Epoxy-functional polymeric microbeads

• US 6,602,602 B1
• Filed: 05/08/2002
• Issued: 08/05/2003
• Est. Priority Date: 04/26/1999
• Status: Active Grant

• Current Assignee: Rensselaer Polytechnic Institute
• Original Assignee: Rensselaer Polytechnic Institute
• Inventors: Crivello, James Vincent
• Primary Examiner(s): Moore, Margaret G.
• Application Number:
  US10/019,835
• Time in Patent Office: 454 Days
• Field of Search: 522/170, 428/402, 424/489
• US Class Current: 428/402
• CPC Class Codes: B01D 15/08 Selective adsorption, e.g. chromatography
• CPC Class Codes: B01J 20/26 Synthetic macromolecular compounds
• CPC Class Codes: C08G 59/306 containing silicon
• CPC Class Codes: C08G 59/3254 containing atoms other than carbon, hydrogen, oxygen or nitrogen
• CPC Class Codes: C08J 2363/00 Characterised by the use of epoxy resins; Derivatives of epoxy resins
• CPC Class Codes: C08J 3/12 Powdering or granulating
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: G03F 7/075 Silicon-containing compounds
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

Abstract

Epoxy-functionallized polymeric microbeads and dispersions thereof may be prepared using a cationic non-aqueous dispersion-suspension photopolymerization. The polymeric microbeads may be further modified with a variety of additional groups by reaction with various reagents with the epoxy moities.

Claims

1. A population of polymeric microbeads bearing epoxy functionality on surfaces thereof and having a narrow particle size distribution, such that the particle size of greater than 90% of the polymeric microbeads in said population is equal to ±

20% of the mean particle size, said epoxy functionality arising from one or more multifunctional epoxy monomers chosen from the group consisting of 3,4-epoxycyclohexyl methyl-3′

,4′

-epoxycyclohexane arboxylate, bis-(3,4-epoxycyclohexyl) adipate, 4-vinylcyclohexene dioxide, epoxy silicone resins, limonene dioxide, dicyclopentadiene dioxide, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, 1,4-butanediol diglycidyl ether, diglycidyl ethers of tetrabromo-bisphenol-A, epoxy cresol novolacs, epoxy phenol novolacs, and diglycidyl phthalate.

2. A population of polymeric microbeads according to claim 1, wherein the epoxy functionality arises from one or more multifunctional epoxy monomers chosen from the group consisting of:

3,4-epoxycyclohexyl methyl-3′

,4′

-epoxycyclohexane carboxylate, 4-vinylcyclohexene dioxide and the compounds of formula I and II;

3. Polymeric microbeads according to claim 1 prepared by cationic suspension photopolymerization of 3,4-epoxycyclohexylmethyl 3′

,4′

-epoxycyclohexanecarboxylate in a mineral oil suspending medium, in the presence of (4-decyloxyphenyl) phenyliodonium hexafluoroantimonate.

4. Polymeric microbeads according to claim 1, prepared by cationic suspension photopolymerization of T8 in a mineral oil suspending medium, in the presence of (4-decyloxyphenyl) phenyliodonium hexafluoroantimonate.

5. Polymeric microbeads according to claim 1, prepared by cationic suspension photopolymerization of 4-vinylcyclohexene dioxide in a mineral oil suspending medium, in the presence of (4-decyloxyphenyl) phenyliodonium hexafluoroantimonate.

6. Polymeric microbeads prepared by suspension photopolymerization of one or more multifunctional epoxy monomers chosen from the group consisting of:

3,4-epoxycyclohexylmethyl-3′

,4′

-epoxycyclohexane carboxylate, bis-(3,4-epoxycyclohexyl)adipate, 4-vinylcyclohexene dioxide, epoxy silicone resins, limonene dioxide, dicyclopentadiene dioxide, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, 1,4-butanediol diglycidyl ether, diglycidyl ethers of tetrabromo-bisphenol-A, epoxy cresol novolacs, epoxy phenol novolacs, and diglycidyl phthalate.

7. Polymeric microbeads according to claim 6, wherein the multifunctional epoxy monomers are chosen from the group consisting of:

3,4-epoxycyclohexylmethyl-3′

,4′

-epoxycyclohexane carboxylate, 4-vinylcyclohexene dioxide and the compounds of formula I and II;

8. Polymeric microbeads according to claim 6, prepared by suspension polymerization of one or more multifunctional epoxy monomers and one or more cationically polymerizible monomers.

9. Polymeric microbeads according to claim 6, wherein said cationically polymerizible comonomers are chosen from the group consisting of:

1,2-epoxytetradecane, 1,2-epoxydecane, 1,2-epoxydodecane, epoxidized soybean oil, epoxidized linseed oil, vinyl ethers, 1-propenyl ethers, 1-butenyl ethers, styrene, indene, acenapthalene, α

-methylstyrene, N-vinyl carbazole, oxazoline, tetrahydrofuran, 7-oxabicyclo[2.2.1]heptane, oxetane, substituted oxetanes, thirane, and aziridine.

10. A process for the preparation of polymeric microbeads comprising:

(A) forming a dispersion comprising one or more multifunctional epoxy monomers in a non-aqueous suspending medium in the presence of a photoinitiator; and

(B) exposing the dispersion to a source of light to induce polymerization.

11. The process of claim 10, wherein the photoinitiator is a cationic photoinitiator.

12. The process of claim 10, wherein the one or more multifunctional epoxy monomers are chosen from the group consisting of 3,4-epoxycyclohexylmethyl-3′

,4′

-epoxycyclohexane carboxylate, bis-(3,4-epoxycyclohexyl)adipate, 4-vinylcyclohexene dioxide, epoxy silicone resins, limonene dioxide, dicyclopentadiene dioxide, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, 1,4-butanediol diglycidyl ether, diglycidyl ethers of tetrabromo-bisphenol-A, epoxy cresol novolacs, epoxy phenol novolacs, and diglycidyl phthalate.

13. The process of claim 12, wherein the multifunctional epoxy monomers are chosen from the group consisting of:

3,4-epoxycyclohexylmethyl-3′

,4′

-epoxycyclohexane carboxylate, 4-vinylcyclohexene dioxide and the compounds of formula I and II;

14. The process of claim 10, wherein the dispersion additionally comprises one or more cationically polymerizible comonomers.

15. The process of claim 14, wherein said cationically polymerizible comonomers are chosen from the group consisting of 1,2-epoxytetradecane, 1,2-epoxydecane, 1,2-epoxydodecane, epoxidized soybean oil, epoxidized linseed oil, vinyl ethers, 1-propenyl ethers, 1-butenyl ethers, styrene, indene, acenapthalene, α

-methylstyrene, N-vinyl carbazole, oxazoline, tetrahydrofuran, 7-oxabicyclo[2.2.1]heptane, oxetane, substituted oxetanes, thirane, and aziridine.

16. The process of claim 10, wherein the polymeric microbeads.have a particle size of from 1 μ

m to 500 μ

m.

17. The process of claim 16, wherein the polymeric microbeads have a particle size of from 10 μ

m to 300 μ

m.

18. A method for attaching functional groups to the surface of a polymeric microbead comprising:

(A) preparing a dispersion of polymeric microbeads bearing residual epoxy groups on surfaces thereof by;

(a) forming a dispersion comprising one or more multifunctional epoxy monomers in a non-aqueous suspending medium in the presence of a photoinitiator; and

(b) exposing the dispersion to a source of light to induce polymerization; and

(B) contacting the polymericmicrobeads with a compound which is reactive toward the residual epoxy groups.

19. The method of claim 18, wherein the compound which is reactive toward the residual epoxy groups is chosen from the group consisting of:

acid anhydrides, alcohols, amides, amines, carboxylic acids, isocyanates, Grignard reagents, and thiols.

20. The method of claim 18, wherein the photoinitiator is a cationic photoinitiator.

21. The method of claim 18, wherein the one or more multifunctional epoxy monomers are chosen from the group consisting of:

3,4-epoxycyclohexylmethyl-3′

,4′

-epoxycyclohexane carboxylate, bis-(3,4-epoxycyclohexyl)adipate, 4-vinylcyclohexene dioxide, epoxy silicone resins, limonene dioxide, dicyclopentadiene dioxide, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, 1,4-butanediol diglycidyl ether, diglycidyl ethers of tetrabromo-bisphenol-A, epoxy cresol novolacs, epoxy phenol novolacs, and diglycidyl phthalate.

22. The method of claim 21, wherein the multifunctional epoxy monomers are chosen from the group consisting of:

3,4-epoxycyclohexylmethyl-3′

,4′

-epoxycyclohexane carboxylate, 4-vinylcyclohexene dioxide and the compounds of formula I and II;

23. The method of claim 18, wherein the dispersion additionally comprises one or more cationically polymerizible comonomers.

24. The method of claim 23, wherein said cationically polymerizible comonomers are chosen from the group consisting of 1,2-epoxytetradecane, 1,2-epoxydecane, 1,2-epoxydodecane, epoxidized soybean oil, epoxidized linseed oil, vinyl ethers, 1-propenyl ethers, 1-butenyl ethers, styrene, indene, acenapthalene, α

-methylstyrene, N-vinyl carbazole, oxazoline, tetrahydrofuran, 7-oxabicyclo[2.2.1]heptane, oxetane, substituted oxetanes, thirane, and aziridine.

25. The method of claim 18, wherein the polymeric microbeads have a particle size of from 1 μ

m to 500 μ

m.

26. The method of claim 25, wherein the polymeric microbeads have a particle size of from 10 μ

m to 300 μ

m.