Polymerizable compositions containing (meth)acrylate monomers having sulfide linkages

Patent metadata

Field	Value
Publication number	US-9334345-B2
Application number	US-201213605100-A
Country	US
Kind code	B2
Filing date	Sep 6, 2012
Priority date	Sep 8, 2011
Publication date	May 10, 2016
Grant date	May 10, 2016

Abstract

Provided is a polymerizable composition including (meth)acrylate monomers having at least two sulfide (—S—) linkages in the monomer. The polymerizable compositions include a first (meth)acrylate monomer represented by the following Formula (I),

where L 1 is selected from a multivalent optionally substituted hydrocarbyl group optionally interrupted with at least one of —C(O)—, —S—, —O— and combinations thereof, and a divalent linking group represented by the following Formula (A).

In Formula (A), Y is O or S. Also in Formula (I), L 2 is independently for each n a divalent optionally substituted hydrocarbyl group optionally interrupted with at least one of —O— and —S—, R 1 is independently selected for each n from hydrogen and methyl, and n is from 2 to 6. The polymerizable compositions also may include a polymerization moderator. Also provided are polymerizates including photochromic articles and optical elements prepared from such polymerizable compositions.

First claim

We claim:

1. A polymerizable composition comprising:
(a) at least one first (meth)acrylate functional monomer represented by the following Formula (I),

wherein,
L 1 is selected from:
a divalent linking group represented by the following Formula (A),

wherein Y is O or S,

multivalent linear or branched optionally substituted C 1 -C 25 alkyl,
multivalent optionally substituted C 3 -C 12 cycloalkyl, and
combinations thereof, optionally interrupted with at least one of —S—, —O—, and combinations thereof,
L 2 is independently for each n a divalent optionally substituted hydrocarbyl group optionally interrupted with at least one of —O— and —S—,
R 1 is independently selected for each n from hydrogen and methyl, and n is from 2 to 6;
(b) at least one second (meth)acrylate functional monomer represented by the following Formula (III),

wherein,
L 4 is a multivalent optionally substituted hydrocarbyl group optionally interrupted with at least one of —C(O)—, —S—, —O— and combinations thereof,
L 5 is independently for each u a divalent optionally substituted hydrocarbyl group,
R 9 and R 10 are each independently selected for each u from hydrogen and methyl,
and
u is from 2 to 6;
(c) optionally, a polymerization moderator; and
(d) optionally, at least one monoethylenically unsaturated monomer.

2. The polymerizable composition of claim 1 wherein,
L 2 is independently for each n selected from divalent optionally substituted linear or branched C 1 -C 25 alkyl, divalent optionally substituted C 3 -C 12 cycloalkyl, divalent optionally substituted aryl, and combinations thereof optionally interrupted with at least one of —O— and —S—.

3. The polymerizable composition of c a wherein,
L 1 is selected from multivalent linear or branched C 1 -C 10 alkyl optionally interrupted with at least one of —S—, —O— and combinations thereof, and
L 2 is independently for each n selected from divalent linear or branched C 1 -C 10 alkyl optionally interrupted with at least one —O—.

4. The polymerizable composition of claim 3 wherein,
L 1 is selected from multivalent linear or branched C 1 -C 10 alkyl interrupted with at least one —S— group, and
n is 2 or 3.

5. The polymerizable composition of claim 1 wherein,
n is 2, and
L 1 is represented by the following Formula (B),
—(R 2 —S) p —R 3   (B)

wherein,
R 2 for each p is independently selected from linear or branched optionally substituted C 1 -C 10 alkyl, and optionally substituted C 3 -C 12 cycloalkyl,
R 3 is selected from linear or branched optionally substituted C 1 -C 10 alkyl, and optionally substituted C 3 -C 12 cycloalkyl, and
p is 0 to 10.

6. The polymerizable composition of claim 5 wherein,
L 2 is represented by the following Formula (C),
—(R 4 —O) q —R 5 —  (C)

wherein,
R 4 for each p is independently selected from linear or branched optionally substituted C 1 -C 10 alkyl, and optionally substituted C 3 -C 12 cycloalkyl,
R 5 is selected from linear or branched optionally substituted C 1 -C 10 alkyl, and optionally substituted C 3 -C 12 cycloalkyl, and
q is 0 to 10.

7. The polymerizable composition of claim 1 wherein,
n is 2,
L 1 is selected from,
(i) a divalent linking group represented by the following Formula (D),
—C(R 6 )(R 7 )—  (D)

wherein
R 6 and R 7 are each independently selected from hydrogen, linear or branched optionally substituted C 1 -C 10 alkyl, and optionally substituted C 3 -C 12 cycloalkyl, or R 6 and R 7 together form a C 4 -C 12 optionally substituted cycloalkyl,
and
(ii) the divalent linking group represented by Formula (A), and

L 2 is represented by the following Formula (B),
—(R 2 —S) p —R 3 —  (B)

wherein,
R 2 for each p is independently selected from linear or branched optionally substituted
C 1 -C 10 alkyl, and optionally substituted C 3 -C 12 cycloalkyl,
R 3 is selected from linear or branched optionally substituted C 1 -C 10 alkyl, and optionally substituted C 3 -C 12 cycloalkyl, and
p is 0 to 10.

8. The polymerizable composition of claim 1 further comprising at least one thio(meth)acrylate functional monomer represented by the following Formula (II),

wherein,
L 3 is a multivalent optionally substituted hydrocarbyl group optionally interrupted with at least one of —C(O)—, —S—, —O— and combinations thereof,
R 8 is independently selected for each t from hydrogen and methyl, and
t is from 2 to 6.

9. The polymerizable composition of claim 8 wherein,
L 3 is selected from multivalent linear or branched optionally substituted C 1 -C 25 alkyl, multivalent optionally substituted C 3 -C 12 cycloalkyl, multivalent optionally substituted aryl, and combinations thereof optionally interrupted with at least one of —C(O)—, —S—, —O— and combinations thereof.

10. The polymerizable composition of claim 1 wherein,
L 4 is selected from multivalent linear or branched optionally substituted C 1 -C 25 alkyl, multivalent optionally substituted C 3 -C 12 cycloalkyl, multivalent optionally substituted aryl, and combinations thereof optionally interrupted with at least one of —C(O)—, —S—, —O— and combinations thereof, and
L 5 is independently for each u selected from divalent linear or branched optionally substituted C 1 -C 25 alkyl, divalent optionally substituted C 3 -C 12 cycloalkyl, divalent optionally substituted aryl and combinations thereof.

11. The polymerizable composition of claim 1 , wherein said polymerization moderator is present and comprises at least one of, 1-isopropyl-4-methyl-1,4-cyclohexadiene; 1-isopropyl-4-methyl-1,3-cyclohexadiene, 1-methyl-4-(propan-2-ylidene)cyclohex-1-ene; 2,6-dimethyl-2,4,6-octatriene, and alpha-methyl styrene dimer.

12. The polymerizable composition of claim 1 , further comprising a free radical initiator that is thermally activated.

13. The polymerizable composition of claim 12 , wherein said free radical initiator is selected from organic peroxy compounds, azobis(organonitrile) compounds, N-acyloxyamine compounds, O-imino-isourea compounds, and combinations thereof.

14. The polymerizable composition of claim 13 , wherein said free radical initiator is selected from at least one organic peroxy compound.

15. The polymerizable composition of claim 14 , wherein said free radical initiator comprises at least one of 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, and 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane.

16. The polymerizable composition of claim 13 , wherein said free radical initiator is selected from at least one of 1-acetoxy-2,2,6,6-tetramethylpiperidine, and 1,3-dicyclohexyl-O—(N-cyclohexylideneamino)-isourea.

17. A polymerizable composition comprising:
(a) at least one first (meth)acrylate functional monomer represented by the following Formula (I),

wherein,
n is 2,

L 1 is represented by the followi

Assignees

• Herold Robert D
• Bojkova Nina V
• Graham Marvin J
• Hickenboth Charles R
• Mccollum Gregory J
• Retsch Jr William H
• Zhou Hongying
• Ppg Ind Ohio Inc

Inventors

• Herold Robert D
• Bojkova Nina V
• Graham Marvin J
• Hickenboth Charles R
• Mccollum Gregory J
• Retsch Jr William H
• Zhou Hongying

Classifications

• C08F222/10

  Esters · CPC title

• G02B1/04 Primary

  made of organic materials, e.g. plastics (G02B1/08 takes precedence) · CPC title

• C08G75/00

  Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule · CPC title

• C08F36/20

  unconjugated · CPC title

• C07C323/12

  the carbon skeleton being acyclic and saturated · CPC title