Stable thiol-ene compositions

• US 5,358,976 A
• Filed: 12/23/1992
• Issued: 10/25/1994
• Est. Priority Date: 11/13/1989
• Status: Expired due to Fees

• Current Assignee: Loctite (R&D) Limited
• Original Assignee: Loctite (R&D) Limited
• Inventors: Richardson, Sarah C., Quigley, Killian, Dowling, Joseph P.
• Primary Examiner(s): McCamish, Marion E.
• Assistant Examiner(s): KOECKERT JR, ARTHUR
• Application Number:
  US07/996,837
• Time in Patent Office: 671 Days
• Field of Search: 522/18, 522/180, 522/14, 522/16, 522/17, 522/18, 524/189
• US Class Current: 522/18
• CPC Class Codes: C08G 75/045 from mercapto compounds and unsaturated compounds
• CPC Class Codes: C08G 75/12 Polythioether-ethers C08G75/0245 takes precedence
• CPC Class Codes: C08G 75/14 Polysulfides
• CPC Class Codes: C08K 5/32 Compounds containing nitrogen bound to oxygen
• CPC Class Codes: C08L 81/02 Polythioethers; Polythioether-ethers
• CPC Class Codes: Y10T 428/31533 Of polythioether

Abstract

Curable norbornene-thiol compositions are stabilized by addition of a non-acidic Nitroso compound.

Claims

1. A composition polymerizable to a crosslinked polythioether comprising

i) an '"'"'ene compound having a plurality of groups of the formula ##STR6## where Q is CR¹₂, O,S, NR¹ or S₂, each R¹ is independently H or alkyl, and m is 0-10;

ii) a compound having at least two pendant or terminally positioned --SH functional groups per average molecule, the ratio of reactive carbon-carbon unsaturated groups in the '"'"'ene compound (i) to --SH functional groups on the thiol compound (ii) being in the range from about 0.75/1 to about 1.5/1;

iii) a stabilizing amount of a non-acidic nitroso compound selected from the group consisting of N-nitroso amines, N-nitroso amino acids, N-nitroso amides, N-nitroso hydroxylamine salts, nitrosobenzene, 4-nitroso-N,N-dimethylaniline, 1-nitrosopyrrolidine and 2-methyl-2-nitrosopropane; and

iv) a phenyl ketone photoinitiator.

2. A composition according to claim 1, wherein the nitroso compound is an N-nitroso amine, an N-nitroso hydroxylamine salt, an N-nitroso amino acid or an N-nitroso amide.

3. A composition according to claim 2 wherein the nitroso compound is a hydroxylamine derivative of the formula

4. A composition according to claim 3 wherein the nitroso compound is the aluminum or ammonium salt of N-nitrosophenylhydroxylamine.

5. A composition according to claim 1 wherein the '"'"'ene compound (i) has the groups of formula I attached to a backbone of carbon-carbon atom structure, the backbone optionally interrupted by one or more hetero atoms.

6. A composition according to claim 1 wherein the compound (ii) having the --SH functional groups is an organic poly-β

-mercaptoacetate or poly-β

-mercaptopropionate ester.

7. A method of stabilizing a composition polymerizable to a crosslinked polythioether, the composition comprising

(i) an '"'"'ene compound having a plurality of groups of the formula ##STR7## where Q is CR¹₂, O, S, NR¹ or SO₂, each R¹ is independently H or alkyl, and m is 0-10, and

(ii) a compound having at least two pendant or terminally positioned --SH functional groups per average molecule, the ratio of reactive carbon-carbon unsaturated groups in the '"'"'ene compound (i) to --SH functional groups in the thiol compound (ii) being the range from about 0.75/1 to about 1.5/1;

and

iii) a phenyl ketone photoinitiator;

the method comprising adding thereto a stabilizing amount of a non-acidic nitroso compound selected from the group consisting of N-nitroso amines, N-nitroso amino acids, N-nitroso amides, N-nitroso hydroxylamine salts, nitrosobenzene, 4-nitroso-N,N-dimethylaniline, 1-nitrosopyrrolidine and 2-methyl-2-nitrosopropane.

8. A composition polymerizable to a crosslinked polythioether comprising

i) an '"'"'ene compound having a plurality of groups of the formula ##STR8## where Q is CR¹₂, O, S, NR¹ or SO₂, each R¹ is independently H or alkyl, and m is 0-10;

ii) a compound having at least two pendant or terminally positioned --SH functional groups per average molecule, the ratio of reactive carbon-carbon unsaturated groups in the '"'"'ene compound (i) to --SH functional groups in the thiol compound (ii) being in the range from about 0.75/1 to about 1.5/1;

iii) a stabilizing amount of a nitroso compound;

iv) a phenyl ketone photoinitiator;

wherein the nitroso compound is selected from the group consisting of N-nitrosodiethylamine, nitrosobenzene, N-nitrosobenzylmethylamine, N-nitroso-N-phenyl glycine, 2-methyl-2-nitrosopropane, 1-nitrosopyrrolidine, 2-nitroso-1-napthol, N-methyl-N-nitroso-p-toluene sulphonamide, and 4-nitroso-N,N-dimethylamiline.