US4871824A
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Variably crosslinked polymeric supports
Assignee: 3M Co
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Filing: 1988-02-19
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Granted: 1989-10-03
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Expires: 2008-02-19
Abstract
Abstract Azlactone-functional polymer beads are useful reactive supports for the attachment of functional materials to provide novel adduct beads. The adduct beads are useful as complexing agents, catalysts, polymeric reagents, chromatographic supports, and as enzyme- or other biomacromolecule-bearing supports. Novel carboxylate-functional polymer beads, are intermediates in the preparation of the azlactone-functional beads. Azlactone-functional beads have units of the formula: ##STR1## wherein R 1 is H or CH 3 , R 2 and R 3 independently can be an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon and 0 to 3 S, N, and nonperoxidic O heteroatoms, or R 2 and R 3 taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms, and n is an integer 0 or 1, the azlactone functional beads having more than 5 and up to 99 molar parts of crosslinking monomer incorporated therein.
Inventors
- 👤 Steven M. Heilmann
- 👤 Jerald K. Rasmussen
- 👤 Larry R. Krepski
- 👤 Dean S. Milbrath
- 👤 Patrick L. Coleman
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 06:01
CPC Classifications
A; A61; A61K; A61K39/00; A61K39/395; A61K39/39516; A61K39/39525; B; B01; B01J; B01J20/00; B01J20/22; B01J20/26; C; C07; C07K; C07K17/00; C07K17/02; C07K17/08; C08; C08F; C08F20/00; C08F20/02; C08F20/52; C08F20/54; C08F20/58; C08F8/00; C12; C12N; C12N11/00; C12N11/02; C12N11/08; C12N11/082; C12N11/087
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
23 words
A crosslinked, hydrophilic, azlactone-functional polymer bead having more than 5 and up to 99 molar parts of ethyienically unsaturated crosslinking monomer incorporated therein.
Claim 2
Dependent Claim
23 words
A crosslinked, hydrophilic, azlactone-functional polymer bead having more than 5 and up to 99 molar parts of ethyienically unsaturated crosslinking monomer incorporated therein.
Claim 3
Dependent Claim
183 words
An azlactone-functional polymer bead which is the reaction product of: (a) a carboxylate-functional polymeric bead which is the polymerization product of: (i) 0 to 89 molar parts of at least one free radically addition polymerizable, water soluble monomer; (ii) 1 to less than 95 molar parts of a water soluble salt of N-(meth)acryloylamino acid having the formula ##STR15## wherein R 1 is H or CH 3 , R 2 and R 3 independently are an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon and 0 to 3 S, N, and nonperoxidic O heteroatoms, or R 2 and R 3 taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms, n is an integer 0 or 1, and M is a water-solubilizing cation; and (iii) greater than 5 and up to 99 molar parts of at least one ethylenically unsaturated crosslinking monomer; and (b) a cyclizing agent.
Claim 4
Dependent Claim
183 words
An azlactone-functional polymer bead which is the reaction product of: (a) a carboxylate-functional polymeric bead which is the polymerization product of: (i) 0 to 89 molar parts of at least one free radically addition polymerizable, water soluble monomer; (ii) 1 to less than 95 molar parts of a water soluble salt of N-(meth)acryloylamino acid having the formula ##STR15## wherein R 1 is H or CH 3 , R 2 and R 3 independently are an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon and 0 to 3 S, N, and nonperoxidic O heteroatoms, or R 2 and R 3 taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms, n is an integer 0 or 1, and M is a water-solubilizing cation; and (iii) greater than 5 and up to 99 molar parts of at least one ethylenically unsaturated crosslinking monomer; and (b) a cyclizing agent.
Claim 5
Dependent Claim
103 words
An azlactone-functional bead according to claim 1 having units of the formula: ##STR16## wherein R 1 is H or CH 3 , R 2 and R 3 independently can be an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon and unitary heteroatoms, or R 2 and R 3 taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms, and n is an integer 0 or 1.
Claim 6
Dependent Claim
12 words
The azlactone-functional bead according to claim 3 wherein R 1 is hydrogen.
Claim 7
Dependent Claim
15 words
The azlactone-functional bead according to claim 3 wherein R 2 and R 3 are methyl.
Claim 8
Dependent Claim
44 words
A carboxylate-functional polymeric bead which is the reaction product of: (i) 0 to 89 molar parts of free radically addition polymerizable, water soluble monomers, (ii) 1 to less than 95 molar parts of a water soluble salt of N-(meth)acryloylamino acid having the formula. ##STR17##
Claim 9
Dependent Claim
44 words
A carboxylate-functional polymeric bead which is the reaction product of: (i) 0 to 89 molar parts of free radically addition polymerizable, water soluble monomers, (ii) 1 to less than 95 molar parts of a water soluble salt of N-(meth)acryloylamino acid having the formula. ##STR17##
Claim 10
Dependent Claim
38 words
A carboxylate-functional bead according to claim 6 having units of the formula: ##STR18## wherein R 1 , R 2 , R 3 and n are as previously defined, and M is a water-solubilizing cation, and n=0 or 1.
Claim 11
Dependent Claim
21 words
The carboxylate-functional bead according to claim 7 wherein R 1 , R 2 , and R 3 are methyl and n=0.
Claim 12
Dependent Claim
82 words
An adduct bead having units of the formula ##STR19## wherein R 1 , R 2 , R 3 , and n are as previously defined, n=0 or 1, X is --O--, --S--, --NH--, or --NR 4 wherein R 4 is alkyl or aryl, and G is the residue of HXG which performs the complexing, catalyzing, separating, or reagent function of the adduct beads, said bead containing greater than 5 and up to 99 molar parts of ethylenically unsaturated crosslinking monomer incorporated therein.
Claim 13
Dependent Claim
82 words
An adduct bead having units of the formula ##STR19## wherein R 1 , R 2 , R 3 , and n are as previously defined, n=0 or 1, X is --O--, --S--, --NH--, or --NR 4 wherein R 4 is alkyl or aryl, and G is the residue of HXG which performs the complexing, catalyzing, separating, or reagent function of the adduct beads, said bead containing greater than 5 and up to 99 molar parts of ethylenically unsaturated crosslinking monomer incorporated therein.
Claim 14
Dependent Claim
21 words
The adduct bead according to claim 9 wherein R 1 , R 2 , and R 3 are methyl and n=0.
Claim 15
Dependent Claim
21 words
The adduct bead according to claim 9 wherein HXG is selected from the group consisting of biomacromolecules, catalysts, reagents, and dyes.
Claim 16
Dependent Claim
12 words
The adduct bead according to claim 9 which is a complexing agent.
Claim 17
Dependent Claim
12 words
The adduct bead according to claim 9 which is a chromatographic support.
Claim 18
Dependent Claim
11 words
The adduct bead according to claim 9 which is a catalyst.
Claim 19
Dependent Claim
12 words
The adduct bead according to claim 9 which is a polymeric reagent.
Claim 20
Independent Claim
175 words
A method comprising the steps of: (a) polymerizing together (i) 0 to 89 molar parts of at least one free radically addition polymerizable, water soluble monomer, (ii) 1 to less than 95 molar parts of at least one water soluble salt of N-(meth)acryloylamino acid having the formula ##STR20## wherein R 1 is H or CH 3 , R 2 and R 3 independently are an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon and 0 to 3 S, N, and nonperoxidic O heteroatoms, or R 2 and R 3 taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms, n is an integer 0 or 1, and M is a water-solubilizing cation, and (iii) greater than 5 and up to 99 molar parts of at least one ethylenically unsaturated crosslinking monomer, (b) isolating the resulting carboxylate-functional polymer beads.
Claim 21
Independent Claim
175 words
A method comprising the steps of: (a) polymerizing together (i) 0 to 89 molar parts of at least one free radically addition polymerizable, water soluble monomer, (ii) 1 to less than 95 molar parts of at least one water soluble salt of N-(meth)acryloylamino acid having the formula ##STR20## wherein R 1 is H or CH 3 , R 2 and R 3 independently are an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon and 0 to 3 S, N, and nonperoxidic O heteroatoms, or R 2 and R 3 taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms, n is an integer 0 or 1, and M is a water-solubilizing cation, and (iii) greater than 5 and up to 99 molar parts of at least one ethylenically unsaturated crosslinking monomer, (b) isolating the resulting carboxylate-functional polymer beads.
Claim 22
Dependent Claim
28 words
The method according to claim 16 further comprising the steps of: (c) reacting said carboxylate-functional beads with a cyclizing agent, and (d) isolating the resulting azlactone-functional polymer beads.
Claim 23
Dependent Claim
38 words
The method according to claim 17 further comprising the steps of: (e) reacting the azlactone-functional polymer beads with a functional material capable of reacting with said azlactone in a ring-opening reaction, and (f) isolating the resulting adduct beads.
Claim 24
Dependent Claim
15 words
The method according to claim 18 wherein said step (e) takes place in aqueous solution.
Claim 25
Dependent Claim
22 words
The method according to claim 18 wherein said functional material is selected from the group consisting of proteins, catalysts, reagents, and dyes.
Claim 26
Dependent Claim
93 words
An adduct bead having units of the formula ##STR21## wherein R 1 , R 2 , R 3 , and n are as previously defined, n=0 or 1, X is --O--, --S--, --NH--, or --NR 4 wherein R 4 is alkyl or aryl, and G is the residue of HXG which performs the complexing, catalyzing, separating, or reagent function of the adduct beads, said bead containing greater than 20 and up to 99 molar parts of crosslinking monomer incorporated therein and having a degree of swelling less than 3 times the unswelled volume.
Claim 27
Dependent Claim
93 words
An adduct bead having units of the formula ##STR21## wherein R 1 , R 2 , R 3 , and n are as previously defined, n=0 or 1, X is --O--, --S--, --NH--, or --NR 4 wherein R 4 is alkyl or aryl, and G is the residue of HXG which performs the complexing, catalyzing, separating, or reagent function of the adduct beads, said bead containing greater than 20 and up to 99 molar parts of crosslinking monomer incorporated therein and having a degree of swelling less than 3 times the unswelled volume.
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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) | 1992-10-02 | 1993-04-03 | 1993-10-03 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-10-02 | 1997-04-03 | 1997-10-03 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-10-02 | 2001-04-03 | 2001-10-03 | $7700.00 | Window Closed / Lapsed |