Energy-activatable salts with fluorocarbon anions

• US 5,554,664 A
• Filed: 11/17/1995
• Issued: 09/10/1996
• Est. Priority Date: 03/06/1995
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Lamanna, William M., Mahoney, Wayne S., Palazzotto, Michael C., Kropp, Michael A.
• Primary Examiner(s): CHAPMAN, MARK A
• Application Number:
  US08/558,245
• Time in Patent Office: 298 Days
• Field of Search: 522/25, 522/29, 522/31
• US Class Current: 522/25
• CPC Class Codes: C08F 2/50 with sensitising agents
• CPC Class Codes: H05K 3/321 by conductive adhesives

Abstract

An energy-sensitive (e.g., thermal, radiation or photosensitive) initiator, curative, and/or catalytic salt that has an anion comprising a tris-(highly fluorinated alkylsulfonyl)methide, tris-(fluorinated arylsulfonyl)methide, bis-(highly fluorinated alkyl)sulfonyl imide, bis-(fluorinated aryl)sulfonyl imide, mixed aryl- and alkylsulfonyl imides and methides and any combinations thereof, has improved solubility in organic solvents, exhibit minimal corrosiveness when coatings and adhesives are prepared using the initiator, curative and/or catalytic salts, generates a highly reactive initiator, curative, and/or catalyst upon activation by energy.

Claims

1. An energy activatable salt wherein the energy activatable salt has

(1) a cation comprising at least one of (a) an organometallic cation, wherein the organometallic cation comprises (i) substituted or unsubstituted aromatic compounds based on arene or cyclopentadienyl ligands and, (ii) a transition metal atom, (b) an I-, P-, C- and S-centered organic onium cation, or (c) a mixture thereof, and

(2) a sufficient number of an anion to neutralize the charge of the cation, wherein the anion comprises a tris-(highly fluorinated alkylsulfonyl)methide, tris-(fluorinated arylsulfonyl)methide, bis-(highly fluorinated alkylsulfonyl)imide, bis-(fluorinated arylsulfonyl)imide, mixed aryl- and alkylsulfonyl imides and methides and any combinations thereof and

with the proviso that the salt is not a diazonium salt, an ammonium salt, or a simple metal salt.

2. The compound according to claim 1 wherein the salt is a photosensitive salt.

3. A photosensitive compound according to claim 2 in an organic solution wherein the photosensitive compound is spectrally sensitized by a cationic dye having an anion selected from the group consisting of (a) a highly fluorinated alkylsulfonyl methide, (b) a fluorinated arylsulfonyl methide, (c) a highly fluorinated alkyl sulfonyl imide or (d) a fluorinated arylsulfonyl imide, (e) mixed aryl- and alkylsulfonyl imides and methides and (f) any combinations thereof.

4. The compound according to claim 1 wherein the salt is a thermally sensitive salt.

5. The compound according to claim 1 wherein the salt comprises a anion having one of a formula:

space="preserve" listing-type="equation">(R.sub.f SO.sub.2).sub.3 C.sup.-

or

space="preserve" listing-type="equation">(R.sub.f SO.sub.2).sub.2 N.sup.-

wherein each R_f is independently selected from the group consisting of highly fluorinated or perfluorinated alkyl or fluorinated aryl radicals and may be cyclic, when a combination of any two R_f groups are linked to form a bridge, further, the R_f alkyl chains contain from 1-20 carbon atoms and may be straight, branched, or cyclic, such that divalent oxygen, trivalent nitrogen or hexavalent sulfur may interrupt the skeletal chain, further when R_f contains a cyclic structure, such structure has 5 or 6 ring members, optionally, 1 or 2 of which are heteroatoms.

6. The compound according to claim 5 wherein the salt comprises at least one of (C₂ F₅ SO₂)₂ N^-, (C₄ F₉ SO₂)₂ N^-, (C₈ F₁₇ SO₂)₃ C^-, (CF₃ SO₂)₃ C^-, (CF₃ SO₂)₂ N^-, (C₄ F₉ SO₂)₃ C^-, (CF₃ SO₂)₂ (C₄ F₉ SO₂)C^-, (CF₃ SO₂)(C₄ F₉ SO₂)N^-, [(CF₃)₂ NC₂ F₄ SO₂ ]₂ N^-, (CF₃)₂ NC₂ F₄ SO₂ C^- (SO₂ CF₃)₂, (3,5-bis(CF₃)C₆ H₃)SO₂ N^- SO₂ CF₃, ##STR8##

7. The compound according to claim 1 wherein the cation is organic onium cations, including aliphatic or aromatic Group IVA-VIIA (CAS version) centered onium salts, wherein aryl is an unsubstituted or substituted aromatic moiety having up to four independently selected substituents and the substituents on the aryl ring have less than 30 carbon atoms and up to 10 heteroatoms selected from N,S, non-peroxidic O, P, As, Si, Sn, B, Ge, Te, or Se.

8. The compound according to claim 7 wherein the cation includes aliphatic or aromatic I-, S-, P- or C-centered onium salts.

9. The compound according to claim 7 wherein the anion is at least one of (CF₃ SO₂)₂ N^-, (CF₃ SO₂)₃ C^-, and (C₄ F₉ SO₂)₃ C^- anions and the cation is at least one of diphenyliodonium, ditolyliodonium, didodecylphenyliodonium, (4-octyloxyphenyl)phenyliodonium, and bis(methoxyphenyl)iodonium.

10. The compound according to claim 7 wherein the anion is at least one of (CF₃ SO₂)₂ N^-, (CF₃ SO₂)₃ C^-, and (C₄ F₉ SO₂)₃ C^- anions and the cation is a least one of triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium, and 1,4-phenylene-bis(diphenylsufonium).

11. The compound according to claim 1 wherein the cation is an organometallic complex cation essentially free of metal hydride or metal alkyl functionality and has the formula:

space="preserve" listing-type="equation">[(L.sup.1)(L.sup.2)M].sup.+q

wherein

M is a metal selected from the group consisting of Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Pd, Pt and Ni,

L¹ is 1 or 2 cyclic, polyunsaturated ligands that can be the same or different ligand selected from the group consisting of substituted and unsubstituted cyclopentadienyl, cyclohexadienyl, and cycloheptatrienyl, cycloheptatriene, cyclooctatetraene, heterocyclic compounds and aromatic compounds selected from substituted or unsubstituted arene compounds and compounds having 2 to 4 fused rings, and units of polymers each capable of contributing 3 to 8 electrons to the valence shell of M;

L² is none, or 1 to 3 nonanionic ligands contributing an even number of electrons that can be the same or different ligand selected from the group of carbon monoxide, ketones, olefins, ethers, nitrosonium, phosphines, phosphites, and related derivatives of arsenic and antimony, organonitriles, amines, alkynes, isonitriles, dinitrogen, with the proviso that the total electronic charge contributed to M results in a net residual positive charge of q to the complex; and

q is an integer having a value of 1 or 2, the residual charge of the complex cation.

12. The compound according to claim 11 wherein the cation is an organometallic cation wherein M is a metal selected from the group consisting of Cr, Mo, W, Mn, Fe, Ru, Co, Pd and Ni.

13. The compound according to claim 11 wherein the anion is at least one of (CF₃ SO₂)₂ N^-, (CF₃ SO₂)₃ C^-, and (C₄ F₉ SO₂)₃ C^- anions and the cation is at least one of bis(η

⁵ -cyclopentadienyl)iron(1+), bis(η

⁵ -methylcyclopentadienyl)iron (1+), (η

⁵ -cyclopentadienyl)(η

⁵ -methylcyclopentadienyl)iron(1+), and bis(η

⁵ -trimethylsilylcyclopentadienyl)iron(1+).

14. The compound according to claim 11 wherein the anion is at least one of (CF₃ SO₂)₂ N^-, (CF₃ SO₂)₃ C^-, and (C₄ F₉ SO₂)₃ C^- anions and the cation is at least one of bis(η

⁶ -xylenes)iron(2+), bis(η

⁶ -mesitylene)iron(2+), bis(η

⁶ -durene) iron(2+), bis(η

⁶ -pentamethylbenzene)iron(2+), and bis(η

⁶ -dodecylbenzene)iron (2+).

15. The compound according to claim 11 wherein the anion is at least one of (CF₃ SO₂)₂ N^-, (CF₃ SO₂)₃ C^-, and (C₄ F₉ SO₂)₃ C^- anions and the cation is at least one of (η

⁵ -cyclopentadienyl)(η

⁶ -xylenes)iron(1+), (η

⁵ -cyclopentadienyl)(η

⁶ -toluene)iron(1+), (η

⁵ -cyclopentadienyl)(η

⁶ -mesitylene)iron(1+), (η

⁵ -cyclopentadienyl)(η

⁶ -pyrene)iron(1+), (η

⁵ -cyclopentadienyl)(η

⁶ -naphthalene)iron(1+), and (η

⁵ -cyclopentadienyl)(η

⁶ -dodecylphenyl)iron(1+).

16. The compound according to claim 1 further comprising a photosensitizer or a photoaccelerator.

17. An photosensitive compound in an organic solvent, wherein the photosensitive compound is the energy activatable salt according to claim 1.

18. The photosensitive compound in an organic solvent according to claim 17 wherein the photosensitive compound comprises a photocatalyst or photoinitiator for polymerization of a polymerizable compound, which polymerizable compound is also present in the organic solvent and the energy activable salt further includes diazonium salts of the (a) a highly fluorinated alkylsulfonyl methide, (b) a fluorinated arylsulfonyl methide, (c) a highly fluorinated alkyl sulfonyl imide or (d) a fluorinated arylsulfonyl imide anion, (e) mixed aryl- and alkylsulfonyl imides and methides and (f) any combinations thereof.

19. An energy activable compound in an organic solvent, wherein the energy activable compound is the energy activable salt according to claim 1.

20. A curable composition comprising the energy-activatable salt according to claim 1 and one or more monomers, the cure of which can be initiated or catalyzed by species released upon energy activation of the energy activable salt, wherein the energy activable salt further includes diazonium salts of the (a) a highly fluorinated alkylsulfonyl methide, (b) a fluorinated arylsulfonyl methide, (c) a highly fluorinated alkyl sulfonyl imide or (d) a fluorinated arylsulfonyl imide anion, (e) mixed aryl- and alkylsulfonyl imides and methides and (f) any combinations thereof.

21. The curable composition according to claim 20 wherein the monomer(s) are polymerizable by (1) cationic addition or (2) acid-catalyzed step-growth polymerization.

22. The curable composition according to claim 20 wherein the monomer is selected from the group consisting of ethylenically-unsaturated free-radically polymerizable monomers.

23. The curable composition according to claim 20 wherein the monomer is selected from the group consisting of epoxides and vinyl ether monomers.

24. The curable composition according to claim 20 further comprising conductive particles and optionally a thermoplastic resin and the monomer is an epoxy resin.

25. A conductive adhesive, wherein the conductive adhesive is prepared by energy activated curing of the curable composition according to claim 24.

26. The curable composition according to claim 24 wherein the monomer is an electronic grade epoxy resin.

27. A non-corrosive adhesive or coating, wherein the non-corrosive adhesive or coating is prepared by energy activated curing of the curable composition according to claim 20.