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US5541316A
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US
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Process for the production of polysaccharide-based polycarboxylates
Assignee: Henkel AG and Co KGaA
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Filing: 1993-02-03
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Granted: 1996-07-30
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Expires: 2013-02-03
Abstract
Abstract A process for the production of polycarboxylic acids or salts thereof from polysaccharides by oxidation with nitrogen dioxide/dinitrogen tetroxide with at least partial conversion of the primary alcohol groups of the polysaccharides into carboxyl groups and optionally at least partial neutralization of the carboxylic acid groups formed is provided. The oxidation reaction is carried out in a closed reaction system in the presence of oxygen under pressures of 2 bar to 10 bar and at a temperature above room temperature. Nitrogen dioxide/dinitrogen tetroxide is used in such quantities that, in the event of a theoretically complete shift of the equilibrium onto the nitrogen dioxide side, the nitrogen dioxide is present in quantities of at most 2 mole equivalents, based on the content of monomer unit of the polysaccharide containing one primary alcohol group.
Inventors
- 👤 Konrad Engelskirchen
- 👤 Herbert Fischer
- 👤 Hans-Wilhelm Verholt
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 23:44
CPC Classifications
C; C08; C08B; C08B31/00; C08B31/18; C08B15/00; C08B15/02; C08B15/04; C08B37/00; C11; C11D; C11D3/00; C11D3/16; C11D3/20; C11D3/22; C11D3/222; C11D3/223
Claims Analysis
Total Claims: 40
Claim 1
Independent Claim
141 words
A process for the production of polycarboxylic acids or salts thereof, comprising: oxidizing a polysaccharide with nitrogen dioxide/dinitrogen tetroxide with at least partial conversion of the primary alcohol groups of the polysaccharides into carboxyl groups and optionally at least partial neutralization of the carboxylic acid groups formed, said oxidizing being carried out in a closed reaction system in the presence of a gas comprising oxygen under a pressure of 2 bar to 10 bar and at a temperature above room temperature to form the polycarboxylic acid, wherein nitrogen dioxide/dinitrogen tetroxide is used in such a quantity that, in the event of a theoretically complete shift of the equilibrium to nitrogen dioxide, the nitrogen dioxide would be present in a quantity of at most 2 mole equivalents, based on the content of monomer units of the polysaccharide containing one primary alcohol group.
Claim 2
Dependent Claim
141 words
A process for the production of polycarboxylic acids or salts thereof, comprising: oxidizing a polysaccharide with nitrogen dioxide/dinitrogen tetroxide with at least partial conversion of the primary alcohol groups of the polysaccharides into carboxyl groups and optionally at least partial neutralization of the carboxylic acid groups formed, said oxidizing being carried out in a closed reaction system in the presence of a gas comprising oxygen under a pressure of 2 bar to 10 bar and at a temperature above room temperature to form the polycarboxylic acid, wherein nitrogen dioxide/dinitrogen tetroxide is used in such a quantity that, in the event of a theoretically complete shift of the equilibrium to nitrogen dioxide, the nitrogen dioxide would be present in a quantity of at most 2 mole equivalents, based on the content of monomer units of the polysaccharide containing one primary alcohol group.
Claim 3
Dependent Claim
18 words
The process as claimed in claim 1 wherein said oxidizing temperature is from 30° C. to 70° C.
Claim 4
Dependent Claim
18 words
The process as claimed in claim 2 wherein said oxidizing temperature is from 40° C. to 60° C.
Claim 5
Dependent Claim
28 words
The process as claimed in claim 1 wherein said oxidizing is carried out under the pressure of 2 bar to 6 bar, as measured at the reaction temperature.
Claim 6
Dependent Claim
23 words
The process as claimed in claim 4 wherein the pressure in the reaction system is established by introduction of gaseous oxygen under pressure.
Claim 7
Dependent Claim
27 words
The process as claimed in claim 5 wherein the pressure in the reaction system is established by said introduction only once, at the beginning of the reaction.
Claim 8
Dependent Claim
23 words
The process as claimed in claim 5 wherein the pressure in the reaction system is established by said introduction repeatedly during the reaction.
Claim 9
Dependent Claim
23 words
The process as claimed in claim 5 wherein the pressure in the reaction system is established by said introduction continuously during the reaction.
Claim 10
Dependent Claim
50 words
The process as claimed in claim 5 wherein in said introduction of oxygen, said oxygen is in the form of a mixture with at least one gas which is inert under the reaction conditions, said oxygen making up from 1% by volume to 30% by volume of the gas mixture.
Claim 11
Dependent Claim
24 words
The process as claimed in claim 9 wherein said oxygen makes up from 3% by volume to 10% by volume of the gas mixture.
Claim 12
Dependent Claim
29 words
The process as claimed in claim 9 wherein said inert gas is a gas selected from the group consisting of helium, argon, carbon dioxide, nitrogen, and a mixture thereof.
Claim 13
Dependent Claim
13 words
The process as claimed in claim 9 wherein said inert gas is nitrogen.
Claim 14
Dependent Claim
22 words
The process as claimed in claim 9 wherein the pressure in the reaction system is established by introduction of air under pressure.
Claim 15
Dependent Claim
85 words
The process as claimed in claim 5 wherein a pressure of less than 10 bar is established in the reaction system before the beginning of the oxidation reaction by introduction under pressure of an inert gas and after the beginning of the reaction, oxygen or a mixture of 1% by volume to 30% by volume oxygen with the inert gas is repeatedly introduced under pressure so that the oxygen partial pressure in the reaction system is in the range from 0.1 bar to 10 bar.
Claim 16
Dependent Claim
107 words
The process as claimed in claim 5 wherein a pressure of from 2 bar to 6 bar is established in the reaction system before the beginning of the oxidation reaction by introduction under pressure of an inert gas selected from the group consisting of nitrogen, helium, argon, carbon dioxide or a mixture thereof, and after the beginning of the reaction oxygen or a mixture of 3% by volume to 10% by volume of oxygen with at least one of said inert gases is continuously introduced under pressure so that the oxygen partial pressure in the reaction system is in the range from 0.5 bar to 6 bar.
Claim 17
Dependent Claim
29 words
The process as claimed in claim 1 wherein said polysaccharide is in the form of a suspension in a liquid, said liquid being substantially inert under the reaction conditions.
Claim 18
Dependent Claim
14 words
The process as claimed in claim 16 wherein said liquid is a halogenated hydrocarbon.
Claim 19
Dependent Claim
13 words
The process as claimed in claim 16 wherein said liquid is carbon tetrachloride.
Claim 20
Dependent Claim
21 words
The process as claimed in claim 1 wherein said polysaccharide is oxidized in the absence of a suspension medium or solvent.
Claim 21
Dependent Claim
20 words
The process as claimed in claim 1 wherein said polysaccharide is oxidized in the presence of a flow-promoting solid additive.
Claim 22
Dependent Claim
29 words
The process as claimed in claim 20 wherein said additive is selected from the group consisting of magnesium oxide, calcium fluoride, calcium phosphate, pyrogenic silicon dioxide and mixtures thereof.
Claim 23
Dependent Claim
30 words
The process as claimed in claim 20 wherein said additive is present in an amount of 0.1% by weight to 5% by weight based on the polysaccharide to be oxidized.
Claim 24
Dependent Claim
30 words
The process as claimed in claim 22 wherein said additive is present in an amount of 0.25% by weight to 1% by weight based on the polysaccharide to be oxidized.
Claim 25
Dependent Claim
38 words
The process as claimed in claim 19 wherein said oxidizing is carried out in a moving bed or in a fluidized bed of the polysaccharide to be oxidized using a throughflowing gas containing nitrogen dioxide/dinitrogen tetroxide and oxygen.
Claim 26
Dependent Claim
16 words
The process as claimed in claim 1 wherein said polysaccharide is a polyglucosan of native origin.
Claim 27
Dependent Claim
24 words
The process as claimed in claim 1 wherein said polysaccharide comprises at least one member selected from the group consisting of starch and cellulose.
Claim 28
Dependent Claim
26 words
The process as claimed in claim 26 wherein said polysaccharide comprises a native starch selected from potato starch, wheat starch, cornstarch, tapioca starch and mixtures thereof.
Claim 29
Dependent Claim
62 words
The process as claimed in claim 1 wherein said nitrogen dioxide/dinitrogen tetroxide is used in such quantity that, in the event of a theoretically complete shift of the equilibrium to nitrogen dioxide, the nitrogen dioxide would be present in a quantity of 0.1 to 1 mole equivalent, based on the content of monomer units of the polysaccharide containing one primary alcohol group.
Claim 30
Dependent Claim
42 words
The process as claimed in claim 28 wherein said polysaccharide is a polyglucosan and said oxidizing is carried out so that, on a statistical average, at least 15 mole-% of the polycarboxylic acid comprises oxidized anhydroglucose units of the formula I: ##STR2##
Claim 31
Dependent Claim
40 words
The process as claimed in claim 29 wherein the polycarboxylic acid contains at least 25 mole-% of oxidized anhydroglucose units of the formula I in the molecule, the oxidation product being free from significant quantities of other secondary oxidation products.
Claim 32
Dependent Claim
28 words
The process as claimed in claim 30 wherein the polycarboxylic acid contains 35 mole-% to 40 mole-% of oxidized anhydroglucose units of the formula I in the molecule.
Claim 33
Dependent Claim
47 words
The process as claimed in claim 29 wherein the polycarboxylic acid comprises at least one selectively oxidized polyglucosan, the polyglucosan being selected from the group consisting of cellulose and starch, containing up to about 95 mole-% of oxidized anhydroglucose units of the formula I in the molecule.
Claim 34
Dependent Claim
45 words
The process as claimed in claim 29 wherein the polycarboxylic acid comprises at least one selectively oxidized polyglucosan, the polyglucosan being selected from the group consisting of cellulose and starch, containing about 40 mole-% to 80 mole-% of oxidized anhydroglucose units of the formula I.
Claim 35
Dependent Claim
48 words
The process as claimed in claim 1 wherein the carboxyl groups of the polycarboxylic acid are at least partly neutralized after the oxidizing by treatment with an aqueous solution containing at least one member selected from the group consisting of alkali metal hydroxide, ammonium hydroxide and organic base,
Claim 36
Dependent Claim
32 words
In a detergent or cleaning composition, the improvement comprising: introducing the polycarboxylic acids or salts thereof produced by the process claimed in claim 1 as a builder or co-builder in said composition.
Claim 37
Dependent Claim
36 words
The detergent or cleaning composition as claimed in claim 35 wherein the quantity of said polycarboxylic acids or salts thereof is 0.5% by weight to 10% by weight based on the total weight of the composition.
Claim 38
Dependent Claim
34 words
The detergent or cleaning composition of claim 35 wherein the quantity of said polycarboxylic acids or salts thereof is 2% by weight to 7% by weight based on the total weight of the composition.
Claim 39
Dependent Claim
17 words
The detergent or cleaning composition as claimed in claim 35 wherein a zeolite is a principle builder.
Claim 40
Dependent Claim
38 words
The detergent or cleaning composition as claimed in claim 38 wherein the detergent or cleaning composition contains zeolite NaA as the principal builder in a weight ratio to said polycarboxylic acids or salts thereof of 3:1 to 4:1.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1999-07-30 | 2000-01-29 | 2000-07-30 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2003-07-30 | 2004-01-29 | 2004-07-30 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2007-07-30 | 2008-01-29 | 2008-07-30 | $7700.00 | Window Closed / Lapsed |