Alkoxysilyl functional silicone based materials

• US 6,716,908 B2
• Filed: 01/30/2002
• Issued: 04/06/2004
• Est. Priority Date: 01/30/2002
• Status: Expired due to Fees

• Current Assignee: Dow Corning Corporation (Dow, Inc.)
• Original Assignee: Dow Corning Corporation (Dow, Inc.)
• Inventors: Schulz, William James Jr., Lomas, Arnold Wade
• Primary Examiner(s): Robertson, Jeffrey B.
• Application Number:
  US10/060,713
• Publication Number:
  US 20030158326A1
• Time in Patent Office: 797 Days
• Field of Search: 524/588, 524/267, 524/268, 524/862, 524/863, 524/866, 524/861, 525/478, 525/479, 525/101, 525/105, 424/401, 424/70.12
• US Class Current: 524/588
• CPC Class Codes: A61K 8/89 Polysiloxanes
• CPC Class Codes: A61K 8/891 saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
• CPC Class Codes: A61K 8/893 modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
• CPC Class Codes: A61K 8/895 containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
• CPC Class Codes: A61Q 1/02 Preparations containing skin colorants, e.g. pigments preparations in powder form A61Q1/12
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: C08G 77/38 Polysiloxanes modified by chemical after-treatment C08G77/045 takes precedence
• CPC Class Codes: C08G 77/50 by carbon linkages C08G77/485 takes precedence
• CPC Class Codes: C08L 83/14 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C08L83/10 takes precedence

Abstract

There are disclosed alkoxysilyl functional silicone based materials that are thermodynamically stable, methods for making them and their uses. The methods comprise cross-linking of reactants that are dispersed in a diluent.

Claims

1. A thermodynamically stable material comprising:

(A) a cross-linked siloxane comprising;

alkoxysilyl functionality, —

X—

SiR⁴_n(OR⁵)_3-n, and

cross-links, —

E¹—

Y—

E²—

, with each end of such cross-links bonded to a silicon,

wherein,

X is a divalent group that is a hydrocarbon, a siloxane or some combination of these,

R⁴ and R⁵ are independently monovalent hydrocarbon groups,

E¹ and E² are independently —

CH₂CH₂ or —

CH═

CH—

,

Y is a divalent group that is a hydrocarbon, a siloxane or some combination of these and

n is 0 to 2; and

(B) a diluent.

2. The material of claim 1 wherein:

(A) is a cross-liked siloxane comprising;

alkoxysilyl functionality, —

X—

SiR⁴_n(OR⁵)_3-n, and

cross-links, —

E¹—

Y—

E²—

, with each end of such cross-links bonded to a silicon,

wherein,

X is a divalent hydrocarbon group having from 2 to 12 carbons,

R⁴ and R⁵ are independently monovalent hydrocarbon groups having from 1 to 30 carbons,

E¹ and E² are —

CH₂CH₂—

,

Y is a divalent hydrocarbon group having from 1 to 30 carbons or a siloxane and

n is 0 to 2.

3. The material of claim 1 wherein:

(A) is a cross-linked alkoxysilyl functional siloxane of average formula;

 

where,

R¹ is a monovalent hydrocarbon group;

R² is —

(CH₂)_dSiR⁴_n(OR⁵)_3-n;

R³ is —

E¹—

Y—

E²—

R⁹ or a siloxane containing —

E¹—

Y—

E²—

R⁹ with E¹ in this last mentioned siloxane bonded to silicon as well as to Y,

R⁴ and R⁵ are independently monovalent hydrocarbon groups;

E¹ and E² are independently —

CH₂CH₂—

or —

CH═

CH—

;

Y is a divalent group that is a hydrocarbon, a siloxane or some combination of these;

R⁹ is

a is 0-100,000,000;

b is 1-50,000,000;

c is 1-10,000,000;

4<

=cc<

=2c+2;

d is 2-12;

n is 0-2.

4. The material of claim 3 where,

in (A):

R¹ is a monovalent hydrocarbon group having 1 to 12 carbons,

R³ is —

E¹—

Y—

E²—

R⁹,

R⁴ is a monovalent hydrocarbon group having 1 to 12 carbons,

R⁵ is methyl, ethyl, isopropyl, phenyl or benzyl,

E¹ and E² are —

CH₂CH₂, and

Y is a divalent hydrocarbon group having from 1 to 30 carbons; and

(B) is a siloxane other than that chosen for (A) or a mixture of siloxanes not containing that chosen for (A).

5. The material of claim 3 where the weight ratio of (A):

(B) is from 1;

100 to 10;

1.

6. The material of claim 3 where in (A),

R³ is —

E¹—

Y—

E²—

R⁹,

Y is

R¹⁰ is a monovalent hydrocarbon group and

p is 0 to 20,000.

7. The material of claim 6 where

in (A):

R¹ is methyl,

R⁴ and R⁵ are independently monovalent hydrocarbon groups having from 1 to 30 carbons,

E¹ and E² are —

CH₂CH₂— and

R¹⁰ is methyl.

8. The material of claim 1 wherein

(A) is a cross-linked alkoxysilyl functional siloxane of average formula:

 

where,

R¹¹ is a monovalent hydrocarbon group;

R⁴² is a monovalent hydrocarbon group or —

(CH₂)_dSiR⁴_n(OR⁵)_3-n, with the proviso that R⁴² is at least in part —

(CH₂)_dSiR⁴_n(OR⁵)_3-n;

R¹³ is —

E¹—

R¹⁶—

Y—

R¹⁷—

E²—

R¹⁹, or a siloxane containing —

E¹—

R¹⁶—

Y—

R¹⁷—

E²—

R¹⁹ with E¹ as this last mentioned siloxane bonded to silicon and R¹⁶;

Q is on average at least 80 mole percent (SiO₂) with the balance made up of one or more other types of siloxane units;

R⁴ and R⁵ are independently monovalent hydrocarbon groups;

E¹ and E² are independently —

CH₂CH₂—

or —

CH═

CH—

;

R¹⁶ and R¹⁷ are independently divalent hydrocarbon groups or nullities;

Y is a divalent group that is a hydrocarbon, a siloxane or a combination of these

R¹⁹ is

j is 1 to 100;

q is 1 to 500,000;

r is 1 to 1,000,000;

t is 1 to 100,000;

d is 2 to 12; and

n is 0 to 2, with the proviso that

q+t;

r is 0.5 to 4.0.

9. The material of claim 8 where in (A):

R¹¹ is a monovalent hydrocarbon group having from 1 to 40 carbons;

R¹³ is —

E¹—

R¹⁶—

Y—

R¹⁷—

E²—

R¹⁹;

R⁴ and R⁵ are independently monovalent hydrocarbon groups having from 1 to 30 carbons;

R¹⁶ and R¹⁷ are independently divalent hydrocarbons groups having from 1 to 8 carbons or a nullity;

Y is

R²⁰ is a monovalent hydrocarbon group having from 1 to 40 carbons; and

v is 0 to 20,000.

10. The material of claim 1 wherein:

(A) is a cross-linked alkoxysilyl functional siloxane comprising subunits of formula;

 

where,

R¹ is a monovalent hydrocarbon group;

R² is —

(CH₂)_dSiR⁴_n(OR⁵)_3-n;

R³ is —

E¹—

Y—

E²—

R⁹ or a siloxane containing —

E¹—

Y—

E²—

R⁹ with E¹ in this last mentioned siloxane bonded to silicon as well as to Y,

R⁴ and R⁵ are independently monovalent hydrocarbon groups;

E¹ and E² are independently —

CH₂CH₂—

or —

CH═

CH—

;

Y is a divalent group that is a hydrocarbon, a siloxane or some combination of these;

R⁹ is

a is 0-1,000;

b is 1-500;

c is 1-100;

4<

=cc<

=2c+2;

d is 2-12;

n is 0-2.

11. The material of claim 1 wherein

(A) is a cross-linked alkoxysilyl functional siloxane comprising subunits of formula:

 

where,

R¹¹ is a monovalent hydrocarbon group;

R⁴² is a monovalent hydrocarbon group or —

(CH₂)_dSiR⁴_n(OR⁵)_3-n, with the proviso that R⁴² is at least in part —

(CH₂)_dSiR⁴_n(OR⁵)_3-n;

R¹³ is —

E¹—

R¹⁶—

Y—

R¹⁷—

E²—

R¹⁹ or a siloxane containing —

E¹—

R¹⁶—

Y—

R¹⁷—

E²—

R¹⁹ with E¹ in this last mentioned siloxane bonded to silicon and R¹⁶;

Q is on average at least 80 mole percent (SiO₂) with the balance made up of one or more other types of siloxane units;

R⁴ and R⁵ are independently monovalent hydrocarbon groups;

E¹ and E² are independently —

CH₂CH₂—

or —

CH═

CH—

;

R¹⁶ and R¹⁷ are independently divalent hydrocarbon groups or nullities;

Y is a divalent group that is a hydrocarbon, a siloxane or a combination of these

R¹⁹ is

j is 1 to 100;

q is 1 to 500;

r is 1 to 1000;

t is 1 to 100;

d is 2 to 12; and

n is 0 to 2, with the proviso that

q+t;

r is 0.5 to 4.0.

23. A material, comprising the composition of claim 1, that is a personal care product.

24. The material of claim 23 that is a hair, skin or underarm care product.

25. The material of claim 24 that is a conditioner, moisturizer, body wash, cosmetic foundation, blush, lipstick, eye liner, mascara, eye shadow, antiperspirant or deodorant.

12. A method of making a thermodynamically stable material, the method comprising cross-linking, in the presence of a hydrosilylation catalyst,

(1) an ≡

SiH functional siloxane and,

(2) an alpha, omega diene, diyne or ene-yne,

with the provisos

that at least one of (1) and (2) has alkoxysilyl functionality, —

X—

SiR⁴_n(OR⁵)_3-n,

where,

X is a divalent group that is a hydrocarbon a siloxane or some combination of these,

R⁴ and R⁵ are independently monovalent hydrocarbon groups and

n is 0 to 2,

that (1) and (2) are dispersed in a diluent, and

that the weight ratio of (1)+(2)+ the product of the cross-linking of (1) and (2);

diluent is 1;

100 to 10;

1.

17. The method of claim 12, wherein

(1) is an ≡ Si—

H functional polyorganosiloxane and

(2) is a polyorganosiloxane resin having alpha-omega diene or diyne or ene-yne functionality.

18. The method of claim 17 wherein at least 80 mole percent of subunits in the polyorganosiloxane resin of (2) are (SiO₂) and ((Rⁱ)₃SiO_0.5), where Rⁱ is a monovalent hydrocarbon group, the ratio in (2) of siloxane units other than SiO₂ to SiO₂ units there is 0.5 to 4.0, and X in the alkoxysilyl functionality is a hydrocarbon.

22. The product of the method of claim 18.

13. The method of clam 12 wherein

(1) is an ≡

SiH functional siloxane having alkoxysilyl functionality of the form,

—

X—

SiR⁴_n(OR⁵)_3-n, where,

X is a divalent group that is a hydrocarbon, a siloxane or some combination of these,

R⁴ and R⁵ are independently monovalent hydrocarbon groups and

n is 0 to 2.

14. The method of claim 13 where,

(1) is an alkoxysilyl functional siloxane of average formula:

 

where,

R¹ is a monovalent hydrocarbon group;

R² is —

(CH₂)_dSiR⁴_n(OR⁵)_3-n;

R⁴ and R⁵ are independently monovalent hydrocarbon groups;

a is 0-1,000;

b is 1-500;

c is 1-100;

2<

=cc<

=2c+2;

d is 2-12; and

n is 0-2;

(2) is E³—

Y—

E⁴ or a siloxane containing E³—

Y—

E⁴, where

E³ and E⁴ are independently CH₂═

CH—

or CH≡

C—

; and

Y is a multivalent group that is a hydrocarbon, a siloxane or some combination of these.

15. The method of claim 13, wherein,

(1) is on average

[(CH₃)₃SiO_0.5]_i[(CH₃)₂HSiO]_u[(CH₃)₂SiO]_c[(CH₃)HSiO]_d[(CH₃)R²SiO]_k[(CH₃)₂R²SiO_0.5]_m;

R² is —

(CH₂)_pSiR⁴_n(OR⁵)_3-n;

R⁴ and R⁵ are independently monovalent hydrocarbon groups;

i is 0 to 2;

u is 0 to 2;

i+u+m=2;

c is 0 to 20,000;

d is 0 to 2000;

u+d>

=2;

k is 0 to 2000;

m is 0 to 2;

k+m>

=1;

p is 2 to 12;

n is 0 to 2; and

(2) is on average

[(CH₂═

CH)(CH₃)₂SiO_0.5]_e[(CH₃)₃SiO_0.5]_f[(CH₃)₂SiO]_g[(CH₂═

CH)(CH₃)SiO]_h;

e is 0 to 2;

f is 0 to 2;

e+f=2;

g is 0 to 20,000;

h is 0 to 1000; and

e+h>

=2.

16. The method of claim 13, wherein,

(1) is on average

 

where,

R¹¹ is a monovalent hydrocarbon group;

R⁴² is a monovalent hydrocarbon group or —

(CH₂)_dSiR⁴_n(OR⁵)_3-n, with the proviso that R⁴² is at least in part —

(CH₂)_dSiR⁴_n(OR⁵)_3-n;

Q is on average at least 80 mole percent (SiO₂) with the balance made up of one or more other types of siloxane units;

R⁴ and R⁵ are independently monovalent hydrocarbon groups;

j is 1 to 100;

q is 1 to 500;

r is 1 to 1000;

t is 1 to 100;

d is 2 to 12;

n is 0 to 2;

q+t;

r is 0.5 to 4; and

(2) is on average

where x is 0 to 20,000,

y is 0 to 2000,

z is 0 to 2,

2<

32 z+y<

=2000,

R²¹ is a monovalent terminally aliphatic unsaturated hydrocarbon having from two to twelve carbons, and

R²² is a monovalent hydrocarbon having one to forty carbons.

19. The product of the method of claim 14.

20. The product of the method of claim 15.

21. The product of the method of claim 16.