Photochromic spirooxazine monomers and polysiloxanes

• US 5,322,945 A
• Filed: 02/19/1993
• Issued: 06/21/1994
• Est. Priority Date: 02/19/1993
• Status: Expired due to Term

• Current Assignee: Yeda Research and Development Co. Ltd. (Weizmann Institute of Science)
• Original Assignee: Yeda Research and Development Co. Ltd. (Weizmann Institute of Science)
• Inventors: Yitzchaik, Shlomo, Krongauz, Valeri, Zelichenok, Alexander, Buchhultz, Frida
• Primary Examiner(s): Shaver, Paul F.
• Application Number:
  US08/019,765
• Time in Patent Office: 487 Days
• Field of Search: 544/69, 544/71, 252/586, 351/163, 350/409, 350/354, 430/345
• US Class Current: 544/69
• CPC Class Codes: C07D 498/10 Spiro-condensed systems
• CPC Class Codes: C07F 7/21 Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
• CPC Class Codes: C08G 77/388 containing nitrogen
• CPC Class Codes: C09D 183/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• CPC Class Codes: G02B 5/23 Photochromic filters

Abstract

A method of making a photochromic polysiloxane includes the steps of forming a photochromic spironaphthooxazine monomer including an alkene terminated side and, by addition reaction, covalently bonding the alkene carbon to [SiH] moieties of a siloxane polymer. Novel spironaphthooxazine monomers and photochromic polysiloxanes are disclosed.

Claims

1. A photochromic polysiloxane including the functional moiety ##STR9## wherein R" is a C₁ through C₁₅ alkyl, R'"'"'" is H or C₄ through C₁₅ alkyl, G is a photochromic radical derived from a compound wherein said compound is a photochromic compound of the formula:

##STR10## wherein R¹ is selected from the group consisting of (A) hydrogen, alkyl, phenyl, benzyl, or an alkyl substituted by halogen, hydroxy, lower alkoxy, carboxyl, lower alkoxycarbonyl, and phenyl and benzyl substituted by cyano or by one or more halogens; and

(B) (CH₂)_n --CH═

CH₂ wherein n is an integer from 1 to 20;

when R¹ is (B), then R² through R⁸ are each selected from the group consisting of hydrogen, lower alkyl, and lower alkyl including substitutions from the group consisting of halogen, hydroxy, and lower alkoxy;

when R¹ is (A) then one of R² through R⁸ is (C) --X--CH₂)_n --CH═

CH₂, wherein n is an integer from 1 to 20 and X is selected from the group consisting of a covalent bond, O, N--R'"'"', (wherein R'"'"' is H or lower alkyl), CO--O, CO--NH, and --CH═

N and the remaining ones of R² through R⁸ are selected from the group consisting of hydrogen, alkyl, and alkyl substituted by halogen, hydroxy and lower alkoxy; and

R⁹ and R¹⁰ form a condensed benzene or pyridine ring, covalently bonded through the alkene carbon of radical R¹ as moiety (B) or of R² through R⁸ as moiety (C); and

the polysiloxanes being cyclic or linear including terminal groups of the formulas (R")₃ --Si--, covalently bonded to the Si atom of an [Si--O] moiety and Si-(R")₃ covalently bonded to the --O-- atom of an [Si--O] moiety.

2. A polysiloxane of claim 1 of the formula ##STR11## wherein k is an integer of at least 30, x and l are integers, the sum of x and l are less than k, one of x and l can equal 0, n is an integer of 1 through 20 and R", R'"'"'" and G are defined as in claim 8.

3. A polysiloxane of claim 2 wherein R" is CH₃, k is 35, l is 0, n is 1 or 4 and G is a radical ##STR12##

4. A polysiloxane of claim 1 of the formula ##STR13## wherein m is an integer of at least 4, n is an integer of 1 through 20, y is an integer less than m, and G is as defined in claim 8.

5. A cyclic polysiloxane of claim 4 wherein m is 4 or 5, n is 1 or 4 and G is a radical ##STR14##

10. A method as set forth in claim 8 further characterized by reacting the siloxane polymer of the formula:

##STR18## with the photochromic spironaphthooxazine monomer as defined in claim 1 to form the photochromic cyclic polysiloxane of the formula;

##STR19## wherein m is an integer equal to at least 4, n is an integer of 1 through 20;

y is an integer less than m and G is as defined in claim 15.

11. A coated article comprising:

a substrate layer; and

a coating layer consisting of a polysiloxane as defined in claim 1.

12. A coated lens comprising:

a lens substrate coated with a polysiloxane as set forth in claim 1.

6. A method of making a photochromic polysiloxane including the steps of:

forming a photochromic spironaphthooxazine monomer including an alkene terminated side chain; and

by, addition reaction, covalently bonding the photochromic spironaphthooxazine monomer through the alkene carbon to [SiH] moieties of a siloxane polymer.

7. A method as set forth in claim 6 wherein said reaction is conducted in the presence of Pt catalyst.

8. A method as set forth in claim 7 further characterized by reacting the siloxane polymer of the formula:

##STR15## photochromic spironaphthooxazine monomer to form the photochromic polysiloxane of the formula;

##STR16## wherein k is an integer of at least 30, x and l are integers, the sum of x and l are less than k and one of x and l can equal zero, n is an integer of 1 through 20, R" is a C₁ through C₁₅ alkyl, R'"'"'" is hydrogen and G is a radical derived from a compound wherein said compound is a photochromic compound of the formula;

##STR17## wherein R¹ is selected from the group consisting of (A) hydrogen, alkyl, phenyl, benzyl, or an alkyl substituted by halogen, hydroxy, lower alkoxy, carboxyl, lower alkoxycarbonyl, and phenyl and benzyl substituted by cyano or by one or more halogens; and

(B) (CH₂)_n --CH═

CH₂ wherein n is an integer from 1 to 20;

when R¹ is (B), then R² through R⁸ are each selected from the group consisting of hydrogen, lower alkyl, and lower alkyl including substitutions from the group consisting of halogen, hydroxy, and lower alkoxy;

when R¹ is (A) then one of R² through R⁸ is (C) --X--(CH₂)_n --CH═

CH₂, wherein n is an integer from 1 to 20 and X is selected from the group consisting of a covalent bond, O, N--R'"'"', (wherein R'"'"' is H or lower alkyl), CO--O, CO--NH, and --CH═

N and the remaining ones of R² through R⁸ are selected from the group consisting of hydrogen, alkyl, and alkyl substituted by halogen, hydroxy and lower alkoxy; and

R⁹ and R¹⁰ form a condensed benzene or pyridine ring.

9. A method as set forth in claim 8 further characterized by reacting the siloxane polymer with the photochromic spironaphthooxazine monomer in the presence of an alkene of C₄ -C₁₅ thus forming a photochromic polysiloxane wherein R'"'"'" is hydrogen and C₄ -C₁₅ are alkyl.