High purity resins for thiol-ene polymerizations and method for producing same

• US 5,399,624 A
• Filed: 04/30/1993
• Issued: 03/21/1995
• Est. Priority Date: 12/21/1990
• Status: Expired due to Fees

• Current Assignee: Loctite Corporation (Henkel AG & Co KGaA)
• Original Assignee: Loctite Corporation (Henkel AG & Co KGaA)
• Inventors: Grabek, Paul J., Jacobine, Anthony F., Glaser, David M.
• Primary Examiner(s): Yoon, Tae H.
• Application Number:
  US08/056,128
• Time in Patent Office: 690 Days
• Field of Search: 528/489, 525/289, 525/350, 525/368, 525/369, 525/290, 526/280, 526/283
• US Class Current: 525/289
• CPC Class Codes: B29C 64/135 the energy source being concentrated, e.g. scanning lasers or focused light sources
• CPC Class Codes: C08F 6/02 Neutralisation of the polymerisation mass, e.g. killing the catalyst short-stopping C08F2/42 also removal of catalyst residues
• CPC Class Codes: C08G 75/045 from mercapto compounds and unsaturated compounds
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/0275 with dithiol or polysulfide compounds

Abstract

A treatment method for polyene resins used in thiol-ene formulations, especially norbornene resins, significantly stabilizes thiol-ene compositions made from batches of polyene resin which otherwise give compositions with poor dark stability. The treatment comprises contacting the polyene with an amphoteric treating agent selected from the group consisting of silicated magnesium oxide, basic aluminum oxide, silica gel, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, barium oxide, and barium hydroxide, and then separating the resin from the treating agent prior to mixture with a polythiol to form a thiol-ene composition. The treatment method significantly reduces ionic content in polyene resins, particularly chloride ion but also sodium and potassium ions. Consequently, treatment is also beneficial with polyene resins which do not produce substantial dark stability problems. Reduction of the ionic content of the resin is desirable to produce cured thiolene polymers with low electrical conductivity and low corrosiveness.

Claims

1. A treatment method for a polyene, the polyene being a plural norbornene functional compound and the method comprising contacting the untreated polyene with an amphoteric treating agent selected from the group consisting of silicated magnesium oxide, basic aluminum oxide, silica gel, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, barium oxide, and barium hydroxide for a contact time and the separating the treated polyene from the treating agent, the contact time being a sufficient time to yield a Cl^- level in the polyene of less than 1.0 ppm after separation from the treating agent.

2. A method as in claim 1 wherein said untreated polyene has a Cl^- level of 3 ppm or greater.

3. A method as in claim 1 wherein said contact time is a sufficient time to produce a Cl^- level of 0.5 ppm or less.

4. A method as in claim 1 wherein said amphoteric treating agent is selected from the group consisting of silicated magnesium oxide, basic aluminum oxide and silica gel.

5. A method as in claim 4 wherein said contact time is a sufficient time to produce a Cl^- level of 0.1 ppm or less and is further sufficient to produce a Na⁺ level of 0.5 ppm or less and a K⁺ level of 0.5 ppm or less.

6. A method as in claim 1 wherein said contact time is further sufficient to produce a Na⁺ level of 1.0 ppm or less.

7. A method as in claim 1 wherein said contact time is further sufficient to produce a K⁺ level of 1.0 ppm or less.

8. A method as in claim 1 wherein the treating agent has an average particle size between 2 microns and 200 microns.

9. A method as in claim 1 wherein the amphoteric treating agent is silicated magnesium oxide.

10. A polyene prepared by the method of claim 1.

11. A polyene prepared by the method of claim 2.

12. A polyene as in claim 11 wherein the amphoteric treating agent is silicated magnesium oxide and said contact time is a sufficient time to produce a Cl^- level of 0.1 ppm or less and is further sufficient to produce a Na⁺ level of 0.5 ppm or less and a K⁺ level of 0.5 ppm or less.

13. A method of preparing a thiol-ene composition comprising:

contacting a polyene with an amphoteric treating agent selected from the group consisting of silicated magnesium oxide, basic aluminum oxide, silica gel, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, barium oxide, and barium hydroxide, the polyene being a plural norbornene functional compound;

separating the resin from the treating agent; and

then,

mixing the polyene with a polythiol;

the polyene being contacted with the treating agent for sufficient time improve the shelf-life of the thiol-ene composition.

14. A method as in claim 13 wherein the treating agent has a particle size between 2 microns and 200 microns.

15. A method as in claim 13 wherein the amphoteric treating agent is silicated magnesium oxide.

16. A method for improving the storage stability of a thiol-ene composition, the composition comprising a mixture of a polythiol and a polyene in amounts effective to cure by addition reaction of thiol groups of the polythiol to ene groups of the polyene so as to form a crosslinked polythioether, the polyene being a compound having plural norbornene groups thereon, the method comprising:

prior to mixing said polyene and said polythiol,

contacting the untreated polyene with an amphoteric treating agent selected from the group consisting of silicated magnesium oxide, basic aluminum oxide, silica gel, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, barium oxide, and barium hydroxide for a contact time, and then

separating the treated polyene from the treating agent, the contact time being a sufficient time to yield a Cl^- level in the polyene of less than 1.0 ppm after separation from the treating agent, and then

mixing the thus treated polyene and the polythiol to form the thiol-ene composition.