Synthesis of acetal compounds

Patent metadata

Field	Value
Publication number	US-9982072-B2
Application number	US-201414917587-A
Country	US
Kind code	B2
Filing date	Oct 22, 2014
Priority date	Oct 30, 2013
Publication date	May 29, 2018
Grant date	May 29, 2018

Abstract

A process for the preparation of optionally asymmetric acetal compounds includes reacting a compound containing a hydroxyl group with a vinylether compound in the presence of a zwitterionic catalyst including at least one basic nitrogen containing structural fragment and at least one sulfonic acid group in its structure, with the proviso that a molar ratio of the basic nitrogen to sulfonic acid is 1:1.

First claim

The invention claimed is:

1. A process for preparation of optionally asymmetric acetal compounds, the process comprising the steps of:
reacting a compound including a hydroxyl group with a vinylether compound in the presence of a zwitterionic catalyst that includes at least one basic nitrogen containing structural fragment and at least one sulfonic acid group; wherein
a molar ratio of the basic nitrogen to sulfonic acid is 1:1.

2. The process according to claim 1 , wherein the at least one basic nitrogen containing structural fragment is selected from the group consisting of a substituted or unsubstituted pyridine group, a quinoline group, an isoquinoline group, an imidazole group, a benzimidazole group, and an aniline group.

3. The process according to claim 1 , wherein the vinylether compound includes at least one vinylether group and at least one other free radical polymerizable ethylenically unsaturated group selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a styrene group, a maleimide group, a vinyl ester group, a vinyl ether group, an allyl ether group, and an allyl ester group.

4. The process according to claim 3 , wherein the at least one other free radical polymerizable ethylenically unsaturated group is an acrylate group.

5. The process according to claim 1 , wherein the compound including a hydroxyl group is a photoreactive compound including a hydroxyl group.

6. The process according to claim 5 , wherein the photoreactive compound including the hydroxyl group is a photoinitiator including a hydroxyl group or a dialkyl aniline coinitiator.

7. The process according to claim 6 , wherein the photoinitiator including the hydroxyl group is selected from the group consisting of benzoinethers, benzil ketals, α,α-dialkoxyacetophenones, α-hydroxyalkylphenones, α-aminoalkylphenones, acylphosphine oxides, acylphosphine sulphides, α-haloketones, α-halosulfones, phenylglyoxalates, benzophenones, thioxanthones, 1,2-diketones, and anthraquinones.

8. The process according to claim 1 , wherein a reaction scheme for the process is represented by:

wherein
A represents a structural moiety including a photoreactive group;
L represents a divalent linking group selected from the group consisting of a substituted or unsubstituted alkylene group, alkenylene group, alkynylene group, arylene group, and a substituted or unsubstituted aliphatic ether containing group;
B represents a free radical polymerizable group selected from the group consisting of an acrylate, a methacrylate, an acrylamide, a methacryl amide, a fumarate, a maleate, and an itaconate; wherein
a starting reaction mixture of the photoreactive compound, the vinylether monomer, and the zwitterionic catalyst includes at least 25 wt % of vinylether monomer based on a total weight of the starting reaction mixture.

9. A process for preparation of optionally asymmetric acetal compounds, the process comprising the steps of:
reacting a compound including a hydroxyl group with a vinylether compound in the presence of a zwitterionic catalyst that includes at least one basic nitrogen containing structural fragment and at least one sulfonic acid group; wherein
a molar ratio of the basic nitrogen to sulfonic acid is 1:1;
a reaction scheme for the process is represented by:

A represents a structural moiety including a photoreactive group;
L represents a divalent linking group selected from the group consisting of a substituted or unsubstituted alkylene group, alkenylene group, alkynylene group, arylene group, and a substituted or unsubstituted aliphatic ether containing group;
B represents a free radical polymerizable group selected from the group consisting of an acrylate, a methacrylate, an acrylamide, a methacryl amide, a fumarate, a maleate, and an itaconate;
a starting reaction mixture of the photoreactive compound, the vinylether monomer, and the zwitterionic catalyst includes at least 25 wt % of vinylether monomer based on a total weight of the starting reaction mixture; and
the optionally asymmetric acetal compound is represented by the Formula (INI):

10. A polymerizable composition comprising:
a polymerizable photoreactive compound including at least one acetal;
a vinylether compound including at least one other polymerizable group;
a zwitterionic catalyst in a concentration of no more than 0.1 wt %, the zwitterionic catalyst including at least one basic nitrogen containing structural fragment and at least one sulfonic acid group in its structure, and a molar ratio of the basic nitrogen to sulfonic acid is 1:1;
optionally one or more polymerization inhibitors; and
optionally one or more free radical polymerizable compounds differing from the vinylether compound including the at least one other polymerizable group; wherein
the wt % is based on a total weight of the polymerizable composition.

11. The polymerizable composition according to claim 10 , wherein the photoreactive compound is an acrylated photoinitiator.

12. The polymerizable composition according to claim 11 , wherein the acrylated photoinitiator is selected from the group consisting of benzoinethers, benzil ketals, α,α-dialkoxyacetophenones, α-hydroxyalkylphenones, α-aminoalkylphenones, acylphosphine oxides, acylphosphine sulphides, α-haloketones, α-halosulfones, phenylglyoxalates, benzophenones, thioxanthones, 1,2-diketones, and anthraquinones.

13. The polymerizable composition according to claim 10 , wherein the vinylether compound including the at least one other polymerizable group is a compound including at least one vinylether group and at least one acrylate group.

14. The polymerizable composition according to claim 10 , wherein the one or more free radical polymerizable compounds differing from the vinylether compound including the at least one other polymerizable group is selected from the group consisting of monofunctional, difunctional, and polyfunctional acrylates.

15. A polymerizable composition comprising:
a polymerizable photoreactive compound including at least one acetal;
a vinylether compound including at least one other polymerizable group;
a zwitterionic catalyst in a concentration of no more than 0.1 wt %, the zwitterionic catalyst including at least one basic nitrogen containing structural fragment and at least one sulfonic acid group in its structure, and a molar ratio of the basic nitrogen to sulfonic acid is 1:1;
optionally one or more polymerization inhibitors; and
optionally one or more free radical polymerizable compounds differing from the vinylether compound including the at least one other polymerizable group; wherein
the wt % is based on a total weight of the polymerizable composition; and
the photoreactive compound is an acrylated photoinitiator represented by the Formula (INI):

Assignees

• Agfa Graphics Nv
• Agfa Nv

Inventors

• Loccufier Johan

Classifications

• C08F120/68 Primary

  Esters · CPC title

• C07C229/60

  with amino and carboxyl groups bound in meta- or para- positions · CPC title

• C07C227/16

  by reactions not involving the amino or carboxyl groups · CPC title

• C07C69/54

  Acrylic acid esters; Methacrylic acid esters · CPC title

• G03F7/038

  Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) · CPC title