Photoinitiators that are soluble in highly fluorinated monomers

• US 5,202,359 A
• Filed: 05/17/1990
• Issued: 04/13/1993
• Est. Priority Date: 05/17/1990
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: McIntyre, Daniel K.
• Primary Examiner(s): McCamish, Marion E.
• Assistant Examiner(s): Chapman, Mark A.
• Application Number:
  US07/525,154
• Time in Patent Office: 1,062 Days
• Field of Search: 522/44, 522/40, 522/46
• US Class Current: 522/44
• CPC Class Codes: C07C 309/65 of a saturated carbon skeleton
• CPC Class Codes: C07C 45/673 by change of size of the carbon skeleton
• CPC Class Codes: C07C 45/71 being hydroxy groups
• CPC Class Codes: C07C 49/84 containing ether groups, groups, groups, or groups
• CPC Class Codes: C07C 69/63 of saturated acids
• CPC Class Codes: C07C 69/708 Ethers
• CPC Class Codes: G03F 7/029 Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur

Abstract

Highly fluorinated alkyl group substituted acetophenones and benzophenones suitable for use as initiators for the polymerization of ethylenically-unsaturated monomers in which conventional initiators have limited solubility. These compounds are particularly suitable for use for the polymerization of highly fluorinated ethylenically-unsaturated monomers.

Claims

1. A phenolic hydroxyl free compound having the structural formula:

##STR24## wherein R¹ represents ##STR25## wherein each of R³, R⁴, and R⁵ independently represents a member selected from the group consisting of hydrogen, halogen, hydroxy, alkyl group, alkoxy group, and phenyl group, provided that at least one of R³, R⁴, or R⁵ is selected from the group consisting of halogen, hydroxy, and alkoxy group, or any two of R³, R⁴, and R⁵ together represent a branched or unbranched alkylene group that forms together with the carbon atoms to which they are attached a 5- or 6-membered carbocyclic ring, or any two of R³, R⁴, and R⁵ together represent carbonyl oxygen, provided that the remaining R³, R⁴, or R⁵ is selected from the group consisting of halogen, hydroxy, alkoxy group, and phenyl group;

each of R² and R⁷ independently represents a member selected from the group consisting of hydrogen, halogen, and lower alkyl group having one to six carbon atoms, or R² and R⁷ together represent a coordinate bond, an oxygen atom, or a sulfur atom joining the phenyl group of Formula I to the phenyl group of the moiety of Formula III;

each R⁶ group independently represents a member selected from the group consisting of hydrogen, lower alkyl group having 1 to 6 carbon atoms, and polyfluoroaliphatic group, --XR_f Y, in which X represents a polyvalent connecting group joining --R_f Y to a phenyl group of Formula I or of a phenyl group of the moiety of Formula II or the moiety of Formula III, R_f represents either (a) a polyfluorinated, saturated, divalent aliphatic group that is straight-chain, branched-chain, or cyclic, and contains no more than one hydrogen atom per four fluorine atoms, or (2) divalent poly(fluorooxyalkylene) group having a number average molecular weight of from about 200 to 20,000, and Y represents a fluorine atom or X, and when Y represents X, the divalent group-13 XR_f X--joins two phenyl groups of Formula I, provided that at least one of R⁶ groups is --XR_f Y and said compound is soluble in ethylenically-unsaturated fluorocarbon compounds.

2. The compound of claim 1, wherein R³, R⁴, or R⁵ represents an alkyl group having one to six carbon atoms.

3. The compound of claim 1, wherein R³, R⁴, or R⁵ represents a haloalkyl group having one to six carbon atoms.

4. The compound of claim 1, wherein R³, R⁴, or R⁵ represents a phenyl group.

5. The compound of claim 1, wherein R³, R⁴, or R⁵ represents a substituted alkyl group, a substituted alkoxy group, or substituted phenyl group wherein the substituents are of sufficiently low polarity that they do not adversely affect solubility of the compound in highly fluorinated monomers.

6. The compound of claim 5, wherein said substituents are selected from the group consisting of halogens and alkoxy groups.

7. The compound of claim 1, wherein R³, R⁴, or R⁵ represents an alkoxy group having one to six carbon atoms.

8. The compound of claim 1, wherein two of R³, R⁴, and R⁵ represent an alkylene group having four to eight carbon atoms.

9. The compound of claim 1, wherein R⁶ represents a divalent aliphatic group having 4 to 24 carbon atoms.

10. The compound of claim 1, selected from the group consisting of 2-ethoxy-1,2-bis[4-perfluorooctylsulfonyloxy)phenyl]-1-ethanone, 1,1-bis[4-(perfluorooctylsulfonyloxy)phenyl]methanone, 1,1-bis[4-1(1,1-dihydropentadecafluorooctyloxy)phenyl]methanone, 2,2-dimethoxy-1-[4-(perfluorohexylsulfonyloxy)phenyl]-1-ethanone, and ##STR26## wherein m and n independently represent numbers ranging from 1 to 200 and the ratio of m to n ranges from 0.2 to 1 to 5 to 1.

11. A composition comprising a free radically polymerizable compound and a compound of claim 1.

12. A coated substrate comprising a substrate bearing thereon a layer of the composition of claim 11.

13. The coated substrate of claim 12, wherein the substrate is selected from the group consisting of paper, glass, metals, and polymers.

14. The compound of claim 1, wherein X represents a polyvalent group selected from the group consisting of:

##STR27## wherein R⁹ represents a divalent alkylene group having 1 to 6 carbon atoms or one or more divalent phenyl groups.

15. A composition comprising a free radically polymerizable compound and a compound of claim 14.

16. A coated substrate comprising a substrate bearing thereon a layer of the composition of claim 15.

17. The coated substrate of claim 16, wherein the substrate is selected from the group consisting of paper, glass, metals, and polymers.