High refractive index compositions and uses thereof

Patent metadata

Field	Value
Publication number	US-12084531-B2
Application number	US-201917415408-A
Country	US
Kind code	B2
Filing date	Dec 17, 2019
Priority date	Dec 18, 2018
Publication date	Sep 10, 2024
Grant date	Sep 10, 2024

Abstract

Compositions including a combination of (meth)acryloyl-terminated monomers and oligomers prepared by co-reacting reactants having active hydrogen groups with an acrylating agent are disclosed. Polymerizates formed using the combinations of (meth)acryloyl-terminated monomers and oligomers exhibit a high hardness, excellent thermomechanical properties, and a high refractive index. The compositions can be used to fabricate optical components.

First claim

What is claimed is:

1. A composition comprising:
(a) a first (meth)acryloyl-terminated monomer, wherein the first (meth)acryloyl-terminated monomer has the structure of Formula (1):

wherein,
each R 1 is independently selected from hydrogen or methyl;
b is selected from 0 or 1; and
a is an integer from 1 to 6; and

(b) a second (meth)acryloyl-terminated monomer comprising two or more (meth)acryloyl groups, wherein;
(i) the second (meth)acryloyl-terminated monomer comprises a branched polythiaalkylene moiety and from 3 to 6 (meth)acryloyl groups; or
(ii) the second (meth)acryloyl-terminated monomer comprises at least one (meth)acryloylthio group and at least one (meth)acryloyloxy group; or
(iii) the second (meth)acryloyl-terminated monomer comprises 2,5-bis[(meth)acryloylthiomethyl]-1,4-dithiane, 4-(meth)acryloylthiomethyl-3,6-dithia-1,8-bis[(meth)acryloylthio]octane, 7-(meth)acryloyloxymethyl-3,6,9,12-tetrathia-1,14-bis[(meth)acryloylthio]tetradecane, 4,8-bis[(meth) acryloylthiomethyl]-3,6,9-trithia-1,11-bis[(meth)acryloylthiolundecane and regioisomers thereof, 2-ethyl-2-((meth)acryloylthiomethyl)-1,3-bis[(meth)acryloylthio]propane, and/or 1,2,3-tris[(meth)acryloylthio]propane;

and
the second (meth)acryloyl-terminated monomer (b) is different than the first (meth)acryloyl-terminated monomer (a).

2. The composition of claim 1 , wherein a is selected from 1 or 2.

3. The composition of claim 1 , wherein the first (meth)acryloyl-terminated monomer comprises bis(2-methacryloylthioethyl)sulfide:

4. The composition of claim 1 , wherein the second (meth)acryloyl-terminated monomer comprises a branched polythiaalkylene moiety and from 3 to 6 (meth)acryloyl groups.

5. The composition of claim 1 , wherein the second (meth)acryloyl-terminated monomer comprises at least one (meth)acryloylthio group and at least one (meth)acryloyloxy group.

6. The composition of claim 1 , wherein the second (meth)acryloyl-terminated monomer comprises 2,5-bis[(meth)acryloylthiomethyl]-1,4-dithiane, 4-(meth)acryloylthiomethyl-3,6-dithia-1,8-bis[(meth)acryloylthio]octane, 7-(meth)acryloyloxymethyl-3,6,9,12-tetrathia-1, 14-bis[(meth)acryloylthio]tetradecane, 4,8-bis[(meth)acryloylthiomethyl]-3,6,9-trithia-1, 11-bis[(meth)acryloylthio]undecane and regioisomers thereof, 2-ethyl-2-(meth)acryloylthiomethyl)-1,3-bis[(meth)acryloylthio]propane, 1,2,3-tris[(meth)acryloylthio]propane, or combinations of any of the foregoing.

7. The composition of claim 1 , wherein the composition further comprises a (meth)acryloyl-terminated oligomer.

8. The composition of claim 1 , wherein the composition comprises from 15 wt % to 60 wt % sulfur, wherein wt % is based on the total weight of the composition.

9. The composition of claim 1 , wherein,
the first (meth)acryloyl-terminated monomer comprises a first (meth)acryloyl equivalents;
the second (meth)acryloyl-terminated monomer comprises a second (meth)acryloyl equivalents; and
a ratio of the first (meth)acryloyl equivalents to the second (meth)acryloyl equivalents is greater than 1:1.

10. The polymerizable composition of claim 1 , further comprising a free radical initiator, wherein the free radical initiator comprises a photoinitiator or a thermally-activated free radical initiator.

11. The polymerizable composition of claim 1 , further comprising at least one third monomer, wherein,
the third monomer comprises one or more ethylenically unsaturated radically polymerizable groups; and
the third monomer is different than the first (meth)acryloyl-terminated monomer and from the second (meth)acryloyl-terminated monomer.

12. The polymerizable composition of claim 1 , wherein the polymerizable composition further comprises one or more of a thermal stabilizer, a UV stabilizer, a UV absorber, a hindered amine light stabilizer, a dichroic material, a photochromic material, a polymerization moderator, a polymerization accelerator, a pigment, a dye, or a combination of any of the foregoing.

13. The polymerizable composition of claim 12 , wherein the polymerization accelerator can comprise an organophosphine, organophosphite, amine, or combinations thereof.

14. A composition comprising the reaction product of reactants comprising:
(i) a first reactant, having two active hydrogen groups, the first reactant having the structure of Formula (5):

wherein b is selected from 0 or 1; and a is an integer from 1 to 6;
(ii) a second reactant comprising two or more active hydrogen groups, wherein
(a) the second reactant comprises a branched polythiaalkylene moiety and from 3 to 6 active hydrogen groups; or
(b) the second reactant comprises at least one thiol group and at least one hydroxyl group; or
(c) the second reactant comprises at least one of 2,5-dimercaptomethyl-1,4-dithiane, 2-ethyl-2-(mercaptomethyl)propane-1,3-dithiol, 1,2,3-trimercaptopropane, 2,2-bis(mercaptomethyl)propane-1,3-dithiol, 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, 1,3-dimercapto-2-propanol, 3-mercapto-1,2-propanediol, 2-mercapto-1,3-propanediol, 2,3-dimercapto-1-propanol, 7-hydroxymethyl-1,14-dimercapto-3,6,9,12-tetrathiatetradecane, and 4,8-bis(mercaptomethyl)-1,11-dimercapto-3,6,9-trithiaundecane or regioisomers thereof;

and wherein
the second reactant is different than the first reactant; and
(iii) a third reactant comprising an acrylating agent.

15. The composition of claim 14 , wherein a is selected from 1 or 2.

16. The composition of claim 14 , wherein the first reactant comprises bis(2-mercaptoethyl)sulfide:

17. The composition of claim 14 , wherein the second reactant comprises 2,5-dimercaptomethyl-1,4-dithiane, 2-ethyl-2-(mercaptomethyl)propane-1,3-dithiol, 1,2,3-trimercaptopropane, 2,2-bis(mercaptomethyl)propane-1,3-dithiol, 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, 1,3-dimercapto-2-propanol, 3-mercapto-1,2-propanediol, 2-mercapto-1,3-propanediol, 2,3-dimercapto-1-propanol, 7-hydroxymethyl-1,14-dimercapto-3,6,9,12-tetrathiatetradecane, 4,8-bis(mercaptomethyl)-1,11-dimercapto-3,6,9-trithiaundecane and regioisomers thereof, or a combination of any of the foregoing.

18. The composition of claim 14 , wherein the acrylating agent comprises (meth)acryloyl chloride, or (meth)acrylic anhydride.

19. The composition of claim 14 , wherein the active hydrogen group equivalents ratio of the first reactant to the second reactant is greater than 1:1.

20. The composition of claim 14 , wherein the reaction product comprises:
a first (meth)acryloyl-terminated monomer, wherein the first (meth)acryloyl-terminated monomer is derived from the first reactant;
a second (meth)acryloyl-terminated monomer, wherein the second (meth)acryloyl-terminated monomer is derived from the second reactant; and
a combination of (meth)acryloyl-terminated oligomers, wherein the combination of (meth)acryloyl-terminated oligomers is derived from the reaction of the first reactant, the second reactant and the acrylating agent.

21. The composition of claim 14 , wherein the composition comprises from 15 wt % to 60 wt % sulfur, wherein wt % is based on the total weight of the com

Assignees

• Ppg Ind Ohio Inc

Inventors

• Herold Robert D
• Hay Jeremy J

Classifications

• G02B1/041

  Lenses · CPC title

• C08F2810/20

  leading to a crosslinking, either explicitly or inherently · CPC title

• B29K2995/0082

  Flexural strength; Flexion stiffness · CPC title

• B29K2995/007

  Hardness · CPC title

• B29K2995/0031

  Refractive · CPC title