Urethane compositions containing carbinol-functional silicone resins

1. A urethane-forming composition comprising: (A) at least one compound containing at least one isocyanate group; and (B) a carbinol-functional silicone resin comprising the units:

(R 1 3 SiO 1/2 ) a (i)

(R 2 2 SiO 2/2 ) b (ii)

(R 3 SiO 3/2 ) c (iii) and

(SiO 4/2 ) d (iv)

wherein R 1 and R 2 are each independently a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group free of aryl groups having at least 3 carbon atoms, or an aryl-containing carbinol group having at least 6 carbon atoms, R 3 is an alkyl group having from 1 to 8 carbon atoms or an aryl group, a has a value of less than or equal to 0.6, b has a value of zero or greater than zero, c has a value of greater than zero, d has a value of less than 0.5, and the value of a+b+c+d=1, and with the proviso that when each R 2 is methyl the value of b is less than 0.3; where the mole ratio of carbinol groups to isocyanate groups is from about 0.8:1 to 1.2:1.

2. A urethane-forming composition comprising: (A) 100 weight parts of at least one compound containing at least one isocyanate group; (B) 3-300 weight parts of a carbinol-functional silicone resin comprising the units:

(R 1 3 SiO 1/2 ) a (i)

(R 2 2 SiO 2/2 ) b (ii)

(R 3 SiO 3/2 ) c (iii) and

(SiO 4/2 ) d (iv)

wherein R 1 and R 2 are each independently a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group free of aryl groups having at least 3 carbon atoms, or an aryl-containing carbinol group having at least 6 carbon atoms, R 3 is an alkyl group having from 1 to 8 carbon atoms or an aryl group, a has a value of less than or equal to 0.6, b has a value of zero or greater than zero, c has a value of greater than zero, d has a value of less than 0.5, and the value of a+b+c+d=1, and with the proviso that when each R 2 is methyl the value of b is less than 0.3; (C) up to 250 weight parts of an organic polyol; and (D) up to 10 weight parts of a cure rate modifier.

3. A urethane composition obtained by a method comprising reacting (A) at least one compound containing at least one isocyanate group; and (B) a carbinol-functional silicone resin comprising the units:

(R 1 3 SiO 1/2 ) a (i)

(R 2 2 SiO 2/2 ) b (ii)

(R 3 SiO 3/2 ) c (iii) and

(SiO 4/2 ) d (iv)

wherein R 1 and R 2 are each independently a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group free of aryl groups having at least 3 carbon atoms, or an aryl-containing carbinol group having at least 6 carbon atoms, R 3 is an alkyl group having from 1 to 8 carbon atoms or an aryl group, a has a value of less than or equal to 0.6, b has a value of zero or greater than zero, c has a value of greater than zero, d has a value of less than 0.5, and the value of a+b+c+d=1, and with the proviso that when each R 2 is methyl the value of b is less than 0.3, where the mole ratio of carbinol groups to isocyanate groups is from about 0.8:1 to 1.2:1.

4. A urethane composition obtained by a method comprising reacting (A) 100 weight parts of at least one compound containing at least one isocyanate group; (B) 3-300 weight parts of a carbinol-functional silicone resin comprising the units:

(R 1 3 SiO 1/2 ) a (i)

(R 2 2 SiO 2/2 ) b (ii)

(R 3 SiO 3/2 ) c (iii) and

(SiO 4/2 ) d (iv)

wherein R 1 and R 2 are each independently a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group free of aryl groups having at least 3 carbon atoms, or an aryl-containing carbinol group having at least 6 carbon atoms, R 3 is an alkyl group having from 1 to 8 carbon atoms or an aryl group, a has a value of less than or equal to 0.6, b has a value of zero or greater than zero, c has a value of greater than zero, d has a value of less than 0.5, and the value of a+b+c+d=1, and with the proviso that when each R 2 is methyl the value of b is less than 0.3; (C) up to 250 weight parts of an organic polyol; and (D) up to 10 weight parts of a cure rate modifier.

5. The urethane-forming composition according to claim 1 further comprising (C) an organic polyol.

6. The urethane-forming composition according to claim 1 , further comprising (D) a cure rate modifier.

7. The urethane-forming composition according to claim 1 wherein:

the alkyl group is methyl;

the aryl group is phenyl;

the carbinol group free of aryl groups having at least 3 carbon atoms is selected from a group having the formula R 4 OH wherein R 4 is selected from

(1) a group having the formula —(CH 2 ) x — where x has a value of 3 to 10,

(2) —CH 2 CH(CH 3 )—,

(3) —CH 2 CH(CH 3 )CH 2 —,

(4) —CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH 2 —, and

(5) a group having the formula —OCH(CH 3 )(CH 2 ) x — wherein x has a value of 1 to 10 and a group having the formula R 6 (OH) wherein R 6 is a group having the formula —CH 2 CH 2 (CH 2 ) x OCH 2 CH— wherein x in each case has a value of 1 to 10;

the aryl-containing carbinol group having at least 6 carbon atoms is a group having the formula R 5 OH wherein R 5 is selected from

(1) a group having the formula —(CH 2 ) x C 6 H 4 — wherein x has a value of 0 to 10,

(2) a group having the formula —CH 2 CH(CH 3 )(CH 2 ) x C 6 H 4 — wherein x has a value of 0 to 10, and

(3) a group having the formula —(CH 2 ) x C 6 H 4 (CH 2 ) x — wherein x has a value of 1 to 10.

8. The urethane-forming composition of claim 1 where a has a typical value of 0.1 to 0.6, b has a typical value of 0 to 0.4, c has a typical value of 0.3 to 0.8, and d has a typical value of 0 to 0.3.

9. The urethane-forming composition according to claim 1 wherein the carbinol-functional silicone resin is selected from carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 2 )CH 3 SiO 2/2 ) b where R 2 =—(CH 2 ) 3 C 6 H 4 OH

((C 6 H 5 )CH 3 SiO 2/2 ) b and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 C 6 H 4 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 C 6 H 4 OH and

(CH 3 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH

(CH 3 SiO 3/2 ) c and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 2 )CH 3 SiO 2/2 ) b where R 2 =—(CH 2 ) 3 OH

((C 6 H 5 )CH 3 SiO 2/2 ) b and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—CH 2 CH(CH 3 )CH 2 OH

((H)(CH 3 ) 2 SiO 1/2 ) a and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH

(CH 3 SiO 3/2 ) c

wherein a has a typical value of 0.1 to 0.6, b has a typical value of zero to 0.4, and c has a typical value of 0.3 to 0.8.

10. The urethane-forming composition according to claim 1 , wherein greater than 10 weight percent of the R 1 +R 2 +R 3 groups are phenyl.

11. The urethane-forming composition according to claim 1 wherein the urethane composition further comprises at least one ingredient selected from fillers, solvents, plasticizers, pigments, colorants, dyes, surfactants, thickeners, heat stabilizers, leveling agents, anti-cratering agents, fillers, sedimentation inhibitors, ultraviolet-light absorbers, promoters, heat stabilizers, ultraviolet-light absorbers, and antioxidants.

12. The urethane-forming composition according to claim 1 wherein the urethane compositions further comprise at least one cell stabilizer and at least one blowing agent, and optionally chain extenders and crosslinkers.

13. The urethane-forming composition according to claim 12 , wherein the cell stabilizer is a silicone polyether and the blowing agent is selected from water, liquid carbon dioxide, CFCs, HCFCs, HFCs, and pentane.

14. The urethane-forming composition of claim 2 , where the mole ratio of carbinol groups to isocyanate groups is from about 0.8:1 to 1.2:1.

15. The urethane composition of claim 4 , where the mole ratio of carbinol groups to isocyanate groups is from about 0.8:1 to 1.2:1.

16. The urethane-forming composition according to claim 2 wherein the carbinol-functional silicone resin is selected from carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 2 )CH 3 SiO 2/2 ) b where R 2 =—(CH 2 ) 3 C 6 H 4 OH

((C 6 H 5 )CH 3 SiO 2/2 ) b and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 C 6 H 4 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 C 6 H 4 OH and

(CH 3 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH

(CH 3 SiO 3/2 ) c and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 2 )CH 3 SiO 2/2 ) b where R 2 =—(CH 2 ) 3 OH

((C 6 H 5 )CH 3 SiO 2/2 ) b and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—CH 2 CH(CH 3 )CH 2 OH

((H)(CH 3 ) 2 SiO 1/2 ) a and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH

(CH 3 SiO 3/2 ) c

wherein a has a typical value of 0.1 to 0.6, b has a typical value of zero to 0.4, and c has a typical value of 0.3 to 0.8.

17. The urethane composition according to claim 4 wherein the carbinol-functional silicone resin is selected from carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 2 )CH 3 SiO 2/2 ) b where R 2 =—(CH 2 ) 3 C 6 H 4 OH

((C 6 H 5 )CH 3 SiO 2/2 ) b and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 C 6 H 4 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 C 6 H 4 OH and

(CH 3 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH

(CH 3 SiO 3/2 ) c and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 2 )CH 3 SiO 2/2 ) b where R 2 =—(CH 2 ) 3 OH

((C 6 H 5 )CH 3 SiO 2/2 ) b and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—CH 2 CH(CH 3 )CH 2 OH

((H)(CH 3 ) 2 SiO 1/2 ) a and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH

(CH 3 SiO 3/2 ) c

wherein a has a typical value of 0.1 to 0.6, b has a typical value of zero to 0.4, and c has a typical value of 0.3 to 0.8.

18. The urethane-forming composition according to claim 14 wherein the carbinol-functional silicone resin is selected from carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 2 )CH 3 SiO 2/2 ) b where R 2 =—(CH 2 ) 3 C 6 H 4 OH

((C 6 H 5 )CH 3 SiO 2/2 ) b and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 C 6 H 4 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 C 6 H 4 OH and

(CH 3 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH

(CH 3 SiO 3/2 ) c and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 2 )CH 3 SiO 2/2 ) b where R 2 =—(CH 2 ) 3 OH

((C 6 H 5 )CH 3 SiO 2/2 ) b and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—CH 2 CH(CH 3 )CH 2 OH

((H)(CH 3 )2SiO 1/2 ) a and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH

(CH 3 SiO 3/2 ) c

wherein a has a typical value of 0.1 to 0.6, b has a typical value of zero to 0.4, and c has a typical value of 0.3 to 0.8.

19. The urethane composition according to claim 15 wherein the carbinol-functional silicone resin is selected from carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 2 )CH 3 SiO 2/2 ) b where R 2 =—(CH 2 ) 3 C 6 H 4 OH

((C 6 H 5 )CH 3 SiO 2/2 ) b and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 C 6 H 4 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 C 6 H 4 OH and

(CH 3 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH

(CH 3 SiO 3/2 ) c and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 2 )CH 3 SiO 2/2 ) b where R 2 =—(CH 2 ) 3 OH

((C 6 H 5 )CH 3 SiO 2/2 ) b and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((CH 3 ) 3 SiO 1/2 ) a

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—CH 2 CH(CH 3 )CH 2 OH

((H)(CH 3 ) 2 SiO 1/2 ) a and

(C 6 H 5 SiO 3/2 ) c ,

carbinol-functional silicone resins comprising the units:

((R 1 )(CH 3 ) 2 SiO 1/2 ) a where R 1 =—(CH 2 ) 3 OH

(CH 3 SiO 3/2 ) c

wherein a has a typical value of 0.1 to 0.6, b has a typical value of zero to 0.4, and c has a typical value of 0.3 to 0.8.