SILICONE-POLYETHER COPOLYMER, ISOCYANATE-FUNCTIONAL SILICONE-POLYETHER COPOLYMER FORMED THEREWITH, SILICONE-POLYETHER-URETHANE COPOLYMER, SEALANTS COMPRISING SAME, AND RELATED METHODS

• US 20200131302A1
• Filed: 06/26/2018
• Published: 04/30/2020
• Est. Priority Date: 06/26/2017
• Status: Active Grant

• Current Assignee: Dow Silicones Corporation (Dow, Inc.)
• Original Assignee: Dow Global Technologies LLC (Dow, Inc.), Dow Silicones Corporation (Dow, Inc.)
• Inventors: GRASMANN, Martin, HAGAN, David, HARKNESS, Brian, HEATH, William H., HLINKA, II, Stephen Michael, JOFFRE, Eric, JOHNSON, William, KRISHNAN, Bindu, XU, Qiuyun, ZHU, Bizhong
• Granted Patent: US 10,738,191 B2
• Time in Patent Office: Days
• CPC Class Codes: B01J 2531/828 Platinum
• CPC Class Codes: B01J 31/124 Silicones or siloxanes or comprising such units
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/242 organometallic compounds containing tin-carbon bonds
• CPC Class Codes: C08G 18/244 tin salts of carboxylic acids
• CPC Class Codes: C08G 18/289 containing silicon
• CPC Class Codes: C08G 18/3203 Polyhydroxy compounds
• CPC Class Codes: C08G 18/4829 Polyethers containing at least three hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/5096 containing silicon
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/755 and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• CPC Class Codes: C08G 18/7671 containing only one alkylene bisphenyl group
• CPC Class Codes: C08G 2190/00 Compositions for sealing or packing joints
• CPC Class Codes: C08G 65/336 containing silicon
• CPC Class Codes: C08G 65/34 from hydroxy compounds or their metallic derivatives C08G65/26 takes precedence
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/18 to alkoxy or aryloxy groups
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/46 containing polyether sequences
• CPC Class Codes: C08G 77/48 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C08G77/42 takes precedence
• CPC Class Codes: C08K 5/0016 : Plasticisers
• CPC Class Codes: C08K 5/0025 : Crosslinking or vulcanising agents; including accelerators
• CPC Class Codes: C08K 5/12 : of cyclic polycarboxylic acids
• CPC Class Codes: C08K 5/5415 : containing at least one Si—O bond
• CPC Class Codes: C08K 5/57 : Organo-tin compounds
• CPC Class Codes: C08L 71/02 : Polyalkylene oxides
• CPC Class Codes: C08L 83/12 : containing polyether sequences
• CPC Class Codes: C09D 171/02 : Polyalkylene oxides
• CPC Class Codes: C09D 183/12 : containing polyether sequences
• CPC Class Codes: C09K 2200/0685 : Containing silicon
• CPC Class Codes: C09K 3/1021 : Polyurethanes or derivatives thereof

Abstract

A silicone-polyether copolymer has the formula X—Y, where X is a silicone moiety having a particular structure and Y is a polyether moiety. An isocyanate-functional silicone-polyether copolymer formed therewith is also disclosed. Further, a silicone-poly-ether-urethane copolymer formed with the isocyanate-functional silicone-polyether copolymer is disclosed. Related methods of preparation as well as sealants and cured products thereof are further disclosed.

Claims

1. A silicone-polyether copolymer having the formula X—

Y, wherein X is a silicone moiety having one of formulas (I)-(III);

2. The silicone-polyether copolymer of claim 1, wherein the polyether moiety Y has the formula

—

(C_nH_2nO)_wH,

wherein each subscript n is independently selected from 2 to 4 in each moiety indicated by subscript w; and

wherein subscript w is from 1 to 200.

3. The silicone-polyether copolymer of claim 1, wherein:

(i) the polyether moiety Y has the formula

—

(C₂H₄₀)_x(C₃H₆O)_y(C₄H₈O)_zH,

 

wherein subscript x is from 0 to 200;

subscript y is from 1 to 200; and

subscript z is from 0 to 200; and

wherein units indicated by subscripts x, y and z may be in randomized or block form in the polyether moiety Y;

(ii) the polyether moiety Y has a number average molecular weight of at least about 100;

or

(iii) both (i) and (ii).

4. The silicone-polyether copolymer of claim 1, wherein:

(i) each R¹ is methyl;

(ii) R² is propyl;

(iii) each a is 0;

(iv) each D¹ is C₂H₄;

or

(v) any combination of (i) to (iv).

5. A method of preparing a silicone-polyether copolymer, said method comprising:

reacting a polyether compound having one terminal unsaturated group and one terminal hydroxyl group and an organosilicon compound in the presence of a hydrosilylation catalyst to give the silicone-polyether copolymer;

wherein the silicone-polyether copolymer is according to claim 1.

6. The method of claim 5, wherein one of provisos I) and II) below is true:

I) the polyether compound has the formula

R³O(C_nH_2nO)_w′

H,

 

wherein R³ is an unsaturated group having from 2 to 6 carbon atoms;

each subscript n is independently selected from 2 to 4 in each moiety indicated by subscript w′

; and

subscript w′

is from 1 to 200;

II)

(i) the polyether compound has the formula

—

R³O(C₂H₄O)_x′

(C₃H₆O)_y′

(C₄H₈O)_z′

H,

 

wherein R³ is an unsaturated group having from 2 to 6 carbon atoms;

subscript x′

is from 0 to 200;

subscript y′

is from 1 to 200; and

subscript z′

is from 0 to 200; and

wherein units indicated by subscripts x′

, y′ and

z′

may be in randomized or block form in the polyether compound;

(ii) the polyether compound has a number average molecular weight of at least about 100;

or

(iii) both (i) and (ii).

8. The method of claim 5, wherein the organosilicon compound is an organohydrogensiloxane compound having one of formulas (IV)-(VI):

10. A method of preparing an isocyanate-functional silicone-polyether copolymer, said method comprising:

reacting a silicone polyether copolymer with a polyisocyanate to give the isocyanate-functional silicone-polyether copolymer;

wherein the silicone polyether copolymer is according to claim 1;

optionally, wherein the isocyanate-functional silicone-polyether copolymer has the following formula;

13. An isocyanate-functional silicone-polyether copolymer formed in accordance with the method of claim 10.

20. A sealant, comprising:

a silicone-polyether copolymer; and

a condensation reaction catalyst;

wherein the silicone-polyether copolymer is according to claim 1.

25. A cured product of the sealant of claim 20.

26. A composite article comprising a substrate and the cured product of claim 25 disposed on the substrate.

7. (canceled)

9. (canceled)

11-12. -12. (canceled)

14. An isocyanate-functional silicone-polyether copolymer having the following formula:

15. A method of preparing a silicone-polyether-urethane copolymer, said method comprising:

reacting an isocyanate-functional silicone-polyether copolymer with a coupling agent having an average of more than one isocyanate-reactive functional group to give the silicone-polyether-urethane copolymer;

wherein the isocyanate-functional silicone-polyether copolymer is according to claim 14.

16. The method of claim 15, wherein the coupling agent comprises at least one of a diol, a triol, a tetraol, a pentaol, and a hexanol.

17. The method of claim 16, wherein the silicone-polyether-urethane copolymer has the formula Q-D″

-Q, wherein D″

is a divalent linking group, and each Q has the following formula;

18. A silicone-polyether-urethane copolymer prepared in accordance with the method of claim 15.

21. A sealant, comprising:

an isocyanate-functional silicone-polyether copolymer; and

a condensation reaction catalyst;

wherein the isocyanate-functional silicone-polyether copolymer is according to claim 14.

19. A silicone-polyether-urethane copolymer having an average of more than one functional group of the following formula:

22. A sealant, comprising:

a silicone-polyether-urethane copolymer; and

a condensation reaction catalyst;

wherein the silicone-polyether-urethane copolymer is according to claim 19.

23-24. -24. (canceled)

27-28. -28. (canceled)