Crosslinked methacrylic anhydride copolymers

• US 5,539,071 A
• Filed: 06/06/1995
• Issued: 07/23/1996
• Est. Priority Date: 05/29/1992
• Status: Expired due to Term

• Current Assignee: Rohm and Haas Company (Dow, Inc.)
• Original Assignee: Rohm and Haas Company (Dow, Inc.)
• Inventors: Steffler, Larry W.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): Cheng, Wu C.
• Application Number:
  US08/467,674
• Time in Patent Office: 413 Days
• Field of Search: 526/208, 526/212, 526/303.1, 526/307.6, 526/316, 526/321, 526/328.5, 526/347
• US Class Current: 526/208
• CPC Class Codes: B01D 15/3809 of the antigen-antibody type, e.g. protein A, G, L chromatography
• CPC Class Codes: B01J 20/26 Synthetic macromolecular compounds
• CPC Class Codes: B01J 39/20 obtained by reactions only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: B01J 43/00 Amphoteric ion-exchange, i.e. using ion-exchangers having cationic and anionic groups; Use of material as amphoteric ion-exchangers; Treatment of material for improving their amphoteric ion-exchange properties ion-exchange chromatography processes B01D15/36
• CPC Class Codes: C08F 20/08 Anhydrides
• CPC Class Codes: C08F 220/08 Anhydrides
• CPC Class Codes: C08F 2800/20 as weight or mass percentages
• CPC Class Codes: C08F 2810/20 leading to a crosslinking, either explicitly or inherently
• CPC Class Codes: C08F 8/12 Hydrolysis
• CPC Class Codes: C08F 8/32 by reaction with amines
• CPC Class Codes: C08F 8/44 Preparation of metal salts or ammonium salts
• CPC Class Codes: C08J 2333/02 Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• CPC Class Codes: C08J 9/20 by suspension polymerisation in the presence of the blowing agent

Abstract

Suspension-polymerized, crosslinked copolymers of methacrylic anhydride yield beads suitable as precursors for weak-acid and other ion exchange resins, affinity chromatography materials and other materials which require spherical polymers having reactive anhydride groups for their preparation. Both gel and macroporous beads of these copolymers may be made by the process of the invention.

Claims

1. A process for making crosslinked, spherical copolymer beads having a particle size between about 10 μ

m and about 2 mm which comprises

a. suspending droplets of a monomer mixture comprising methacrylic anhydride in an amount that is at least 50% by weight of the monomer, a crosslinking monomer and a monomer-soluble, free-radical polymerization initiator in an aqueous suspending medium,

b. heating the droplets above the decomposition temperature of the polymerization initiator until the monomer mixture has polymerized to form copolymer beads, and

c. separating the copolymer beads from the suspending medium.

2. The process of claim 1 wherein the copolymer beads are macroporous and the monomer mixture further comprises a porogen.

3. The process of claim 2 wherein the porogen is selected from the group consisting of iso-octane, methyl isobutyl ketone, methyl isobutyl carbinol, xylene, toluene and di-n-butyl ether.

4. The process of claim 3 wherein the porogen is iso-octane.

5. The process of claim 3 wherein the porogen is methyl isobutyl ketone.

6. The process of claim 3 wherein the porogen is methyl isobutyl carbinol.

7. The process of claim 3 wherein the porogen is xylene.

8. The process of claim 3 wherein the porogen is toluene.

9. The process of claim 1 wherein the crosslinking monomer is an aliphatic, polyethylenically unsaturated monomer.

10. The process of claim 9 wherein the aliphatic crosslinking monomer is selected from the group consisting of ethylene glycol dimethacrylate, ethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, divinylketone, allyl acrylate, diallyl maleate, diallyl fumarate, diallyl succinate, diallyl carbonate, diallyl malonate, diallyl oxalate, diallyl adipate, diallyl sebacate, divinylsebacate, N,N'"'"'-methylenediacrylamide and N,N'"'"'-methylene dimethacrylamide.

11. The process of claim 10 wherein the aliphatic crosslinking monomer ethylene glycol dimethacrylate.

12. The process of claim 10 wherein the aliphatic crosslinking monomer ethylene glycol diacrylate.

13. The process of claim 10 wherein the aliphatic crosslinking monomer trimethylolpropane diacrylate.

14. The process of claim 10 wherein the aliphatic crosslinking monomer trimethylolpropane triacrylate.

15. The process of claim 10 wherein the aliphatic crosslinking monomer trimethylolpropane dimethacrylate.

16. The process of claim 10 wherein the aliphatic crosslinking monomer trimethylolpropane trimethacrylate.

17. The process of claim 1 wherein the crosslinking monomer is an aromatic crosslinking monomer.

18. The process of claim 17 wherein the aromatic crosslinking monomer is selected from the group consisting of divinylbenzene, trivinylbenzene, divinyltoluenes, divinylnaphthalenes, diallyl phthalate, divinylxylene and divinylethylbenzene.

19. The process of claim 18 wherein the aromatic crosslinking monomer is divinylbenzene.

20. The process of claim 1 wherein the polymerization initiator has a decomposition point below about 60°

C.

21. The process of claim 1 wherein the polymerization initiator is a peroxide initiator or a hydroperoxide initiator.

22. The process of claim 21 wherein the peroxide or hydroperoxide polymerization initiator is selected from the group consisting of benzoyl peroxide, t-butyl hydroperoxide, cumene peroxide, α

-cumyl peroxyneodecanoate, tetralin peroxide, acetyl peroxide, caproyl peroxide, t-butyl perbenzoate, t-butyl diperphthalate, di(4-t-butylcyclohexyl)peroxydicarbonate and methyl ethyl ketone peroxide.

23. The process of claim 22 wherein the initiator is α

-cumyl peroxyneodecanoate.

24. The process of claim 22 wherein the initiator is di(4-t-butylcyclohexyl)peroxydicarbonate.

25. The process of claim 21 wherein the peroxide initiator or hydroperoxide initiator is present at a level of from about 0.01 percent to about 3 percent, by weight, based on the total weight of the monomers.

26. The process of claim 1 wherein the polymerization initiator is an azo initiator.

27. The process of claim 26 wherein the azo polymerization initiator is selected from the group consisting of azodiisobutyronitrile, azodiisobutyramide, azobis(α

,α

-dimethylvaleronitrile), azobis(α

-methylbutyronitrile ), dimethyl azobis(methylvalerate), diethyl azobis(methylvalerate) and dibutyl azobis(methylvalerate).

28. The process of claim 26 wherein the azo polymerization initiator is present at from about 0.01 percent to about 2 percent, by weight, based on the total weight of the monomers.