Silicone surfactant for use in polyurethane foams prepared using vegetable oil based polyols
View Patent ↗Silicone surfactants for use in polyurethane foams prepared using natural oils based polyols comprise silicone copolymers possessing alkyl and polyalkylene oxide polyether pendants. The silicone surfactants yield foams having improved physical properties as compared to other surfactant compositions when used in vegetable oil based urethane foams.
1. A method of producing a flexible polyurethane foam comprising:
A) preparing a mixture comprising:
(1) a polyol comprising a vegetable oil derived polyol,
(2) an organic polyisocyanate,
(3) at least one catalyst for the production of polyurethane foams,
(4) water, and
(5) a surfactant; having the formula:
R—Si(CH 3 ) 2 O—{Si(CH 3 ) 2 O—} x —{SiCH 3 R 1 O—} a —{SiCH 3 R 2 O—} b —{SiCH 3 R 3 O—} c —{SiCH 3 R 4 O—} d —{SiCH 3 R 5 O—} e —Si(CH 3 ) 2 —R
or
R 6 —Si(CH 3 ) 2 O—{SiCH 3 R 6 O} m —[SiCH 3 {O—(SiCH 3 R 6 O) m —Si(CH 3 ) 2 R 6 }O] n —{SiCH 3 R 6 O} m —Si(CH 3 ) 2 —R 6 ,
wherein:
R 1 , R 2 , and R 3 are polyalkylene oxide polyethers of the formula:
—B—C n H 2n O—(C 2 H 4 O) f —(C 3 H 6 O) g —(C 4 H 8 O) h —Z,
and where
R 1 has a blend average molecular weight in the range of from about 3000 to about 6000 grams/mole and ethylene oxide comprises from about 20 to about 60 weight percent of the alkylene oxide content of R 1 ;
R 2 has a blend average molecular weight in the range of from about 800 to about 2900 grams/mole and ethylene oxide comprises from about 20 to about 60 weight percent of the alkylene oxide content of R 2 ;
R 3 has a blend average molecular weight in the range of from about 130 to about 800 grams/mole and ethylene oxide comprises from about 0 to about 100 weight percent of the alkylene oxide content of R 3 ;
R 4 is a C 1 to C 12 substituted or unsubstituted alkyl group, an alkaryl group, or an aryl group;
R 5 is a C 14 to C 30 substituted or unsubstituted alkyl or alkaryl group;
B is a moiety capable of undergoing hydrosilation to form Si—C bonds, or a moiety capable of undergoing condensation to form Si—O—C bonds;
Z is selected from the group consisting of hydrogen, C 1 -C 8 alkyl or alkaryl moieties, —C(O)Z 1 , —C(O)OZ 1 , and —C(O)NHZ 1 , wherein Z 1 represents mono-functional C 1 -C 8 alkyl or aryl moieties;
each R is independently selected from the group consisting of R 1 , R 2 , R 3 , R 4 , and R 5 ;
each R 6 is independently selected from the group consisting of R 1 , R 2 , R 3 , R 4 , and R 5 but at least one R 6 must be R 5 ;
x is 40 to 150;
y is 5 to 40 and equals a+b+c+d+e, where b or c, but not both, may be 0, d/(a+b+c+e)=0 to 1, e>0, and a+b>0;
m=10 to 100;
n≦4; and
f, g, and h can be independently selected to have any value such that the defined blend average molecular weights of the polyethers R 1 , R 2 , and R 3 are met; and
B) reacting components 1)-5) of the mixture to form a flexible polyurethane foam.
2. The method of claim 1 , wherein said polyol further comprises a polyether polyol.
3. The method of claim 1 , wherein said vegetable oil derived polyol comprises a hydroxylated vegetable oil.
4. The method of claim 1 , wherein said vegetable oil derived polyol comprises a alkoxylated vegetable oil.
5. The method of claim 2 , wherein said polyol comprises from about 10 to about 60 weight percent of said vegetable oil derived polyol and about 40 to about 90 weight percent polyether polyol.
6. The method of claim 1 , wherein R 5 is a C 16 to C 20 substituted or unsubstituted alkyl or alkaryl group.
7. The method of claim 1 , wherein Z comprises —C(O)CH 3 or CH 3 .
8. The method of claim 1 , wherein B comprises an allyl derivative.
9. The method of claim 1 , further comprising the step of blowing the polyurethane foam with a pressurized gas.
10. The method of claim 1 , wherein at least one of the following is true:
a) x in the range of from 60 to about 80,
b) y in the range of from 5 to about 20,
c) a+c in the range of from 5 to about 15, or
d) e in the range from about 5 to 10.
11. The method of claim 1 , wherein at least one of the following is true:
a) The R 1 moieties are in the range of from about 35 to about 55% by weight of EO and have a blend average molecular weight greater than 3500 daltons;
b) The R 2 moieties are in the range of from about 35 to about 55% by weight of EO and have a blend average molecular weight in the range of from about 1100 to about 2300 daltons; or c) The R 3 moieties range from 0 up to about 100% by weight of EO and have a blend average molecular weight in the range of from about 300 to about 750 daltons.
12. A flexible polyurethane foam comprising the reaction product of:
(1) a polyol comprising a vegetable oil derived polyol,
(2) an organic polyisocyanate,
(3) at least one catalyst for the production of polyurethane foams,
(4) water, and
(5) a surfactant; having the formula:
R—Si(CH 3 ) 2 O—{Si(CH 3 ) 2 O—} x —{SiCH 3 R 1 O—} a —{SiCH 3 R 2 O—} b —{SiCH 3 R 3 O—} c —{SiCH 3 R 4 O—} d —{SiCH 3 R 5 O—} e —Si(CH 3 ) 2 − R
or
R 6 —Si(CH 3 ) 2 O—{SiCH 3 R 6 O} m —[SiCH 3 {O—(SiCH 3 R 6 O) m —Si(CH 3 ) 2 R 6 }O] n —{SiCH 3 R 6 O} m —Si(CH 3 ) 2 —R 6 ,
wherein:
R 1 , R 2 , and R 3 are polyalkylene oxide polyethers of the formula:
—B—C n H 2n O—(C 2 H 4 O) f —(C 3 H 6 O) g —(C 4 H 8 O) h —Z,
where
R 1 has a blend average molecular weight in the range of from about 3000 to about 6000 grams/mole and ethylene oxide comprises from about 20 to about 60 weight percent of the alkylene oxide content of R 1 ;
R 2 has a blend average molecular weight in the range of from about 800 to about 2900 grams/mole and ethylene oxide comprises from about 20 to about 60 weight percent of the alkylene oxide content of R 2 ;
R 3 has a blend average molecular weight in the range of from about 130 to about 800 grams/mole and ethylene oxide comprises from about 0 to about 100 weight percent of the alkylene oxide content of R 3 ;
R 4 is a C 1 to C 12 substituted or unsubstituted alkyl group, an alkaryl group, or an aryl group;
R 5 is a C 14 to C 30 substituted or unsubstituted alkyl or alkaryl group;
B is a moiety capable of undergoing hydrosilation to form Si—C bonds, or a moiety capable of undergoing condensation to form Si—O—C bonds;
Z is selected from the group consisting of hydrogen, C 1 -C 8 alkyl or alkaryl moieties, —C(O)Z 1 , —C(O)OZ 1 , and —C(O)NHZ 1 , where Z 1 represents mono-functional C 1 -C 8 alkyl or aryl moieties;
each R is independently selected from the group consisting of R 1 , R 2 , R 3 , R 4 , and R 5 ;
each R 6 is independently selected from the group consisting of R 1 , R 2 , R 3 , R 4 , and R 5 but at least one R 6 must be R 5 ;
x is 40 to 150;
y is 5 to 40 and equals a+b+c+d+e, where b or c, but not both, may be 0, d/(a+b+c+e)=0 to 1, e>0, and a+b>0;
m=10 to 100;
n≦4; and
f, g, and h can be independently selected to have any value such that the defined blend average molecular weights of the polyethers R 1 , R 2 , and R 3 are met.
13. The foam of claim 12 , wherein said polyol further comprises a polyether polyol.
14. The method of claim 12 , wherein said vegetable oil derived polyol comprises a hydroxylated vegetable oil.
15. The method of claim 12 , wherein said vegetable oil derived polyol comprises a alkoxylated vegetable oil.
16. The foam of claim 13 , wherein said polyol comprises from about 10 to about 60 weight percent of said vegetable oil derived polyol and about 40 to about 90 weight percent said polyether polyol.
17. The foam of claim 12 , wherein R 5 is a C 16 to C 20 substituted or unsubstituted alkyl or alkaryl group.
18. The foam of claim 12 , wherein Z comprises —C(O)CH 3 or CH 3 .
19. The foam of claim 12 , wherein B comprises an allyl derivative.
20. The foam of claim 12 , wherein at least one of the following is true:
a) The R 1 moieties are in the range of from about 35 to about 55% by weight of EO and have a blend average molecular weight greater than 3500 daltons;
b) The R 2 moieties are in the range of from about 35 to about 55% by weight of EO and have a blend average molecular weight in the range of from about 1100 to about 2300 daltons; or c) The R 3 moieties range from 0 up to about 100% by weight of EO and have a blend average molecular weight in the range of from about 300 to about 750 daltons.
21. The foam of claim 12 , wherein at least one of the following is true:
a) x in the range of from 60 to about 80,
b) y in the range of from 5 to about 20,
c) a+c in the range of from 5 to about 15, or
d) e in the range from about 5 to 10.
22. A method of producing a flexible polyurethane foam comprising:
A) preparing a mixture comprising:
(1) a polyol comprising from about 10 to about 40 percent by weight of a vegetable oil derived polyol,
(2) an organic polyisocyanate,
(3) at least one catalyst for the production of polyurethane foams,
(4) water, and
(5) a surfactant; having the formula:
R—Si(CH 3 ) 2 O—{Si(CH 3 ) 2 O—} x —{SiCH 3 R 1 O—} a —{SiCH 3 R 2 O—} b —{SiCH 3 R 3 O—} c —{SiCH 3 R 4 O—} d —{SiCH 3 R 5 O—} e —Si(CH 3 ) 2 —R
or
R 6 —Si(CH 3 ) 2 O—{SiCH 3 R 6 O} m —[SiCH 3 {O—(SiCH 3 R 6 O) m —Si(CH 3 ) 2 R 6 }O] n —{SiCH 3 R 6 O} m —Si(CH 3 ) 2 —R 6 ,
wherein:
R 1 , R 2 , and R 3 are polyalkylene oxide polyethers of the formula:
—B—C n H 2n O—(C 2 H 4 O) f —(C 3 H 6 O) g —(C 4 H 8 O) h —Z,
and where
R 1 has a blend average molecular weight in the range of from about 3000 to about 6000 grams/mole and ethylene oxide comprises from about 20 to about 60 weight percent of the alkylene oxide content of R 1 ;
R 2 has a blend average molecular weight in the range of from about 800 to about 2900 grams/mole and ethylene oxide comprises from about 20 to about 60 weight percent of the alkylene oxide content of R 2 ;
R 3 has a blend average molecular weight in the range of from about 130 to about 800 grams/mole and ethylene oxide comprises from about 0 to about 100 weight percent of the alkylene oxide content of R 3 ;
R 4 is a C 1 to C 12 substituted or unsubstituted alkyl group, an alkaryl group, or an aryl group;
R 5 is a C 16 to C 20 substituted or unsubstituted alkyl or alkaryl group;
B is a moiety capable of undergoing hydrosilation to form Si—C bonds, or a moiety capable of undergoing condensation to form Si—O—C bonds;
Z is selected from the group consisting of hydrogen, C 1 -C 8 alkyl or alkaryl moieties, —C(O)Z 1 , —C(O)OZ 1 , and —C(O)NHZ 1 , where Z 1 represents mono-functional C 1 -C 8 alkyl or aryl moieties;
each R is independently selected from the group consisting of R 1 , R 2 , R 3 , R 4 , and R 5 ;
each R 6 is independently selected from the group consisting of R 1 , R 2 , R 3 , R 4 , and R 5 but at least one R 6 must be R 5 ;
x is 40 to 150;
y is 5 to 40 and equals a+b+c+d+e, where b or c, but not both, may be 0, d/(a+b+c+e)=0 to 1, e>0, and a+b>0;
m=10 to 100;
n≦4; and
f, g, and h can be independently selected to have any value such that the defined blend average molecular weights of the polyethers R 1 , R 2 , and R 3 are met; and
B) reacting components 1)-5) of the mixture to form a flexible polyurethane foam.