US-12617970-B2 - Urethane compounds comprising perfluorinated group, hydrolysable silane group, and (meth)acryl group

Abstract

A compound is described having following formula: (I) Also described is a mixture of compounds comprising the reaction product of i) a urethane compound comprising a perfluorooxyalkyl moiety and at least two (meth)acryl groups; and ii) a silane compound comprising hydrolysable groups and a group selected from amine or mercapto group; wherein i) and ii) are reacted at an equivalent ratio of excess compound i) such that (meth)acryl groups remain unreacted. Methods and articles are also described.

Inventors

• Thomas P. Klun
• Matthew R.D. Smith
• HENRIK B. VAN LENGERICH
• Kayla C. Niccum
• Christopher S. Lyons

Assignees

• 3M INNOVATIVE PROPERTIES COMPANY

Dates

Publication Date

20260505

Application Date

20210607

Claims (16)

1. 1 . A compound comprising a perfluorinated group and a hydrolysable silane group having the following formula: R i is the residue of a polyisocyanate; R f is a monovalent perfluorooxyalkyl group; Q is independently a covalent bond or an organic linking group having a valency of at least 2; X is O, S or NR, wherein R is H or an alkyl group having 1 to 4 carbons; R 4 is H or CH 3 ; R 1 is —S— or —N(R 5 )—, wherein R 5 is C 1 -C 4 alkyl or —R 2 Si(Y) b (R 3 ) 3-b ; R 2 is a divalent alkylene group optionally comprising one or more catenary oxygen atoms; Y is a hydrolysable group; R 3 is a non-hydrolysable group; b is 1, 2, or 3; m is at least 1; n is at least 1; for each n, p+a is no greater than 6 with the provisos that for at least one n, a is at least 1; and for at least one n, p is at least 1.
2. 2 . The compound of claim 1 wherein R i is the residue of a polyisocyanate selected from diisocyanate compounds and triisocyanate compounds.
3. 3 . The compound of claim 1 wherein R i comprises residues of diisocyanate oligomerization products.
4. 4 . The compound of claim 1 wherein m+n averages from 2 to 10.
5. 5 . The compound of claim 1 wherein R i is the residue of a diisocyanate, m+n averages 2, and both a and p average at least 1.
6. 6 . The compound of claim 1 wherein R i is the residue of a triisocyanate, m+n averages 3, n averages 2, and for each n, both a and p average at least 1.
7. 7 . The compound of claim 1 wherein R i is the residue of a triisocyanate, m+n averages 3, n averages 2, wherein for the first n, a is 0 and p averages 1; and for the second n, a averages 1 and p averages zero.
8. 8 . The compound of claim 1 wherein R i is the residue of a polyisocyanate such that m+n averages at least 4, 5, 6, 7, 8, 9, or 10; n averages at least 3, 4, 5, 6, 7, 8, 9, or 10, wherein for at least one n, a averages 0 and p averages 1; and for at least one n, a averages 1 and p averages zero.
9. 9 . An article comprising: a film or film layer comprising a cured polymerizable composition comprising the compound or mixture of compounds of claim 1 .
10. 10 . The article of claim 9 wherein the polymerizable composition further comprises non-fluorinated or fluorinated free-radically polymerizable monomer(s), oligomer(s), or a combination thereof.
11. 11 . The article of claim 9 wherein the film layer is disposed on a surface of a substrate.
12. 12 . The article of claim 11 wherein the surface of the substrate comprises a metal oxide.
13. 13 . The article of claim 12 wherein the film layer is disposed on a patterned surface.
14. 14 . The article of claim 13 wherein the patterned surface comprises nanostructures.
15. 15 . The article of claim 9 wherein the film layer is disposed on a patterned surface.
16. 16 . The article of claim 15 wherein the patterned surface comprises nanostructures.

Description

SUMMARY Although various compounds have been described, industry would find advantage in fluorinated compounds that improve adhesion to metal oxide containing surfaces. In one embodiment, a compound is described having the following formula: Ri, is the residue of a polyisocyanate;Rf is a monovalent perfluorooxyalkyl group;Q is independently a covalent bond or an organic linking group having a valency of at least 2;X is O, S or NR, wherein R is H or an alkyl group having 1 to 4 carbons;R4 is H or CH3;R1 is —S— or —N(R5)—, wherein R5 is C1-C4 alkyl or —R2Si(Y)b(R3)3-b;R2 is a divalent alkylene group optionally comprising one or more catenary oxygen atoms;Y is a hydrolysable group;R3 is a non-hydrolysable group;b is 1, 2, or 3;m is at least 1;n is at least 1;for each n, p+a is no greater than 6 with the provisos thatfor at least one n, a is at least 1; andfor at least one n, and p is at least 1. In another embodiment, a mixture of compounds is described comprising the reaction product of i) a urethane compound comprising a perfluorooxyalkyl moiety and at least two (meth)acryl groups; and ii) a silane compound comprising hydrolysable groups and a group selected from amine or mercapto group; wherein i) and ii) are reacted at an equivalent ratio of excess compound i) such that (meth)acryl groups remain unreacted. In another embodiment, a method of making a cured composition is described comprising providing a polymerizable composition comprising the compound or mixture of compounds as described herein; and curing the (meth)acryl groups. In other embodiments, articles are described comprising a film or film layer comprising the polymerizable composition comprising the compound or mixture of compounds as described herein. The polymerizable composition may further comprise other non-fluorinated or fluorinated free-radically polymerizable monomer(s), oligomer(s), or a combination thereof. In some embodiments, the film layer is disposed on a surface of a substrate, such as a (e.g. nanostructured) patterned surface. In some embodiments, the surface of the substrate comprises a metal oxide. BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1N-1V are side view of an illustrative process; FIGS. 2P-2S are side view of another illustrative process. DETAILED DESCRIPTION Presently described are urethane compounds comprising a perfluorinated group, a hydrolysable silane group, and a (meth)acryl group according to Formula 1. As used herein the term “catenary” refers to substituting a carbon atom of a carbon chain with a substituent (e.g. O or N). Thus, a pendent substituent (e.g. —OH) bonded to a carbon atom is not a catenary oxygen atom. The compounds described herein can be prepared by any suitable method. In some embodiments, a mixture of compounds is described comprising the Michael addition reaction product of i) a urethane compound comprising a perfluorooxyalkyl moiety and at least two (meth)acryl groups; and ii) a silane compound comprising hydrolysable groups and a group selected from amine or mercapto group. As used herein, “(meth)acryl” means (meth)acrylate, thio(meth)acrylate or (meth)acrylamide. In some embodiments, acryl is preferred i.e. acrylate, thioacrylate, and acrylamide. Compounds i) and ii) respectively are reacted at an equivalent ratio such that there is an excessive number of (meth)acryl groups with respect to the number of active hydrogens of the amine or mercapto groups. Mercapto groups have one active hydrogen. However, amines can have one or two active hydrogens. For example, primary amines contain two active hydrogens and can Michael add to potentially two acryl groups. Secondary amines have only one active hydrogen and can Michael add to only one acryl group. In some embodiments, the equivalent ratio of i) to ii) is at least 1.1:1, 1.2:, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1. In some embodiments, the equivalent ratio of i) to ii) ranges from 2:1 to 99:1. In some embodiments, the equivalent ratio of i) to ii) is at least 3:1, 4:1:, 5:1, 6:1, 7:1, 8:1, or 9:1. An illustrative synthesis is depicted as follows: The i) urethane compound comprising a perfluorooxyalkyl moiety and at least two (meth)acryl groups and ii) silane compound comprising hydrolysable groups and a group selected from amine or mercapto group are combined in a suitable solvent. When a homogeneous mixture or solution is obtained a catalyst is optionally added, and the reaction mixture is heated at a temperature, and for a time sufficient for the reaction to occur. Progress of the reaction can be determined by monitoring the olefin concentration by use of 1H Fourier Transform Nuclear Magnetic Resonance (FT-NMR). In typical embodiments, the solvent is non-fluorinated, such as in the case of ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl amyl ketone and N-methyl pyrrolidone (NMP); ethers such as tetrahydrofuran, 2-methyl tetrahydrofuran and methyl tetrahydrofurfuryl ether; esters such as methyl