IP Library Granted Patent US 10,385,212
Granted Patent B2
US 10,385,212 · App. 15/327,274 · Granted Aug 20, 2019

Silicone emulsions

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Quick Facts
Patent No.
US 10,385,212
App. No.
15/327,274
Granted
Aug 20, 2019
Kind
B2
Abstract

The present invention provides water dilutable silicone emulsions comprising a silicone and a silicone polyether; a coating composition comprising the emulsions; a process of making the emulsions; and uses of the emulsions.

Claims (94)

1. A silicone emulsion comprising:

A) 10 to 95 wt % of a silicone having a viscosity of at least 500,000 cP at 25° C.;

B) 0.1 to 30 wt % of a silicone polyether;

C) 0 to 90 wt % of water;

D) 0 to 30 wt % of a co-surfactant; and

E) 0 to 30 wt % of a non-aqueous polar co-solvent;

wherein the silicone polyether B) comprises a cross-linked reaction product comprising a polydiorganosiloxane-polyoxyalkylene copolymer in a block arrangement of segments comprising at least one of: (AB)p, A(BA)p and B(AB)p, wherein A denotes a polyoxyalkylene segment, B denotes a polydiorganosiloxane segment, and p is an integer greater than zero; and

wherein the combined weight ratio of D) and E) to B) is from 0 to 5.

2. The silicone emulsion according to claim 1 , wherein the silicone polyether B) is formed by reacting:

i) a terminal di-SiH functional polyorganosiloxane; and

ii) a dialkenyl functional polyoxyalkylene;

wherein the molar ratio of SiH to alkenyl in ii) is from 1:1 to 1:2.5; and optionally, wherein a sufficient amount of water C) to sum all ingredients of the emulsion to 100weight percent is present.

3. The silicone emulsion according to claim 2 , wherein:

the co-surfactant D) is present; and/or

the non-aqueous polar solvent E) is present;

with the proviso that if both D) and E) are present, the combined weight ratio of D) and E) to B) is no greater than 5.

4. The silicone emulsion according to claim 2 , wherein the SiH functional polyorganosiloxane i) has the average formula

RRR 1 SiO(RRSiO) x SiRRR 1   (III)

wherein each R is independently an alkyl having 1 to 6 carbon atoms or an aryl having 6to 10 carbon atoms, R 1 is hydrogen, and x is 1 to 1,000.

5. The silicone emulsion according to claim 2 , wherein the dialkenyl functional polyoxyalkylene ii) is a dialkenyl functional ethylene oxide/propylene oxide copolymer having the average formula

CH 2 ═CR 2 (CH 2 ) n —O[C 2 H 4 O) c (C 3 H 6 O) d ]—(CH 2 ) n —CR 2 ═CH 2   (IV)

wherein R 2 is hydrogen or an alkyl having 1 to 12 carbon atoms, c is from 1 to 400, d is from 0 to 100, n is 0 to 10, and the ratio of c/(c+d) is from 0.5 to 1.

6. The silicone emulsion according to claim 1 , wherein the silicone A) is a polydimethylsiloxane having a viscosity of at least 1,000,000 cP at 25° C. and is hydroxy terminated or vinyl terminated.

7. The silicone emulsion according to claim 1 , wherein the silicone polyether B) has a weight average molecular weight greater than 10,000 g/mol.

8. The silicone emulsion according to claim 1 , wherein:

the emulsion comprises water C) and is an aqueous continuous emulsion; and/or

the silicone polyether B) is water soluble or water dispersible.

9. A silicone emulsion comprising:

A) 10 to 95 wt % of a silicone having a viscosity of at least 500,000 cP at 25° C.;

B) 0.1 to 30 wt % of a silicone polyether;

C) 0 to 90 wt % of water;

D) 0 to 30 wt % of a co-surfactant; and

E) 0 to 30 wt % of a non-aqueous polar co-solvent;

wherein the combined weight ratio of D) and E) to B) is from 0 to 5;

wherein the silicone polyether B) comprises a cross-linked reaction product formed by reacting:

i) a SiH functional polyorganosiloxane;

ii) a monoalkenyl functional polyoxyalkylene; and

iii) a dialkenyl functional polyorganosiloxane;

wherein the molar ratio of SiH to alkenyl in ii) is from 1:0.5 to 1:1.5 and the molar ratio of SiH to alkenyl in iii) is from 1:0.01 to 1:0.5, with the proviso that the total alkenyl:SiH is from 1.5:1 to 1:1; and

optionally, wherein a sufficient amount of water C) to sum all ingredients of the emulsion to 100 weight percent is present.

10. The silicone emulsion according to claim 9 , wherein:

the co-surfactant D) is present, where the weight ratio of D) to B) is no greater than 5; and/or

the non-aqueous polar co-solvent E) is present, where the weight ratio of E) to B) is no greater than 5;

with the proviso that if both D) and E) are present, the combined weight ratio of D) and E) to B) is no greater than 5.

11. The silicone emulsion according to claim 9 , wherein the SiH functional polyorganosiloxane i) has the average formula

R 3 SiO(RRSiO) x (R 1 RSiO) y SiR 3   (I)

wherein each R is independently an alkyl having 1 to 6 carbon atoms or an aryl having 6 to 10 carbon atoms, R 1 is hydrogen, x is 1 to 1,000, and y is greater than 1 to 100; and

wherein the dialkenyl functional polyorganosiloxane iii) is a vinyl terminal polydimethylsiloxane.

12. The silicone emulsion according to claim 9 , wherein the monoalkenyl functional polyoxyalkylene ii) is a monoalkenyl functional ethylene oxide/propylene oxide copolymer having the average formula

CH 2 ═CR 2 (CH 2 ) n —[(C 2 H 4 O) c (C 3 H 6 O) d ]—OR 3   (II)

wherein R 2 is hydrogen or an alkyl having 1 to 12 carbon atoms, R 3 is hydrogen, acyl, or an alkyl having 1 to 12 carbon atoms, c is from 1 to 400, d is from 0 to 100, n is 0 to 10, and the ratio of c/(c+d) is from 0.5 to 1.

13. A coating composition comprising:

a) the silicone emulsion according to claim 9 ;

b) an acrylic emulsion or a polyurethane dispersion; and

c) optionally, a polar organic solvent.

14. A process for making a silicone emulsion comprising:

I) forming a dispersion by combining:

A) 10 to 95 wt % of a silicone having a viscosity of at least 500,000 cP at 25° C.;

B) 0.1 to 30 wt % of a silicone polyether comprising a cross-linked reaction product formed by reacting;

i) a SiH functional polyorganosiloxane,

ii) a monoalkenyl functional polyoxyalkylene, and

iii) a dialkenyl functional polyorganosiloxane,

wherein the molar ratio of SiH to alkenyl ii) is from 1:0.5 to 1:1.5and the molar ratio of SiH to alkenyl in iii) is from 1:0.01 to 1:0.5, with the proviso that the total alkenyl:SiH is from 1.5:1 to 1:1; and

C) optionally, a co-surfactant and/or co-solvent;

II) mixing and homogenizing A), B), and optionally C) from step I) to form the silicone emulsion; and

III) optionally, adding water and/or other polar additives to the silicone emulsion.

15. The process according to claim 14 , further comprising in step II) adding 5 to 700 parts water for every 100 parts of the step I) dispersion and mixing and homogenizing A), B), optionally C) and the water to form the silicone emulsion.

16. The process according to claim 14 , wherein:

the silicone A) is a silicone gum that is a hydroxy terminated polydimethylsiloxane;

the SiH functional polyorganosiloxane i) has the average formula

R 3 SiO(RRSiO) x (R 1 RSiO) y SiR 3   (I)

wherein each R is independently an alkyl having 1 to 6 carbon atoms or an aryl having 6 to 10 carbon atoms, R 1 is hydrogen, x is 1 to 1,000, and y is greater than 1 to 100;

the monoalkenyl functional polyoxyalkylene ii) is a monoalkenyl functional ethylene oxide/propylene oxide copolymer; and

the dialkenyl functional polyorganosiloxane iii) is a vinyl terminal polydimethylsiloxane.

17. The process according to claim 16 , wherein the monoalkenyl functional ethylene oxide/propylene oxide copolymer ii) has the average formula

CH 2 ═CR 2 (CH 2 ) n —[(C 2 H 4 O) c (C 3 H 6 O) d ]—OR 3   (II)

wherein R 2 is hydrogen or an alkyl having 1 to 12 carbon atoms, R 3 is hydrogen, acyl, or an alkyl having 1 to 12 carbon atoms, c is from 1 to 400, d is from 0 to 100, n is 0 to 10, and the ratio of c/(c+d) is from 0.5 to 1.

18. The process according to claim 14 , wherein:

the co-surfactant C1) is present, where the weight ratio of C1) to B) is no greater than 5; and/or

the co-solvent C2) is present and is a non-aqueous polar co-solvent, where the weight ratio of C2) to B) is no greater than 5;

with the proviso that if both C1) and C2) are present, the combined weight ratio of C1) and C2) to B) is no greater than 5.

19. A process for making a mechanical silicone emulsion comprising:

I) forming a dispersion by combining:

A) 10 to 95 wt % of a silicone having a viscosity of at least 500,000 cP at 25° C.; and

B) 0.1 to 30 wt % of a silicone polyether comprising a cross-linked reaction product formed by reacting

i) a terminal di-SiH functional polyorganosiloxane, and

ii) a dialkenyl functional polyoxyalkylene,

wherein the molar ratio of SiH to alkenyl in ii)is from 1:1 to 1:2.5; and

II) mixing and homogenizing A) and B) from step I) to form a silicone emulsion.

20. The process according to claim 19 , wherein the step I) further comprises combining:

a co-surfactant C1); and/or

a co-solvent C2).

21. The process according to claim 19 , further comprising adding water and/or other polar additives to the silicone emulsion.

22. The process according to claim 19 , wherein the silicone polyether B) comprises a polydiorganosiloxane-polyoxyalkylene copolymer in a block arrangement of segments comprising at least one of: (AB)p, A(BA)p, and B(AB)p wherein A denotes a polyoxyalkylene segment, B denotes a polydiorganosiloxane segment, and p is an integer greater than zero.

Assignments (4)
CHANGE OF NAME Recorded Feb 28, 2018
From: DOW CORNING CORPORATION
To: DOW SILICONES CORPORATION
Reel/Frame 045470/0188 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 26, 2017
From: LENOBLE, BERTRAND; RAYNAUD, ELODIE
To: DOW CORNING EUROPE S.A.
Reel/Frame 041098/0518 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 26, 2017
From: KENNEDY, ROBERT D.; LILES, DONALD; LIU, YIHAN
To: DOW CORNING CORPORATION
Reel/Frame 041098/0523 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 26, 2017
From: DOW CORNING EUROPE S.A.
To: DOW CORNING CORPORATION
Reel/Frame 041098/0529 →