Patent US4011392A successfully refreshed from Google Patents.
US4011392A
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Mixed starch esters and the use thereof
Assignee: Sherwin Williams Co
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Filing: 1975-09-02
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Granted: 1977-03-08
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Expires: 1995-09-02
Abstract
Abstract This invention is directed to mixed esters of starch and to the method of preparing and the use of said starch esters which are derived from (a) low molecular weight hydrolyzed starch having a plurality of anhydroglucose units and (b) at least about 0.5 mole of acylating agent per anhydroglucose unit consisting of mono- and polycarboxylic acid anhydrides and acyl halides. These anionic esters of starch with average molecular weights ranging up to 100,000 are characterized as having a high degree of substitution, i.e. ranging up to 3.0 wherein at least about 0.1 of the total degree of substitution consist of ester groups having pendant carboxyl radicals derived from anhydrides of polycarboxylic acids.
Inventors
- 👤 Stephen Edward Rudolph
- 👤 Raymond Charles Glowaky
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 17:32
CPC Classifications
C; C08; C08B; C08B31/00; C08B31/02; C08B31/04; C09; C09D; C09D103/00; C09D103/04; C09D103/06
Claims Analysis
Total Claims: 46
Claim 1
Independent Claim
142 words
Mixed esters of starch characterized as having an average molecular weight ranging up to about 100,000 and an average degree of substitution ranging from about 0.5 to 3.0 wherein at least about 0.1 of the total degree of substitution consists of ester groups having pendant carboxyl groups; said esters of starch derived from a. low molecular weight hydrolyzed starch and the derivatives thereof having a plurality of anhydroglucose units and b. at least about 0.5 mole of acylating agent for each anhydroglucose unit of the hydrolyzed starch and the derivatives thereof; said acylating agent consisting of (i) from about 0.1 to 2.9 moles of at least one anhydride of a polycarboxylic acid and (ii) from about 0.1 to 2.9 moles of at least one agent selected from the class consisting of anhydrides of monocarboxylic acids and the acyl halides of monocarboxylic acids.
Claim 2
Dependent Claim
142 words
Mixed esters of starch characterized as having an average molecular weight ranging up to about 100,000 and an average degree of substitution ranging from about 0.5 to 3.0 wherein at least about 0.1 of the total degree of substitution consists of ester groups having pendant carboxyl groups; said esters of starch derived from a. low molecular weight hydrolyzed starch and the derivatives thereof having a plurality of anhydroglucose units and b. at least about 0.5 mole of acylating agent for each anhydroglucose unit of the hydrolyzed starch and the derivatives thereof; said acylating agent consisting of (i) from about 0.1 to 2.9 moles of at least one anhydride of a polycarboxylic acid and (ii) from about 0.1 to 2.9 moles of at least one agent selected from the class consisting of anhydrides of monocarboxylic acids and the acyl halides of monocarboxylic acids.
Claim 3
Dependent Claim
25 words
The mixed esters of starch of claim 1 further characterized in that the anhydride of the polycarboxylic acid is a monoanhydride of a dicarboxylic acid.
Claim 4
Dependent Claim
24 words
The mixed esters of starch of claim 1 further characterized in that the anhydride of the polycarboxylic acid is a monoanhydride of tricarboxylic acid.
Claim 5
Dependent Claim
24 words
The mixed esters of starch of claim 1 further characterized in that the anhydride of the polycarboxylic acid is a dianhydride of tetracarboxylic acid.
Claim 6
Dependent Claim
24 words
The mixed esters of starch of claim 1 further characterized in that at least one of the carboxylic acid anhydrides is a heterocyclic anhydride.
Claim 7
Dependent Claim
22 words
The mixed esters of starch of claim 2 further characterized in that the dicarboxylic acid monoanhydride is an aromatic dicarboxylic acid monoanhydride.
Claim 8
Dependent Claim
30 words
The mixed esters of starch of claim 1 further characterized in that the polycarboxylic acid anhydride is a cyclic dicarboxylic acid anhydride having at least 3 carbon atoms per molecule.
Claim 9
Dependent Claim
22 words
The mixed esters of starch of claim 1 further characterized in that the monocarboxylic acid anhydride is an aliphatic monocarboxylic acid anhydride.
Claim 10
Dependent Claim
31 words
The mixed esters of starch of claim 8 further characterized in that the aliphatic monocarboxylic acid anhydride is a lower aliphatic monocarboxylic acid having 2 to 8 carbon atoms per molecule.
Claim 11
Dependent Claim
22 words
The mixed esters of starch of claim 1 further characterized in that the monocarboxylic acid anhydride is an aromatic monocarboxylic acid anhydride.
Claim 12
Dependent Claim
20 words
The mixed esters of starch of claim 6 further characterized in that the aromatic dicarborylic acid monoanhydride is phthalic anhydride.
Claim 13
Dependent Claim
32 words
The mixed esters of starch of claim 1 further characterized in that at least one of the acyl halides of the monocarboxylic acids is an acyl chloride of an aliphatic monocarboxylic acid.
Claim 14
Dependent Claim
32 words
The mixed esters of starch of claim 1 further characterized in that at least one of the acyl halides of the monocarboxylic acids is an acyl chloride of an aromatic monocarboxylic acid.
Claim 15
Dependent Claim
23 words
The mixed esters of starch of claim 13 further characterized in that the acyl chloride of the aromatic monocarboxylic acid is benzoyl chloride.
Claim 16
Dependent Claim
37 words
The mixed esters of starch of claim 1 further characterized in that said esters are derived from (i) at least one anhydride of a dicarboxylic acid and (ii) at least one anhydride of an aliphatic monocarboxylic acid.
Claim 17
Dependent Claim
26 words
The mixed esters of starch of claim 15 further characterized in that the anhydride of the dicarboxylic acid is an anhydride of an aromatic dicarboxylic acid.
Claim 18
Dependent Claim
34 words
The mixed esters of starch of claim 1 further characterized in that said esters are derived from (i) at least one cyclic dicarboxylic acid anhydride and (ii) at least one aliphatic monocarboxylic acid anhydride.
Claim 19
Dependent Claim
29 words
The mixed esters of starch of claim 1 further characterized in that said esters are derived from (i) at least one aliphatic polycarboxylic acid anhydride and (ii) isatoic anhydride.
Claim 20
Dependent Claim
36 words
The mixed esters of starch of claim 1 further characterized in that said esters are derived from (i) at least one aliphatic dicarboxylic acid anhydride and (ii) at least one acyl halide of a monocarboxylic acid.
Claim 21
Dependent Claim
31 words
The mixed esters of starch of claim 1 further characterized in that the hydrolyzed starch comprises branched and linear anhydroglucose units and has a dextrose equivalent value ranging up to 40.
Claim 22
Dependent Claim
21 words
The mixed esters of starch of claim 20 further characterized in that the hydrolyzed starch consists essentially of linear anhydroglucose units.
Claim 23
Dependent Claim
35 words
The mixed esters of starch of claim 1 further characterized in that the esters of starch are derived from about 0.5 to 3.0 moles of the acylating agent for each anhydroglucose unit of the starch.
Claim 24
Dependent Claim
54 words
The mixed esters of starch of claim 1 further characterized as having average molecular weights ranging up to about 80,000 and an average degree of substitution of at least 1.0 wherein at least about 0.1 of the degree of substitution consists of ester groups having pendant carboxyl groups derived from anhydrides of dicarboxylic acids.
Claim 25
Dependent Claim
150 words
Mixed esters of starch characterized as having an average molecular weight ranging up to about 100,000 and an average degree of substitution ranging from about 1.0 to 3.0 wherein at least about 0.1 of the total degree of substitution consists of ester groups having pendant carboxyl groups; said esters of starch derived from a. low molecular weight hydrolyzed starch and the derivatives thereof having a dextrose equivalent value ranging up to about 40 and a plurality of anhydroglucose units and b. at least about 1.0 mole of acylating agent for each anhydroglucose unit of hydrolyzed starch and the derivatives thereof; said acylating agent consisting of (i) from about 0.3 to 2.3 mole of at least one anhydride of a polycarboxylic acid and (ii) from about 0.7 to 2.7 moles of at least one agent selected from the class consisting of anhydrides of monocarboxylic acids and acyl halides of monocarboxylic acids.
Claim 26
Dependent Claim
150 words
Mixed esters of starch characterized as having an average molecular weight ranging up to about 100,000 and an average degree of substitution ranging from about 1.0 to 3.0 wherein at least about 0.1 of the total degree of substitution consists of ester groups having pendant carboxyl groups; said esters of starch derived from a. low molecular weight hydrolyzed starch and the derivatives thereof having a dextrose equivalent value ranging up to about 40 and a plurality of anhydroglucose units and b. at least about 1.0 mole of acylating agent for each anhydroglucose unit of hydrolyzed starch and the derivatives thereof; said acylating agent consisting of (i) from about 0.3 to 2.3 mole of at least one anhydride of a polycarboxylic acid and (ii) from about 0.7 to 2.7 moles of at least one agent selected from the class consisting of anhydrides of monocarboxylic acids and acyl halides of monocarboxylic acids.
Claim 27
Dependent Claim
159 words
A process for preparing mixed esters of starch characterized as having an average molecular weight ranging up to about 100,000 and an average degree of substitution ranging from about 0.5 to 3.0, wherein at least about 0.1 of the total degree of substitution consists of ester groups having pendant carboxyl groups; which comprises reacting in an organic medium substantially free of water at temperatures ranging up to about 150° C; a. low molecular weight hydrolyzed starch and the derivatives thereof having a plurality of anhydroglucose units and b. at least about 0.5 mole of acylating agent for each anhydroglucose unit of the hydrolyzed starch and the derivatives thereof; said acylating agent consisting of (i) from about 0.1 to 2.9 moles of at least one anhydride of a polycarboxylic acid and (ii) from about 0.1 to 2.9 of at least one agent selected from the class consisting of the anhydrides of monocarboxylic acids and the acyl halides of monocarboxylic acids.
Claim 28
Dependent Claim
159 words
A process for preparing mixed esters of starch characterized as having an average molecular weight ranging up to about 100,000 and an average degree of substitution ranging from about 0.5 to 3.0, wherein at least about 0.1 of the total degree of substitution consists of ester groups having pendant carboxyl groups; which comprises reacting in an organic medium substantially free of water at temperatures ranging up to about 150° C; a. low molecular weight hydrolyzed starch and the derivatives thereof having a plurality of anhydroglucose units and b. at least about 0.5 mole of acylating agent for each anhydroglucose unit of the hydrolyzed starch and the derivatives thereof; said acylating agent consisting of (i) from about 0.1 to 2.9 moles of at least one anhydride of a polycarboxylic acid and (ii) from about 0.1 to 2.9 of at least one agent selected from the class consisting of the anhydrides of monocarboxylic acids and the acyl halides of monocarboxylic acids.
Claim 29
Dependent Claim
19 words
The process of claim 25 further characterized in that at least one of the anhydrides is a heterocyclic anhydride.
Claim 30
Dependent Claim
19 words
The process of claim 25 further characterized in that the polycarboxylic acid anhydride is an aromatic dicarboxylic acid anhydride.
Claim 31
Dependent Claim
19 words
The process of claim 25 further characterized in that the monocarboxylic acid anhydride is an aliphatic monocarboxylic acid anhydride.
Claim 32
Dependent Claim
25 words
The process of claim 25 further characterized in that the acyl halide of the monocarboxylic acid is an acyl chloride of an aliphatic monocarboxylic acid.
Claim 33
Dependent Claim
36 words
The process of claim 25 further characterized in that the mixed esters of starch are derived from (i) at least one anhydride of a dicarboxylic acid and (ii) at least one anhydride of a monocarboxylic acid.
Claim 34
Dependent Claim
23 words
The process of claim 30 further characterized in that the anhydride of the monocarboxylic acid is an anhydride of an aliphatic monocarboxylic acid.
Claim 35
Dependent Claim
38 words
The process of claim 25 further characterized in that the mixed esters of starch are derived from (i) at least one anhydride of an aromatic polycarboxylic acid and (ii) at least one anhydride of an aliphatic monocarboxylic acid.
Claim 36
Dependent Claim
18 words
The process of claim 25 further characterized in that the organic medium contains at least one organic solvent.
Claim 37
Dependent Claim
14 words
The process of claim 33 further characterized in that the organic solvent comprises pyridine.
Claim 38
Dependent Claim
18 words
The process of claim 25 further characterized in that the reaction temperature ranges up to about 85° C.
Claim 39
Dependent Claim
27 words
The mixed esters of starch of claim 1 further characterized in that the low molecular weight hydrolyzed starch derivative has a D. S. value less than 0.1.
Claim 40
Dependent Claim
23 words
The mixed esters of starch of claim 36 further characterized in that the low molecular weight hydrolyzed starch derivative is an ester derivative.
Claim 41
Dependent Claim
23 words
The mixed esters of starch of claim 36 further characterized in that the low molecular weight hydrolyzed starch derivative is an ether derivative.
Claim 42
Dependent Claim
24 words
The process of claim 25 further characterized in that the low molecular weight hydrolyzed starch derivative has a D. S. value less than 0.1.
Claim 43
Dependent Claim
23 words
The mixed esters of starch of claim 1 further characterized in that the pendant carboxyl groups are reacted with an inorganic metal compound.
Claim 44
Dependent Claim
24 words
The mixed esters of starch of claim 40 further characterized in that the inorganic metal compound is an alkali or alikaline earth metal compound.
Claim 45
Dependent Claim
21 words
The mixed esters of starch of claim 1 further characterized in that the pendant carboxyl groups are reacted with an amine.
Claim 46
Dependent Claim
20 words
The process of claim 25 further characterized in that the pendant carboxyl groups are reacted with an inorganic metal compound.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-03-07 | 1980-09-06 | 1981-03-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-03-07 | 1984-09-06 | 1985-03-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-03-07 | 1988-09-06 | 1989-03-08 | $7700.00 | Window Closed / Lapsed |