Block ABA silicone polyalkyleneoxicie copolymers, methods of preparation, and applications for employing the same
View Patent ↗There is provided herein a linear tri-block copolymer having the average formula (1): ABA (1) wherein A is a polyalkyleneoxide unit or an aliphatic modified polyalkyleneoxide unit both of the general formula: R 5 O(C a H 2a O) d Y and wherein B is an internal polysiloxane unit of the general formula: [X(C a H 2a O) b R 2 [SiO(R 1 ) 2 ] c Si(R 1 ) 2 R 2 (OC a H 2a ) b X] wherein X and Y are divalent organic groups selected from a secondary amine or a tertiary amine and a ring-opened epoxide, such that when X is a ring-opened epoxide, Y is a secondary or tertiary amine, and when Y is a ring-opened epoxide, X is a secondary or tertiary amine. In addition, there is provided herein a method of making a linear tri-block copolymer having the average formula (1) and personal care and softener compositions comprising the same, specifically a hair conditioner.
1. A linear tri-block copolymer represented by the average formula (1):
ABA (1)
wherein A is a polyalkyleneoxide unit or an aliphatic modified polyalkyleneoxide unit both of the general formula:
R 5 (C a H 2a O) d Y
and wherein B is an internal polysiloxane unit of the general formula:
[X(C a H 2a O) b R 2 [SiO(R 1 ) 2 ] c Si(R 1 ) 2 R 2 (OC a H 2a ) b X]
wherein
R 1 is an alkyl containing from 1 to 4 carbon atoms,
R 2 is a divalent organic moiety containing from 1 to 30 carbon atoms,
each a in unit A and unit B is independently an integer of from 2 to 4,
each b is independently 0 or an integer of from 1 to 100,
c is an integer of from 1 to 1000,
R 5 is of the formula (C n H 2n+1 )— with n=1-30, or of the formula (C n H 2n−1 )— with n=2-30, or of the formula (C n H 2n+3 )— with n=4-30,
d is an integer of from 1 to 100,
provided that the sum of all the b values and the d value is an integer of from 1 to 100,
X and Y are divalent organic groups selected from a secondary amine, a tertiary amine and a ring-opened epoxide, such that when X is a ring-opened epoxide, Y is a secondary or tertiary amine, and when Y is a ring-opened epoxide, X is a secondary or tertiary amine.
2. The copolymer of claim 1 wherein the ring-opened epoxide which is represented by either X or Y is aliphatic, cycloaliphatic or aromatic.
3. The copolymer of claim 1 wherein the ring-opened epoxide which is represented by either X or Y contains at least one of a hydroxyl group and an ether linkage.
4. The copolymer of claim 1 wherein the ring-opened epoxide is selected from the the group consisting of:
—CH 2 CH(OH)(CH 2 ) v CH(OH)CH 2 —,
—CH[CH 2 OH](CH 2 ) v CH[CH 2 OH]—,
—CH 2 CH(OH)(CH 2 ) v CH[CH 2 OH]—,
—(CH 2 ) v OCH 2 CH(OH)CH 2 —, and
—(CH 2 ) v OCH 2 CH(CH 2 [OH])—,
wherein v is an integer of from 2 to 6.
5. The copolymer of claim 1 wherein the ring opened epoxide is derived an epoxycyclohexyl alkylene group containing from 2 to 20 carbon atoms in the alkylene moiety.
6. The copolymer of claim 5 wherein the epoxycyclohexyl alkylene group is ω-(3,4-epoxycycohexyl)alkylene.
7. The copolymer of claim 5 wherein the epoxycyclohexyl alkylene group is selected from the group consisting of β-(3,4-epoxycyclohexyl)ethylene, β-(3,4-epoxycyclohexyl)-β-methylethylene, and β-(3,4-epoxy-4-methylcyclohexyl)-β-methylethylene.
8. The copolymer of claim 1 wherein the secondary or tertiary amine represented by either X or Y are of the general formula:
wherein R 3 may be H, an alkyl or alkenyl group with containing from 1 to 30 carbons, and R 4 is a divalent alkylene, divalent cycloaliphatic alkylene or a divalent aralkylene group, any of which divalent groups may include heteroatoms, and g is 0 or 1.
9. The copolymer of claim 8 wherein R 3 is methyl.
10. The copolymer of claim 8 wherein R 4 is a divalent alkylene group of less than 10 carbon atoms.
11. The copolymer of claim 1 wherein R 1 is methyl, a is 2 or 3, the sum of all the b values and the d value is from 10 to 50, c is from 10 to 100 and the ring-opened epoxide is selected from the group consisting of
—CH 2 CH(OH)(CH 2 ) v CH(OH)CH 2 —,
—CH[CH 2 OH](CH 2 ) v CH[CH 2 OH]—,
—CH 2 CH(OH)(CH 2 ) v CH[CH 2 OH]—,
—(CH 2 ) v OCH 2 CH(OH)CH 2 —, and
—(CH 2 ) v OCH 2 CH(CH 2 [OH])—, and
wherein v is an integer of from 2 to 6.
12. A method for making a linear tri-block copolymer represented by the formula (1) ABA, wherein A is a polyalkyleneoxide unit or an aliphatic modified polyalkyleneoxide unit both of the general formula R 5 (C a H 2a O) d Y, and wherein B is an internal polysiloxane unit of the general formula:
[X(C a H 2a O) b R 2 [SiO(R 1 ) 2 ] c Si(R 1 ) 2 R 2 (OC a H 2a ) b X],
wherein R 1 is an alkyl containing from 1 to 4 carbon atoms,
R 2 is a divalent organic moiety containing from 1 to 30 carbon atoms,
each a in unit A and unit B is independently an integer of from 2 to 4,
each b is independently 0 or an integer of from 1 to 100,
c is an integer of from 1 to 1000,
R 5 is of the formula (C n H 2n−1 )— with n=1-30, or of the formula (C n H 2n−1 )— with N=2-30, or of the formula (C n H 2n−3 )— with n=4-30,
d is an integer of from 1 to 100,
provided that the sum of all the b values and the d value is an integer of from 1 to 100,
X and Y are divalent organic groups selected from a secondary amine, a tertiary amine and a ring-opened epoxide, such that when X is a ring-opened epoxide, Y is a secondary or tertiary amine, and when Y is a ring-opened epoxide, X is a secondary or tertiary amine, wherein the method comprises:
reacting a compound of the formula (2):
Q(C a H 2a O) b R 2 [SiO(R 1 ) 2 ] c Si(R 1 ) 2 R 2 (OC a H 2a ) b Q (2), and a compound of the general formula (3): R 5 (C a H 2a O) d Z (3), wherein R 1 , R 2 , R 5 , a, b, c and d are as defined and each Q independently and Z is either a primary or secondary amine, or an epoxy-containing group, with the proviso that if Q is a primary or secondary amine, Z is epoxy-containing group, and if Z is a primary or secondary amine, then Q is an epoxy-containing group.
13. The method of claim 12 wherein the compound of the general formula (2) is made by reacting α,ω-hydrogenpolysiloxane of the general formula (4):
[HSiO(R 1 ) 2 ] c Si(R 1 ) 2 H (4)
with an unsaturated epoxide containing a terminal olefinic bond, in the presence of a hydrosilylation catalyst.
14. The method of claim 12 wherein the compound of the general formula (3) is R(OCH 2 CH 2 ) a [OCH(CH 3 )CH 2 ] b NH 2 wherein R is R 5 and a and b are as defined.
15. The method of claim 12 wherein the compound of the general formula (3) is selected from the group consisting of Jeffamine® M-600, Jeffamine® M-1000, Jeffamine® M-2005 and Jeffamine® XTJ-682.
16. The method of claim 12 wherein the reaction of compounds of the formulae (2) and (3) is conducted in a 1 to about 20% excess of compound of the formula (3).
17. The method of claim 12 wherein following the reaction of compounds of formula (2) and (3) the reaction product can be neutralized by a direct addition of a Bronstedt acid and/or undergo solvent exchange with a non-flammable solvent.
18. A silicone composition comprising the copolymer of claim 1 .
19. A silicone network composition comprising the copolymer of claim 1 .
20. A personal care composition comprising the copolymer of claim 1 .
21. A personal care composition comprising the copolymer of claim 1 wherein the personal care composition is one of a cleanser, a body wash, a soap, a lotion, a cream, shaving cream, hair spray, a conditioner, a shampoo, a deodorant, a moisturizer, and sunblock.
22. A softener composition for a substrate comprising the copolymer of claim 1 wherein the substrate is selected from the group consisting of a hair, a fiber and a textile.
23. The softener composition of claim 22 wherein the fiber is a natural fiber selected from the group consisting of cotton, silk, flax, cellulose, paper and wool.
24. The softener composition of claim 22 wherein the fiber is a synthetic fiber selected from the group consisting of polyester, polyamide, polyacrylonitrile, polyethylene, polypropylene and polyurethane.
25. The softener composition of claim 22 wherein the fiber is an inorganic fiber selected from the group consisting of glass and carbon fibers.
26. A hair conditioner comprising the copolymer of claim 1 .