US4115332A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Water-absorbent starch copolymerizates
Assignee: Primary Products Ingredients Americas LLC
•
Filing: 1977-06-20
•
Granted: 1978-09-19
•
Expires: 1997-06-20
Abstract
Abstract Water-absorbent, starch copolymerizates are prepared by copolymerizing an ethylenically unsaturated starch with other ethylenically unsaturated monomers which contain water-attractant groups or precursors of water-attractant groups. The water-absorbent starch copolymerizates may be easily prepared into the desired configuration for a particular end-use or combined with other substrates or carriers. The unpolymerized starch and monomers or precursors thereof may be applied or incorporated into a suitable carrier or substrate (e.g., cellulosic materials such as textiles, papers, etc.) and copolymerized in situ to provide a composite article of unitary construction with the water-absorbent starch copolymerizate permanently bonded or affixed thereto.
Inventors
- 👤 Austin H. Young
- 👤 Frank Verbanac
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 17:51
CPC Classifications
C; C08; C08F; C08F290/00; C08F290/08; C08F290/10
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
181 words
A water-absorbent starch copolymerizate which is capable of absorbing several times its own weight in water, said starch copolymerizate comprising the copolymerizate product of ethylenically unsaturated starch molecules and ethylenically unsaturated monomers with said ethylenically unsaturated monomers forming a connective polymeric linkage between said copolymerized starch molecules to provide a non-linear lattice of a plurality of starch chains linked together by polymeric linkages represented by the formula: ##STR13## wherein Starch represents a starch chain of D-glucose units, Z represents an organo group which links the ##STR14## to the carbon atom of the starch chain by a sulfur atom or an oxygen atom, R is a member selected from the group consisting of hydrogen and a monovalent organic radical, M represents a plurality of copolymerized ethylenically unsaturated monomers with "p" representing the number of copolymerized monomeric units in said linkage, (W) is a water-attractant group linked to the polymeric linkage and "n" represents the number of (W) moieties contained within the polymeric linkage of said copolymerized monomers with the number of (W) moieties being sufficient to impart water-absorbency properties to said copolymerizate.
Claim 2
Dependent Claim
181 words
A water-absorbent starch copolymerizate which is capable of absorbing several times its own weight in water, said starch copolymerizate comprising the copolymerizate product of ethylenically unsaturated starch molecules and ethylenically unsaturated monomers with said ethylenically unsaturated monomers forming a connective polymeric linkage between said copolymerized starch molecules to provide a non-linear lattice of a plurality of starch chains linked together by polymeric linkages represented by the formula: ##STR13## wherein Starch represents a starch chain of D-glucose units, Z represents an organo group which links the ##STR14## to the carbon atom of the starch chain by a sulfur atom or an oxygen atom, R is a member selected from the group consisting of hydrogen and a monovalent organic radical, M represents a plurality of copolymerized ethylenically unsaturated monomers with "p" representing the number of copolymerized monomeric units in said linkage, (W) is a water-attractant group linked to the polymeric linkage and "n" represents the number of (W) moieties contained within the polymeric linkage of said copolymerized monomers with the number of (W) moieties being sufficient to impart water-absorbency properties to said copolymerizate.
Claim 3
Dependent Claim
46 words
The water-absorbent starch copolymerizate according to claim 1 wherein the Z organo group consists essentially of a ##STR15## and R' is at least one member selected from the group consisting of hydrogen and a mono-organo group joined directly to the nitrogen atom by a monovalent bond.
Claim 4
Dependent Claim
55 words
The water-absorbent starch composition according to claim 1 wherein the ethylenically unsaturated starch molecules consist essentially of starch molecules and appendant ethylenic unsaturated groups of a molecular weight ranging from greater than 50 to less than 300 and the degree of substitution of said ethylenically unsaturated appendant groups range from about 0.002 to about 0.1.
Claim 5
Dependent Claim
25 words
The water-absorbent starch according to claim 3 wherein "W" is at least one member selected from the group consisting of anion, cation, nonion and zwitterion.
Claim 6
Dependent Claim
54 words
The composition according to claim 4 wherein the weight of ethylenically unsaturated monomer in said copolymerizate ranges from about 10 to about 1000 parts by weight for each 100 parts by weight of copolymerized ethylenically unsaturated starch and from about 25 to about 100% of the copolymerized ethylenically unsaturated monomer contains the "W" substitutent.
Claim 7
Dependent Claim
37 words
The water-absorbent starch composition according to claim 4 wherein the copolymerized ethylenically unsaturated starch consists essentially of amylopectin hydrolyzate with a degree of substitution of said starch ethylenic unsaturated groups ranging from about 0.005 to about 0.05.
Claim 8
Dependent Claim
86 words
The water-absorbent starch according to claim 4 wherein the copolymerized ethylenically unsaturated starch consists essentially of an acrylamide starch having a D.S. ranging from about 0.005 to about 0.05 and a D.E. ranging from about 0.25 to about 15, and the copolymerizate contains 100 parts by weight copolymerized ethylenically unsaturated starch hydrolyzate, from about 100 to about 750 parts copolymerized ethylenically unsaturated monomer which contain "W" groups and from 0 to about 200 parts by weight of copolymerized ethylenically unsaturated monomers devoid of said "W" groups.
Claim 9
Independent Claim
239 words
A method for preparing a water-absorbent starch copolymerizate, comprised of a plurality of starch chains linked together by polymeric linkages represented by the formula: ##STR16## wherein Starch represents a starch chain of D-glucose units, Z represents an organo group which links the ##STR17## to the carbon atom of the starch chain by a sulfur atom or an oxygen atom, R is a member selected from the group consisting of hydrogen and a monovalent organic radical, M represents a plurality of copolymerized ethylenically unsaturated monomers which contain a sufficient number of (W) groups to impart water-absorbency to said copolymerized product, "p'" represents the number of copolymerized ethylenically unsaturated monomers linking together said starch chains, said method comprising copolymerizing: (a) starch chains containing appendant, terminal ethylenic unsaturated groups represented by the formula: ##STR18## wherein Starch, Z and R are as defined above, and "a" represents the degree of substitution of said terminal unsaturated groups on said starch chain, and (b) ethylenically unsaturated monomers represented by the formula: M'--W').sub.n' wherein M' represents an ethylenically unsaturated monomer, "(W')" represents at least one member selected from the group consisting of water-attractant group or a precursor of a water-attractant group, and n' in an integer with the proviso that when the copolymerized M'--(W') n' monomer consists essentially of a precursor of said water-attractant group, a sufficient number of the precursor groups are derivatized to a water-attractant group to impart water-absorbing properties to said starch copolymerizate.
Claim 10
Independent Claim
239 words
A method for preparing a water-absorbent starch copolymerizate, comprised of a plurality of starch chains linked together by polymeric linkages represented by the formula: ##STR16## wherein Starch represents a starch chain of D-glucose units, Z represents an organo group which links the ##STR17## to the carbon atom of the starch chain by a sulfur atom or an oxygen atom, R is a member selected from the group consisting of hydrogen and a monovalent organic radical, M represents a plurality of copolymerized ethylenically unsaturated monomers which contain a sufficient number of (W) groups to impart water-absorbency to said copolymerized product, "p'" represents the number of copolymerized ethylenically unsaturated monomers linking together said starch chains, said method comprising copolymerizing: (a) starch chains containing appendant, terminal ethylenic unsaturated groups represented by the formula: ##STR18## wherein Starch, Z and R are as defined above, and "a" represents the degree of substitution of said terminal unsaturated groups on said starch chain, and (b) ethylenically unsaturated monomers represented by the formula: M'--W').sub.n' wherein M' represents an ethylenically unsaturated monomer, "(W')" represents at least one member selected from the group consisting of water-attractant group or a precursor of a water-attractant group, and n' in an integer with the proviso that when the copolymerized M'--(W') n' monomer consists essentially of a precursor of said water-attractant group, a sufficient number of the precursor groups are derivatized to a water-attractant group to impart water-absorbing properties to said starch copolymerizate.
Claim 11
Dependent Claim
50 words
The method according to claim 8 wherein (W') is at least one water-attractant group or a precursor of a water-attractant group selected from the group of anion, cation, nonion, and zwitterion, and Z represents an organo group which links the --CRH-- group to the starch chain by an oxy moiety.
Claim 12
Dependent Claim
45 words
The method according to claim 9 wherein Z comprises an organo group represented by the formula; ##STR19## and R' is at least one member selected from the group consisting of hydrogen and a mono-organo group joined directly to the nitrogen atom by a monovalent bond.
Claim 13
Dependent Claim
45 words
The method according to claim 10 wherein the appendant ethylenic unsaturated groups of the starch chains consist essentially of groups having a molecular weight ranging from about 75 to about 150 and "a" represents a degree of substitution ranging from about 0.002 to about 0.1.
Claim 14
Dependent Claim
52 words
The method according to claim 10 wherein from about 25% to 100% by weight of ethylenically unsaturated monomers contain the "W'" group and the copolymerized weight of ethylenically unsaturated monomer ranges from about 10 to about 1000 parts by weight ethylenically unsaturated monomer for each 100 parts by weight ethylenically unsaturated starch.
Claim 15
Dependent Claim
30 words
The method according to claim 12 wherein the ethylenically unsaturated starch consists essentially of amylopectin hydrolyzate and "a" represents a degree of substitution ranging from about 0.003 to about 0.05.
Claim 16
Dependent Claim
84 words
The method according to claim 9 wherein the ethylenically unsaturated starch consists essentially of an acrylamido starch hydrolyzate having a D.S. ranging from about 0.005 to about 0.10 and a D.E. ranging from about 0.25 to about 15, and 100 parts by weight of the ethylenically unsaturated starch hydrolyzate is copolymerized with from about 100 to about 750 parts copolymerized ethylenically unsaturated monomers containing the "W'" groups and from 0 to about 200 parts by weight ethylenically unsaturated monomers free from said "W'" groups.
Claim 17
Dependent Claim
40 words
The method according to claim 14 wherein Z represents an organo group having the formula: ##STR20## with R' representing either hydrogen or a lower alkyl group of 1 to 3 carbon atoms inclusive, and R represents either hydrogen or methyl.
Claim 18
Dependent Claim
33 words
The method according to claim 15 wherein the starch chains consist essentially of an amylopectin hydrolyzate and "W" represents at least one member selected from the group consisting of an anion and cation.
Claim 19
Dependent Claim
35 words
The method according to claim 8 which includes the additional steps of applying the unpolymerized ethylenically unsaturated starch and ethylenically unsaturated monomers to a substrate and thereafter copolymerizing in situ the applied starch and monomers.
Claim 20
Dependent Claim
35 words
The method according to claim 9 which includes the additional steps of applying the unpolymerized ethylenically unsaturated starch and ethylenically unsaturated monomers to a substrate and thereafter copolymerizing in situ the applied starch and monomers.
Claim 21
Dependent Claim
35 words
The method according to claim 11 which includes the additional steps of applying the unpolymerized ethylenically unsaturated starch and ethylenically unsaturated monomers to a substrate and thereafter copolymerizing in situ the applied starch and monomers.
Claim 22
Dependent Claim
35 words
The method according to claim 14 which includes the additional steps of applying the unpolymerized ethylenically unsaturated starch and ethylenically unsaturated monomers to a substrate and thereafter copolymerizing in situ the applied starch and monomers.
Claim 23
Dependent Claim
35 words
The method according to claim 16 which includes the additional steps of applying the unpolymerized ethylenically unsaturated starch and ethylenically unsaturated monomers to a substrate and thereafter copolymerizing in situ the applied starch and monomers.
Claim 24
Dependent Claim
19 words
The water-absorbent substrate of a unitary construction comprised of a substrate and the water-absorbent starch copolymerizate of claim 1.
Claim 25
Dependent Claim
34 words
In a water-absorbent substrate wherein the substrate is impregnated, coated or combined into a composite stucture of unitary construction with a water-absorbent composition, the improvement which comprises the water-absorbent starch copolymerizate of claim 5.
Claim 26
Dependent Claim
80 words
The water-absorbent substrate according to claim 23 wherein the water-absorbent starch copolymerizate consists essentially of the copolymerization product of 100 parts by weight of acrylamide starch having a D.S. ranging from about 0.005 to about 0.1 and a D.E. ranging from about 0.25 to about 15, from about 100 to about 750 parts copolymerized ethylenically unsaturated monomer which contain "W" groups and from 0 to about 200 parts by weight of copolymerized ethylenically unsaturated monomers devoid of said "W" groups.
Claim 27
Dependent Claim
229 words
A copolymerizable starch-containing composition which can be converted into a water-absorbent starch copolymerizate having a plurality of starch chains linked together by polymeric linkages represented by the formula: ##STR21## wherein Starch represents a starch chain of D-glucose units, Z represents an organo group which links the ##STR22## to the carbon atom of the starch chain by a sulfur atom or an oxygen atom, R is a member selected from the group consisting of hydrogen and a monovalent organic radical, M represents a plurality of copolymerized ethylenically unsaturated monomers with "p" representing the number of copolymerized monomeric units in said linkage, (W) is a water-attractant group linked to the polymeric linkage and "n" represents the number of (W) moieties contained within the polymeric linkage of said copolymerized monomers with the number of (W) moieties being sufficient to impart water-absorbency properties to said copolymerizate, said copolymerizable composition comprising: (a) starch chains containing appendant, terminal ethylenic unsaturated groups represented by the formula: ##STR23## wherein Starch, Z and R are as defined above, and "a" represents the degree of substitution of said terminal unsaturated groups on said starch chain, and (b) ethylenically unsaturated monomers represented by the formula: M'--W').sub.n' wherein M' represents an ethylenically unsaturated monomer, "(W')" represents at least one member selected from the group consisting of a water-attractant group or a precursor of a water-attractant group, and n' is an integer.
Claim 28
Dependent Claim
229 words
A copolymerizable starch-containing composition which can be converted into a water-absorbent starch copolymerizate having a plurality of starch chains linked together by polymeric linkages represented by the formula: ##STR21## wherein Starch represents a starch chain of D-glucose units, Z represents an organo group which links the ##STR22## to the carbon atom of the starch chain by a sulfur atom or an oxygen atom, R is a member selected from the group consisting of hydrogen and a monovalent organic radical, M represents a plurality of copolymerized ethylenically unsaturated monomers with "p" representing the number of copolymerized monomeric units in said linkage, (W) is a water-attractant group linked to the polymeric linkage and "n" represents the number of (W) moieties contained within the polymeric linkage of said copolymerized monomers with the number of (W) moieties being sufficient to impart water-absorbency properties to said copolymerizate, said copolymerizable composition comprising: (a) starch chains containing appendant, terminal ethylenic unsaturated groups represented by the formula: ##STR23## wherein Starch, Z and R are as defined above, and "a" represents the degree of substitution of said terminal unsaturated groups on said starch chain, and (b) ethylenically unsaturated monomers represented by the formula: M'--W').sub.n' wherein M' represents an ethylenically unsaturated monomer, "(W')" represents at least one member selected from the group consisting of a water-attractant group or a precursor of a water-attractant group, and n' is an integer.
Claim 29
Dependent Claim
130 words
The copolymerizable composition according to claim 25 wherein "Z" comprises an organo group represented by the formula: ##STR24## and R' is at least one member selected from the group consisting of hydrogen and a mono-organo group joined directly to the nitrogen atom by a monovalent bond, (W') is at least one water-attractant group or a precursor of a water-attractant group selected from the group of anion, cation, nonion, and zwitterion, and the copolymerizable starch composition contains 100 parts by weight of the ethylenically unsaturated starch having a D.S. from about 0.005 to about 0.10, from about 100 to about 750 parts by weight ethylenically unsaturated monomer which contains the "W'" group and from 0 to about 200 parts by weight ethylenically unsaturated monomers which are free of said "W'" groups.
Claim 30
Dependent Claim
43 words
The copolymerizate composition according to claim 26 wherein the starch chain consists essentially of an amylopectin hydrolyzate having a D.E. ranging from about 0.25 to about 10 and R represents at least one member selected from the group consisting of hydrogen and methyl.
Claim 31
Dependent Claim
226 words
In a method of absorbing water with a water-absorbent substance wherein a water-absorbent substance is placed into a medium which contains water and causing the water-absorbent substance to hydrate and absorb several times its dry weight in water, the improvement which comprises a water-absorbent starch copolymerizate which is capable of absorbing several times its own weight in water with said starch copolymerizate consisting essentially of the copolymerizate product of ethylenically unsaturated starch molecules and ethylenically unsaturated monomers with said ethylenically unsaturated monomers forming a connective polymeric linkage between said copolymerized starch molecules to provide a non-linear lattice of a plurality of starch chains linked together by polymeric linkages represented by the formula: ##STR25## wherein Starch represents a starch chain of D-glucose units, Z represents an organo group which links the ##STR26## to the carbon atom of the starch chain by a sulfur atom or an oxygen atom, R is a member selected from the group consisting of hydrogen and a monovalent organic radical, M represents a plurality of copolymerized ethylenically unsaturated monomers with "p" representing the number of copolymerized monomeric units in said linkage, (W) is a water-attractant group linked to the polymeric linkage and "n" represents the number of (W) moieties contained within the polymeric linkage of said copolymerized monomers with the number of (W) moieties being sufficient to impart water-absorbency properties to said copolymerizate.
Claim 32
Dependent Claim
226 words
In a method of absorbing water with a water-absorbent substance wherein a water-absorbent substance is placed into a medium which contains water and causing the water-absorbent substance to hydrate and absorb several times its dry weight in water, the improvement which comprises a water-absorbent starch copolymerizate which is capable of absorbing several times its own weight in water with said starch copolymerizate consisting essentially of the copolymerizate product of ethylenically unsaturated starch molecules and ethylenically unsaturated monomers with said ethylenically unsaturated monomers forming a connective polymeric linkage between said copolymerized starch molecules to provide a non-linear lattice of a plurality of starch chains linked together by polymeric linkages represented by the formula: ##STR25## wherein Starch represents a starch chain of D-glucose units, Z represents an organo group which links the ##STR26## to the carbon atom of the starch chain by a sulfur atom or an oxygen atom, R is a member selected from the group consisting of hydrogen and a monovalent organic radical, M represents a plurality of copolymerized ethylenically unsaturated monomers with "p" representing the number of copolymerized monomeric units in said linkage, (W) is a water-attractant group linked to the polymeric linkage and "n" represents the number of (W) moieties contained within the polymeric linkage of said copolymerized monomers with the number of (W) moieties being sufficient to impart water-absorbency properties to said copolymerizate.
Claim 33
Dependent Claim
123 words
The improvement according to claim 28 wherein the Z organo group consists essentially of a ##STR27## and R' is at least one member selected from the group consisting of hydrogen and a mono-organo group joined directly to the nitrogen atom by a monovalent bond, "W" is at least one member selected from the group consisting of anion, cation, nonion and zwitterion, the weight of copolymerized ethylenically unsaturated monomer in said copolymerizate ranges from about 10 to about 1000 parts by weight for each 100 parts by weight of copolymerized ethylenically unsaturated starch and from about 25 to about 100% of the copolymerized ethylenically unsaturated monomer contains the "W" substituent and "a" represents a degree of substitution ranging from about 0.003 to about 0.1.
Claim 34
Dependent Claim
84 words
The improvement according to claim 29 wherein the copolymerized unsaturated starch consists essentially of an acrylamide starch having a D.S. ranging from about 0.005 to about 0.05 and a D.E. ranging from about 0.25 to about 15, and the copolymerizate contains 100 parts by weight copolymerized ethylenically unsaturated starch hydrolyzate, from about 100 to about 750 parts copolymerized ethylenically unsaturated monomer which contain "W" groups and from 0 to about 200 parts by weight of copolymerized ethylenically unsaturated monomers free of said "W" groups.
Claim 35
Dependent Claim
29 words
The improvement according to claim 30 wherein the starch chain consists essentially of a amylopectin hydrolyzate having a D.E. of less than 10 and R represents a methyl group.
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) | 1981-09-18 | 1982-03-20 | 1982-09-19 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-09-18 | 1986-03-20 | 1986-09-19 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-09-18 | 1990-03-20 | 1990-09-19 | $7700.00 | Window Closed / Lapsed |