Thiolene compositions on based bicyclic 'ene compounds

• US 4,808,638 A
• Filed: 09/21/1987
• Issued: 02/28/1989
• Est. Priority Date: 10/14/1986
• Status: Expired due to Fees

• Current Assignee: Loctite Corporation (Henkel AG & Co KGaA)
• Original Assignee: Loctite Corporation (Henkel AG & Co KGaA)
• Inventors: Steinkraus, Walter J., Jacobine, Anthony F., Glaser, David M., Rooney, John M., Woods, John
• Primary Examiner(s): Bleutge, John C.
• Assistant Examiner(s): Buttner, David
• Application Number:
  US07/099,676
• Time in Patent Office: 526 Days
• Field of Search: 526/281, 528/205, 522/24, 522/64, 522/66, 522/99, 522/167, 522/168, 522/169, 522/173, 522/180, 528/25, 528/26, 528/30, 528/128, 528/173, 528/344, 528/360, 528/361, 528/364, 528/376
• US Class Current: 522/24
• CPC Class Codes: C08G 75/045 from mercapto compounds and unsaturated compounds
• CPC Class Codes: C08G 75/12 Polythioether-ethers C08G75/0245 takes precedence

Abstract

A curable thiol-ene formulation comprising

(a) a polythiol

(b) a '"'"'ene compound having a plurality of groups of the formula: ##STR1## where Q is CH₂, CHCH₃, C(Ch₃)₂, O, S, NR¹ or SO₂ R¹ is H or alkyl, and m is 0-10, and

(c) an effective amount of a free radical initiator.

Claims

1. A curable thiol-ene formulation, said formulation being cureable to a crosslinked polymer and comprising:

(a) a polythiol,

(b) a '"'"'ene compound having a plurality of '"'"'ene groups of the formula, ##STR20## where Q is CR¹₂, O, S, NR¹ or SO₂, R¹ is H or alkyl, and m is 0-10, said compound free of allyl, methallyl or 1-propenyl groups, wherein the thiol plus '"'"'ene functionality is greater than four and

(c) an effective amount of a free radical initiator.

2. A composition as in claim 1 wherein the free radical initiator is a radical photoinitiator.

3. A composition as in claim 1 wherein the free radical initiator is a peroxide or azonitrile compound.

4. A composition as in claim 1 wherein the '"'"'ene compound is a compound having a plurality of nadimide groups.

5. A composition as in claim 1 wherein the '"'"'ene compound has the formula:

##STR21## where n is an integer of 2 or more, R is an n-valent radical, R⁵ is H or methyl and X is O, S, or NR¹.

6. A composition as in claim 5 where Q is CH₂ or O, X is O and R⁵ is H.

7. A composition as in claim 5 wherein the '"'"'ene compound is:

##STR22## where Q is as defined in claim 1, n'"'"' is 1-6 and x and y are integers of 1 or more.

8. A composition as in claim 4 wherein the '"'"'ene compound is:

##STR23##

9. A composition as in claim 1 wherein the '"'"'ene compound is a norbornenyl acetal resin having a plurality of groups of the formula:

##STR24##

10. A composition as in claim 1 wherein the '"'"'ene resin is a polyorganosilane.

11. A composition as in claim 1 wherein the polythiol is a compound having a plurality of α

-mercaptoacetate, α

-mercaptopropionate or β

-mercaptopropionate ester groups thereon.

12. A composition as in claim 11 wherein the polythiol is a polyorganosiloxane.

13. A composition as in claim 1 wherein the polythiol is a compound having a plurality of alkylthiol groups.

14. A composition as in claim 1 wherein the free radical initiator is a mixture of a peroxide compound and a η

⁵, η

⁶ iron arene complex salt of the formula;

##STR25## where R⁶ is an η

⁶ arene, R⁷ is the anion of a cyclopentadienyl compound, L is a di to heptavalent metal or metaloid, Z is a halogen and k is equal to 1 plus the valence of L.

15. A composition as in claim 14 where LZ_k^- is selected from the group consisting of SbF₆^-, BF₄^-, AsF₆^-, and PF₆^- ;

R⁶ is selected from the group consisting of benzene toluene, xylene, methoxybenzene, chlorobenzene, cumene, p-chlorotoluene, naphthalene, methoxynaphthalene, methylnaphthalene, chloronaphthalene, biphenyl, indene, pyrene, or diphenylsulfide; and

R⁷ is the anion of cyclopentadiene, acetylcyclopentadiene, benzoylcyclopentadiene, butylcyclopentadiene, amylcyclopentadiene or indene.

16. A method of providing a crosslinked polythioether polymer comprising subjecting a composition as in claim 1 to radical generating conditions.

20. A method as in claim 16 where the radical initiator is a photoinitiator and the radical generating conditions comprise exposing the composition to light of a wave length effective to activate the photoinitiator.

21. A method as in claim 20 where the photoinitiator is a visible light active photoinitiator.

22. A method as in claim 20 where the photoinitiator comprises a mixture of a peroxide compound and a η

⁵, η

⁶ -iron arene complex salt of the formula;

##STR28## where R⁶ is an η

⁶ arene, R⁷ is the anion of a cyclopentadieneyl compound, L is a di to heptavalent metal or metaloid, Z is a halogen and k is equal to 1 plus the valence of L.

23. A method as in claim 22 wherein the peroxide compound is a hydroperoxide.

17. A method of providing a polyimide polymer crosslinked by thioether linkages comprising:

providing a formulation comprising a polyimide resin having a plurality of groups of the formula;

##STR26## where Q is CR₂¹, O, S, NR¹ or SO₂ ;

R¹ is H or alkyl and m is 0-10;

a polythiol;

wherein the thiol plus the '"'"'ene functionality is greater than four and an effective amount of a catalyst comprising a mixture of a peroxide compound and a η

⁶, η

⁵ iron arene complex of the formula;

##STR27## where R⁶ is an η

⁶ arene, R⁷ is the anion of a cyclopentadienyl compound, L is a di to heptavalent metal or metaloid, Z is a halogen and k is equal to 1 plus the valence of L.

18. A method as in claim 17 wherein the polyimide resin is a compound having a plurality of nadimide groups.

19. A method as in claim 17 wherein LZ_k^- is selected from the group consisting of SbF₆^-, BF₄^-, AsF₆^-, and PF₆^- ;

R⁶ is selected from the group consisting of benzene toluene, xylene, mesitylene, methoxybenzene, chlorobenzene, cumene, p-chlorotoluene, naphthalene, methoxynaphthalene, methylnaphthalene, chloronapthalene, biphenyl, indene, pyrene, or diphenylsulfide; and

R⁷ is the anion of cyclopentadiene, acetylcyclopentadiene, benzoylcyclopentadiene, butylcyclopentadiene, amylcyclopentadiene and indene.