Highly cross-linked polymeric supports

• US 5,910,554 A
• Filed: 06/06/1997
• Issued: 06/08/1999
• Est. Priority Date: 06/16/1995
• Status: Expired due to Term

• Current Assignee: Regents of The University of Minnesota (University of Minnesota)
• Original Assignee: Regents of The University of Minnesota (University of Minnesota)
• Inventors: Kempe, Maria, Barany, George
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): SAROFIM, NABIL F
• Application Number:
  US08/793,212
• Time in Patent Office: 732 Days
• Field of Search: 526/320
• US Class Current: 526/320
• CPC Class Codes: C07K 1/042 characterised by the nature of the carrier
• CPC Class Codes: C08F 20/28 containing no aromatic rings in the alcohol moiety
• CPC Class Codes: C08F 22/1006 of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
• CPC Class Codes: C08F 290/062 Polyethers

Abstract

A polymer useful as a solid support for a variety of applications is provided. The polymer is prepared from a composition comprising at least one type of olefinic monomer and a multifunctional (meth)acrylate crosslinker of the following formula (I): ##STR1## wherein: (a) R¹, R², and R³ are each independently hydrogen or a methyl group;

(b) R⁴ is hydrogen or an organic group or substituent that can interact in the polymerization and/or crosslinking process or is nonreactive under the conditions of the polymerization and/or crosslinkling process;

(c ) R⁷, R⁸, and R⁹ are each independently --CH₂ --CH₂ --, --CH₂ --CH₂ --CH₂, --CH₂ --CH(CH₃)--, or --CH(CH₃)--CH₂ --;

(d) each of 1, m, and n is no greater than about 100 with the proviso that at least one of 1, m, or n is at least 1.

Claims

1. A polymer prepared from a composition comprising a multifunctional (meth)acrylate crosslinker of the following formula (I):

##STR4## wherein;

(a) R¹, R², and R³ are each independently hydrogen or a methyl group;

(b) R⁴ is hydrogen or an organic group or substituent that can interact in the polymerization and/or crosslinking process or is nonreactive under the conditions of the polymerization and/or crosslinking process;

(c) R⁷, R⁸, and R⁹ are each independently --CH₂ --CH₂ --, --CH₂ --CH₂ --CH₂ --, CH₂ --CH(CH₃)--, or --CH(CH₃)--CH₂ --; and

(d) each of 1, m, and n is no greater than about 100 with the proviso that at least one of 1, m, or n is at least 1.

2. The polymer of claim 1 prepared from a composition further comprising an olefinic monomer.

3. The polymer of claim 2 wherein the olefinic monomer is functionalized with an amino group.

4. The polymer of claim 3 wherein the amino functionalized olefinic monomer is allylamine, 2-aminoethyl methacrylate, or 4-aminostyrene.

5. The polymer of claim 1 wherein each of 1, m, and n is 1-30.

7. The polymer of claim 1 wherein the multifunctional (meth)acrylate crosslinker is used in an amount of at least about 25 mole- %.

8. The polymer of claim 1 wherein the composition further comprises a secondary olefin-containing crosslinker.

9. The polymer of claim 8 wherein the secondary crosslinker is selected from the group consisting of a diacrylate, a dimethacrylate, a diacrylamide, a dimethacrylamide, and a divinylbenzene.

10. The polymer of claim 1 which is in the form of beads.

6. The polymer of claim I wherein the multifunctional (meth)acrylate crosslinker is used in an amount of at least about 10 mole- %.

11. A method of preparing a crosslinked polymer comprising:

(a) combining an olefin-containing monomer and a multifunctional (meth)acrylate crosslinker in a solvent, wherein the multifunctional (meth)acrylate crosslinker has the following formula (I);

##STR5## wherein;

(i) R¹, R², and R³ are each independently hydrogen or a methyl group;

(ii) R⁴ is hydrogen or an organic group or substituent that can interact in the polymerization and/or crosslinking process or is nonreactive under the conditions of the polymerization and/or crosslinking process;

(iii) R⁷, R⁸, and R⁹ are each independently --CH₂ --CH₂ --, --CH₂ --CH₂ --CH₂ --, --CH₂ --CH(CH₃)--, or --CH(CH₃)--CH₂ --; and

(iv) each of 1, m, and n is no greater than about 100 with the proviso that at least one of l, m, or n is at least 1; and

(b) exposing the mixture to conditions to effect polymerization.

12. The method of claim 11 wherein the mixture is exposed to ultraviolet radiation.

13. The method of claim 11 wherein the mixture further includes a free-radical initiator.

14. The method of claim 11 wherein the olefin-containing monomer is functionalized.

15. The method of claim 14 wherein the olefin-containing monomer is functionalized with an amino group.

16. The method of claim 15 wherein the amino functionalized olefinic monomer is allylamine, 2-aminoethyl methacrylate, or 4-aminostyrene.

17. The method of claim 11 wherein the multifunctional (meth)acrylate crosslinker is used in an amount of at least about 10 mole- %.

18. The method of claim 11 wherein the polymerization is carried out at a temperature of about -30 to about 120°

C.

19. The method of claim 11 wherein the polymer is prepared in the form of beads.

20. A method of synthesizing an organic molecule on a solid polymeric support comprising:

(a) providing a solid polymeric support prepared from a composition comprising a multifunctional (meth)acrylate crosslinker of the following formula (I);

##STR6## wherein;

(i) R¹, R², and R³ are each independently hydrogen or a methyl group;

(ii) R⁴ is hydrogen or an organic group or substituent that can interact in the polymerization and/or crosslinking process or is nonreactive under the conditions of the polymerization and/or crosslinking process;

(iii) R⁷, RW, and R⁹ are each independently --CH₂ --CH₂ --, --CH₂ --CH₂ --CH₂ --, --CH,--CH(CH₃)--, or --CH(CH₃)--CH₂ --; and

(iv) each of 1, m, and n is no greater than about 100 with the proviso that at least one of l, m, or n is at least 1; and

(b) attaching an organic group to the solid polymeric support at the functional group site.

21. The method of claim 20 wherein the organic group of step (b) is an amino acid.

22. The method of claim 20 wherein the solid polymeric support is prepared from a composition further comprising a functionalized olefinic monomer.

23. The method of claim 22 wherein the functionalized olefinic monomer is an amino functionalized olefinic monomer.

24. The method of claim 20 which is carried out in a continuous-flow system.