FLUOROALKYL SILICONES

• US 20170166703A1
• Filed: 03/20/2015
• Published: 06/15/2017
• Est. Priority Date: 03/31/2014
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Qiu, Zai-Ming, Rathore, Jitendra S.
• Granted Patent: US 10,442,897 B2
• Time in Patent Office: Days
• CPC Class Codes: C08G 77/08 characterised by the catalysts used
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/14 containing silicon bound to oxygen-containing groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/24 halogen-containing groups
• CPC Class Codes: C08L 83/06 containing silicon bound to oxygen-containing groups C08L83/12 takes precedence
• CPC Class Codes: C08L 83/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• CPC Class Codes: C09D 183/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• CPC Class Codes: C09J 2483/005 in the release coating
• CPC Class Codes: C09J 7/401 characterised by the release coating composition

Abstract

Described herein is a fluoroalkyl silicone comprising the following formula (I) wherein R₁ and R₂ are independently selected from an alkyl group or an aryl group; Rf is a perfluoroalkyl group or a Rf′OCHFCF₂ group wherein Rf′ is a perfluoroalkyl group, and wherein Rf and Rf′ optionally comprise at least one catenary heteroatom; X, Y, and Z are independently selected from an alkyl group, a poly(alkylene oxide) group, or a hydrolysable group, wherein at least one of X, Y, and Z is a hydrolysable group; x is an integer of at least 3; y is an integer of at least 2; and m and n are independently at least 1.

Claims

1. A fluoroalkyl silicone comprising the following formula:

2. The fluoroalkyl silicone of claim 1, wherein the hydrolysable group is selected from RO—

, Cl—

, and RC(O)O—

wherein R is an alkyl group having 1 to 4 carbon atoms.

3. The fluoroalkyl silicone of claim 1, wherein, X, Y, and Z are independently selected from an —

Cl, CH₃O—

, C₂H₅O—

, C₃H₇O—

, CH₃C(O)O—

, and C₂H₅C(O)O—

.

4. The fluoroalkyl silicone of claim 1, wherein the fluoroalkyl silicone comprises a segment -[Q]-, wherein Q is selected from:

(a) formula

5. The fluoroalkyl silicone of claim 1, wherein the ratio of n to m is from 95/5 to 2/98.

6. A method of making the fluoroalkyl silicone of claim 1, comprising

(i) providing:

(a) a perfluoroalkyl alkenyl ether of the formula;

Rf—

O(CH₂)_x-2CH═

CH₂

 

R_f is a perfluoroalkyl group or a Rf′

OCHFCF₂—

group with Rf′

being a perfluoroalkyl group, and x is an integer of at least 3;

(b) a reactive silane of the formula;

XYZSi(CH₂)_y-2CH═

CH₂, where X, Y, and Z are independently selected from an alkyl group, a poly(alkylene oxide) group, or a hydrolysable group, wherein at least one of X, Y, and Z is a hydrolysable group and y is at least 2;

(c) a hydrosilicone of the formula;

7. A cured composition comprises a fluoroalkyl silicone of claim 1 from hydrolysis and dehydration of SiXYZ.

8. A release liner comprising a substrate and a layer of a cured coating of the fluoroalkyl silicone of claim 1 coated on at least one major surface of the substrate.

9. A coatable release solution comprising the alkylfluoro silicone of claim 1 and a solvent.

10. An adhesive article comprising

(i) a release liner comprising a substrate and a coating composition thereon, wherein the coating composition comprises a cured product of the fluoroalkyl silicone of claim 1;

and

(ii) a pressure-sensitive adhesive in contact with the coating composition.

11. The fluoroalkyl silicone of claim 1, wherein Rf and Rf′

are independently selected from —

CF₃, —

CF₂CF₃, —

CF₂C₂F₅, —

CF₂C₃F₇, —

CF₂C₄F₉, —

CF₂C₅F₁₁, CF₃O(CF₂)₂CF₂—

, (CF₃)₂N(CF₂)₂CF₂—

, —

CF₂CF(CF₃)₂, and C₃F₇OCF(CF₃)CF₂.

12. The fluoroalkyl silicone of claim 1, wherein the fluoroalkyl silcone comprises at least one pendent or terminal group of —

(C₃H₆)—

O—

Rf″

wherein Rf″

is perfluoroalkyl group.

13. A curable composition comprising the fluoroalkyl silicone of claim 1 and at least one of a photoinitiator.

14. The method of claim 6, wherein the hydrosilylation step is done in a single step process.

15. The method of claim 6, wherein the hydrosilylation step is done in a two step process, with the first step comprising the hydrosilylation of the perfluoroalkyl alkenyl ether and the hydrosilicone, and the second step comprising the addition and subsequent hydrosilyation of the reactive silane.

16. The method of claim 6, wherein the hydrosilylation step is done in a two step process, with the first step comprising the hydrosilylation of the reactive silane and the hydrosilicone, and the second step comprising the addition and subsequent hydrosilylation of the perfluoroalkyl alkenyl ether.

17. The method of claim 6, further comprising hydrosilylating of the Si—

H groups with a compound of the formula CH₂═

CH—

R₄, where R₄ is C1-C50 alkyl group in the presence of a hydrosilylation catalyst.

18. The method of claim 17, wherein the fluoroalkyl silicone of the formula:

19. The coatable release solution of claim 9, further comprising a non-fluorinated organopolysiloxane polymer or a linear fluoropolymer.

20. The adhesive article according to claim 10, wherein the pressure-sensitive adhesive comprises an adhesive selected from a silicone adhesive and an acrylate adhesive.