US4060506A
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Starch acrylamides and the method for preparing the same
Assignee: Primary Products Ingredients Americas LLC
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Filing: 1976-04-27
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Granted: 1977-11-29
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Expires: 1996-04-27
Abstract
Abstract The invention relates to starch acrylamides containing polymerizable pendant acrylamide groups. The hydrophilic or hydrophobic properties of the starch can be altered or modified by the acrylamide groups or the type of starch chain. The starch acrylamides can be homopolymerized or copolymerized with other ethylenically unsaturated monomers as well as other cross-linking reagents to provide water-resistant, clear, flexible coatings or shaped articles. The hydrophilic starch acrylamide hydrolyzates herein readily disperse into water at a high solids level to provide low-viscosity pastes which may be used as a vehicle to prepare flexible, water-insoluble starch-based coatings. The starch acrylamides may be prepared by etherifying a starch with N-methylol acrylamides in the presence of an acid catalyst and a polymerization inhibitor.
Inventors
- 👤 Frank Verbanac
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 00:39
CPC Classifications
C; C08; C08B; C08B31/00
Claims Analysis
Total Claims: 45
Claim 1
Independent Claim
46 words
A starch acrylamide suitable for use in preparing starch polymerizates which contain recurring and interpolymerized starch acrylamide units, said starch acrylamide comprising a starch chain and appendant acrylamide groups contiguously attached to said starch chain with said appendant group being characterized as containing terminal ##STR8## moieties.
Claim 2
Dependent Claim
46 words
A starch acrylamide suitable for use in preparing starch polymerizates which contain recurring and interpolymerized starch acrylamide units, said starch acrylamide comprising a starch chain and appendant acrylamide groups contiguously attached to said starch chain with said appendant group being characterized as containing terminal ##STR8## moieties.
Claim 3
Dependent Claim
33 words
The starch acrylamide according to claim 2 wherein the starch chain is characterized as containing an average of at least one appendant acrylamide group for each 1000 D-glucose units of said starch chain.
Claim 4
Dependent Claim
20 words
The starch acrylamide according to claim 2 wherein the appendant acrylamide group has a molecular weight of less than 400.
Claim 5
Dependent Claim
18 words
The starch acrylamide according to claim 2 wherein the starch acrylamide is characterized as being dispersible in water.
Claim 6
Dependent Claim
36 words
The starch acrylamide according to claim 4 wherein the acrylamide D.S. ranges from about 0.03 to about 0.2 and the individual appendant acrylamide groups have an average molecular weight ranging from about 100 to about 200.
Claim 7
Dependent Claim
123 words
The starch acrylamide according to claim 1 wherein said starch acrylamide comprises a starch acrylamide represented by the formula: ##STR9## wherein starch represents a starch chain, R 1 is a member selected from the group consisting of hydrogen and a monoorgano group joined directly to the nitrogen atom by a monovalent bond, R represents a member selected from the group consisting of hydrogen and monoorgano group linked to alpha carbon atom of the ethylenically unsaturated group by a monovalent linkage, Q represents an organo group which divalently joins the D group with the acrylamide group; D is a member selected from the group consisting of sulfur and oxygen, and "a" represents the number of acrylamide substituents per anhydroglucose unit of said starch molecule.
Claim 8
Dependent Claim
40 words
The starch acrylamide according to claim 7 wherein D is an oxy group, Q is an alkylene moiety linking the starch D group with the nitrogen atom of said acrylamide group and "a" represents a D.S. of at least 0.0005.
Claim 9
Dependent Claim
36 words
The starch acrylamide according to claim 6 wherein D is an oxy group, R and R 1 are members selected from the group consisting of hydrogen and a monoorgano group containing less than 8 carbon atoms.
Claim 10
Dependent Claim
37 words
The starch acrylamide according to claim 8 wherein R is a member selected from the group consisting of hydrogen and methyl, R 1 is hydrogen and "a" represents a D.S. ranging from about 0.03 to about 0.5.
Claim 11
Dependent Claim
146 words
The starch acrylamide according to claim 1 wherein said starch acrylamide consists essentially of a starch acrylamide represented by the structural formula: ##STR10## wherein starch represents a starch chain, R 1 is a member selected from the group consisting of hydrogen and a monoorgano group joined directly to the nitrogen atom by a monovalent bond, R represents a member selected from the group consisting of hydrogen and monoorgano group linked to alpha carbon atom of the ethylenically unsaturated group by a monovalent linkage, Q 1 represents an organo group which divalently joins the D group with the acrylamide group; D is a member selected from the group consisting of sulfur and oxygen with D linking said Q 1 group to the starch chain, "a" represents the number of acrylamide substituents per anhydroglucose unit of said starch molecule and "n" is an integer of 0 to 1.
Claim 12
Dependent Claim
20 words
The starch acrylamide according to claim 10 wherein "n" is zero and "a" represents a D.S. of at least 0.001.
Claim 13
Dependent Claim
33 words
The starch acrylamide according to claim 10 wherein D is an oxy group, R is a member selected from the group consisting of hydrogen and a lower alkyl and R 1 is hydrogen.
Claim 14
Dependent Claim
19 words
The starch acrylamide according to claim 12 wherein "a" represents a D.S. ranging from about 0.003 to about 0.2.
Claim 15
Dependent Claim
17 words
The starch acrylamide according to claim 13 wherein the starch chain consists essentially of a starch hydrolyzate.
Claim 16
Dependent Claim
38 words
The starch acrylamide according to claim 10 wherein the starch arylamide is characterized as forming a flowable starch acrylamide paste when one part by weight starch acrylamide is admixed with 100 parts by weight water at 95° C.
Claim 17
Dependent Claim
43 words
The starch acrylamide according to claim 15 wherein "n" is zero, D is an oxy group, R 1 is hydrogen and R is a member selected from the group consisting of hydrogen and methyl and "a" represents a D.S. of at least 0.003.
Claim 18
Dependent Claim
27 words
The starch acrylamide according to claim 16 wherein said starch acrylamide is pasted in a sufficient amount of water to provide a homogeneous starch acrylamide paste thereof.
Claim 19
Independent Claim
67 words
A method for preparing a starch acrylamide characterized as containing terminal ##STR11## moieties, said method comprising reacting a starch which contains reactive hydrogen atoms with an N-methylol reactant wherein the N-methylol reactant is characterized as containing a ##STR12## grouping, with the reaction being conducted in the presence of an acid catalyst in an amount sufficient to catalyze the condensation reaction between the starch and the N-methylol reactant.
Claim 20
Independent Claim
67 words
A method for preparing a starch acrylamide characterized as containing terminal ##STR11## moieties, said method comprising reacting a starch which contains reactive hydrogen atoms with an N-methylol reactant wherein the N-methylol reactant is characterized as containing a ##STR12## grouping, with the reaction being conducted in the presence of an acid catalyst in an amount sufficient to catalyze the condensation reaction between the starch and the N-methylol reactant.
Claim 21
Dependent Claim
30 words
The method according to claim 18 wherein the reaction is conducted in the presence of a polymerization inhibitor in an amount sufficient to inhibit the polymerization of said starch acrylamide.
Claim 22
Dependent Claim
19 words
The method according to claim 19 wherein the condensation reaction is conducted at a temperature greater than 50° C.
Claim 23
Dependent Claim
41 words
The method according to claim 20 wherein the reaction is conducted in the presence of a sufficient amount of N-methylol reactant and for a period of time sufficient to provide a starch acrylamide having an acrylamide D.S. of at least 0.03.
Claim 24
Dependent Claim
35 words
The method according to claim 21 wherein a homogeneous blend of the starch, the catalyst, polymerization inhibitor and N-methylol reactant is dry reacted at a temperature ranging from about 75° C. to about 150° C.
Claim 25
Dependent Claim
16 words
The method according to claim 22 wherein contaminants are removed from the dry reacted starch acrylamide.
Claim 26
Dependent Claim
55 words
The method according to claim 19 wherein the starch is etherified with a N-methylol reactant represented by the formula: ##STR13## wherein R 1 is a member selected from the group consisting of hydrogen and a monovalent organo moiety, and R is a member selected from the group consisting of hydrogen and a monovalent organo moiety.
Claim 27
Dependent Claim
31 words
The method according to claim 24 wherein the etherification reaction is conducted under reaction conditions sufficient to provide a starch acrylamide having a D.S. ranging from about 0.005 to about 2.0.
Claim 28
Dependent Claim
34 words
The method according to claim 24 wherein the reaction is conducted in the presence of an acid catalyst in an amount sufficient to catalyze the etherification reaction between the starch and the N-methylol reactant.
Claim 29
Dependent Claim
35 words
The method according to claim 26 wherein a homogenous blend of the starch, N-methylol reactant, polymerization inhibitor and acid catalyst is dry reacted at a temperature ranging from about 75° C. to about 150° C.
Claim 30
Dependent Claim
25 words
The method according to claim 27 wherein R is a member selected from the group consisting of hydrogen and methyl and R 1 is hydrogen.
Claim 31
Dependent Claim
41 words
The method according to claim 28 wherein the starch reacted with the methylol reactants is characterized as forming a homogeneous starch paste when one part by weight of the starch is admixed with 100 parts by weight water at 95° C.
Claim 32
Dependent Claim
41 words
The method according to claim 29 wherein the starch comprises a starch hydrolyzate and the dry reaction is conducted under etherification conditions sufficient to provide a starch acrylamide having an acrylamide D.S. within the range of about 0.03 to about 0.2.
Claim 33
Dependent Claim
56 words
In a method for polymerizing an ethylenically unsaturated starch derivative in the presence of a polymerization initiator, the improvement which comprises interpolymerizing a starch acrylamide wherein the starch acrylamide is characterized as comprising a starch chain and appendant acrylamide groups contiguously attached to said chain with the appendant groups being characterized as containing terminal ##STR14## moieties.
Claim 34
Dependent Claim
56 words
In a method for polymerizing an ethylenically unsaturated starch derivative in the presence of a polymerization initiator, the improvement which comprises interpolymerizing a starch acrylamide wherein the starch acrylamide is characterized as comprising a starch chain and appendant acrylamide groups contiguously attached to said chain with the appendant groups being characterized as containing terminal ##STR14## moieties.
Claim 35
Dependent Claim
35 words
The method according to claim 31 wherein the acrylamide D.S. of said starch acrylamide ranges from about 0.03 to about 1 and the average molecular weight of the appendant acrylamide groups is less than 400.
Claim 36
Dependent Claim
124 words
The method according to claim 31 wherein said starch acrylamide comprises a starch acrylamide represented by the formula: ##STR15## wherein starch represents a starch chain, R 1 is a member selected from the group consisting of hydrogen and a monoorgano group linked to the nitrogen atom by a monovalent carbon linkage, R represents a member selected from the group consisting of hydrogen and monoorgano group linked to the alpha carbon atom of the ethylenically unsaturated group by a monovalent carbon linkage, Q represents an organo group which divalently links the D group to the acrylamide group; D is a member selected from the group consisting of sulfur and oxygen, and "a" represents the number of acrylamide substituents per anhydroglucose unit of said starch molecule.
Claim 37
Dependent Claim
42 words
The method according to claim 33 wherein R is a member selected from the group consisting of hydrogen and methyl, D is an oxy group and R 1 is hydrogen and "a" represents a D.S. ranging from about 0.03 to about 0.5.
Claim 38
Dependent Claim
12 words
The method according to claim 34 wherein Q is a methylene group.
Claim 39
Dependent Claim
36 words
The method according to claim 35 wherein the starch acrylamide is characterized as forming a homogeneous starch paste when one part of the starch acrylamide is admixed with 100 parts by weight water at 95° C.
Claim 40
Dependent Claim
98 words
A polymerized starch acrylamide composition comprising recurring and interpolymerized starch acrylamide units represented by the sturcture: ##STR16## wherein starch represents a starch chain, R 1 is a member selected from the group consisting of hydrogen and a monoorgano group, R represents a member selected from the group consisting of hydrogen and a monoorgano group, Q represents an organo group which divalently links the D group with the nitrogen atom; D is a member selected from the group consisting of sulfur and oxygen, and "a" represents the number of interpolymerized acrylamide substituents per anhydroglucose unit of said starch chain.
Claim 41
Dependent Claim
98 words
A polymerized starch acrylamide composition comprising recurring and interpolymerized starch acrylamide units represented by the sturcture: ##STR16## wherein starch represents a starch chain, R 1 is a member selected from the group consisting of hydrogen and a monoorgano group, R represents a member selected from the group consisting of hydrogen and a monoorgano group, Q represents an organo group which divalently links the D group with the nitrogen atom; D is a member selected from the group consisting of sulfur and oxygen, and "a" represents the number of interpolymerized acrylamide substituents per anhydroglucose unit of said starch chain.
Claim 42
Dependent Claim
78 words
The polymerized starch acrylamide composition according to claim 37 wherein the composition is characterized as yielding a centrifugal residue of at least about 80% of the total polymerized starch composition acrylamide weight when one part by weight of the polymerized starch acrylamide composition is immersed in 100 parts by weight water at 75° C. for 60 minutes and the immersed polymerized starch acrylamide and water is then subjected to a centrifugal force of 1000 g's for 10 minutes.
Claim 43
Dependent Claim
24 words
The polymerized starch acrylamide composition according to claim 37 wherein "a" ranges from about 0.003 to about 1.0 and D is an oxy group.
Claim 44
Dependent Claim
66 words
The polymerized starch acrylamide composition according to claim 38 wherein D is an oxy group, and Q is linked to the nitrogen atom by a methylene moiety, R is a member selected from the group consisting of hydrogen and a lower alkyl, R 1 is a member selected from the group consisting of hydrogen and lower alkyl, and "a" ranges from about 0.003 to about 0.5.
Claim 45
Dependent Claim
42 words
The polymerized starch acrylamide composition according to claim 38 wherein R is a member selected from the group consisting of hydrogen and methyl, R 1 is hydrogen, Q is methylene, D is oxy and "a" ranges from about 0.05 to about 0.2.
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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) | 1980-11-28 | 1981-05-30 | 1981-11-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-11-28 | 1985-05-30 | 1985-11-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-11-28 | 1989-05-30 | 1989-11-29 | $7700.00 | Window Closed / Lapsed |