hydrogen or an alkyl, aryl, or aralkly group having from 1 to 15 carbon atoms, and at least one of R
11
and R
12
are hydrogen and the other is —OH, —NHR′, —OR′, —ONHR′, or —NHCOR′, wherein R′ is an alkyl, aryl, alkaryl, or alicyclic group;
in the presence of NO
x
, under conditions sufficient to convert from 60% to no more than 95% of the polyoxyalkylene polyol composition.
REFERENCES:
patent: 3477990 (1969-11-01), Dante et al.
patent: 4734468 (1988-03-01), Marx
patent: 5136101 (1992-08-01), Fried
patent: 5136102 (1992-08-01), Fried
patent: 5136103 (1992-08-01), Fried
patent: 5155278 (1992-10-01), Fried
patent: 5155279 (1992-10-01), Fried
patent: 5155280 (1992-10-01), Fried
patent: 5162579 (1992-11-01), Fried
patent: 5166422 (1992-11-01), Fried
patent: 5166423 (1992-11-01), Fried
patent: 5175359 (1992-12-01), Fried
patent: 5175360 (1992-12-01), Fried
patent: 5179218 (1993-01-01), Fried
patent: 5239116 (1993-08-01), Fried
patent: 5250727 (1993-10-01), Fried
patent: 5256819 (1993-10-01), Fried
patent: 5336811 (1994-08-01), Fried
patent: 5352824 (1994-10-01), Fried
patent: 5380930 (1995-01-01), Fried
patent: 5387712 (1995-02-01), Fried
patent: 5391822 (1995-02-01), Fried
patent: 5401874 (1995-03-01), Fried
patent: 5488154 (1996-01-01), Fried
patent: 5495045 (1996-02-01), Fried
patent: 5608106 (1997-03-01), Fried et al.
patent: 5608107 (1997-03-01), Fried et al.
patent: 5681903 (1997-10-01), Fried et al.
patent: 2332177 (1974-02-01), None
patent: 0000605 (1979-02-01), None
Addicks Glynnda
Back Gayle Edward
Elmore Jimmie Dale
Fried Herbert Elliott
Wang Pen-Chung
Carmen Dennis V.
Killos Paul J.
Shell Oil Company
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