Compatibilized immiscible polymer blends and molecular sieve membranes thereof
In some aspects, the present disclosure provides a polymer composition which comprises two polymer molecules and a compatibilizing agent. In some embodiments, the polymer composition is useful for the preparation of membranes used in the separation of two or more gases. In some embodiments, the polymer composition comprises a polyimide polymer and a polybenzimidazole polymer which have been compatibilizing with a small molecule or a metal organic framework.
1. A composition comprising a mixture of compounds comprising:
(A) a polyimide polymer of the formula:
wherein:
x is 1-500; wherein each repeating unit can have different substituents at R 1 , R 2 , R 3 , R 4 , R 5 , and n 1 ;
R 1 and R 2 are each independent selected from alkyl (C≤12) , substituted alkyl (C≤12) , aryl (C≤12) , or substituted aryl (C≤12) ;
R 3 and R 4 are each independently selected from hydrogen, halo, hydroxy, amino, cyano, carboxy, nitro, alkyl (C≤12) , substituted alkyl (C≤12) , alkoxy (C≤12) , or substituted alkoxy (C≤12) ;
R 5 is hydrogen, halo, hydroxy, amino, cyano, carboxy, nitro, alkyl (C≤12) , substituted alkyl (C≤12) , aryl (C≤12) , substituted aryl (C≤12) , alkoxy (C≤12) , or substituted alkoxy (C≤12) ; and
n 1 is 0, 1, 2, 3, or 4;
(B) a polybenzimidazole polymer of the formula:
wherein:
z is 1-200;
R 6 and R 7 are each independently selected from hydrogen, halo, hydroxy, amino, cyano, carboxy, nitro, alkyl (C≤12) , substituted alkyl (C≤12) , alkoxy (C≤12) , or substituted alkoxy (C≤12) , alkylamino (C≤12) , substituted alkylamino (C≤12) , dialkylamino (C≤12) , substituted dialkylamino (C≤12) ;
R 8 is hydrogen, halo, hydroxy, amino, cyano, carboxy, nitro, alkyl (C≤12) , substituted alkyl (C≤12) , aryl (C≤12) , substituted aryl (C≤12) , alkoxy (C≤12) , or substituted alkoxy (C≤12) ; and
n 2 is 0, 1, 2, 3, or 4; and
(C) a chemical compound of the formula:
wherein:
R 9 is alkyl (C≤12) , aryl (C≤12) , aralkyl (C≤12) , or a substituted version of any of these groups;
R 10 is amino, cyano, halo, hydroxy, or nitro, or alkyl (C≤8) , cycloalkyl (C≤8) , alkoxy (C≤8) , acyl (C≤8) , amido (C≤8) , acyloxy (C≤8) , alkylamino (C≤8) , dialkylamino (C≤8) , or a substituted version of any of these groups;
n 3 is 0, 1, 2, 3, or 4.
2. The composition of claim 1 , wherein the compound of formula I is further defined as:
wherein:
y and y′ are each independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, provided that the sum of y and y′ is greater than 1 and less than 10 and the product of x and the sum of y and y′ is less than 500;
R 1 , R 2 , R 1 ′, and R 2 ′ are each independent selected from alkyl (C≤12) , substituted alkyl (C≤12) , aryl (C≤12) , or substituted aryl (C≤12) ;
R 3 , R 4 , R 3 ′ and R 4 ′ are each independently selected from hydrogen, halo, hydroxy, amino, cyano, carboxy, nitro, alkyl (C≤12) , substituted alkyl (C≤12) , alkoxy (C≤12) , or substituted alkoxy (C≤12) ;
R 5 and R 5 ′ are each independently selected from hydrogen, halo, hydroxy, amino, cyano, carboxy, nitro, alkyl (C≤12) , substituted alkyl (C≤12) , aryl (C≤12) , substituted aryl (C≤12) , alkoxy (C≤12) , or substituted alkoxy (C≤12) ; and
n 1 and n 1 ′ are each independently selected from 0, 1, 2, 3, or 4.
3. The composition of claim 2 , wherein R 1 , R 2 , R 1 1 , and R 2 ′ are fluoroalkyl (C≤12) .
4. The composition of claim 2 , wherein R 5 is alkyl (C≤12) or substituted alkyl (C≤12) or carboxy.
5. The composition of claim 2 , wherein R 5 ′ is alkyl (C≤12) or substituted alkyl (C≤12) or carboxy.
6. The composition of claim 2 , wherein y is 2, 3, 4, 5, 8, 9, or 10.
7. The composition of claim 2 , wherein y′ is 1, 2, 3, 4, or 5.
8. The composition of claim 1 , wherein (C) is a compound of the formula:
wherein:
R 9 is alkyl (C≤12) , aryl (C≤12) , aralkyl (C≤12) , or a substituted version of any of these groups.
9. The composition of claim 1 , wherein the composition of the polymer of formula I and the polymer of formula II are immiscible when the chemical compound is not present but are miscible when the chemical compound is present.
10. The composition of claim 1 , wherein the composition comprises from about 1 wt % to about 20 wt % of the chemical compound of formula III.
11. A membrane formed from the composition of claim 1 .
12. A method of preparing a composition comprising admixing an immiscible polyimide polymer with polybenzimidazole polymer with a small molecule compatibilizer agent to obtain the composition, wherein the composition comprises a mixture of the polyimide and polybenzimidazole, and wherein the mixture comprises a polymer domain of less than 1.25 μm.
13. The method of claim 12 , wherein the small molecule compatibilizer agent has the formula:
wherein:
R 9 is alkyl (C≤12) , aryl (C≤12) , aralkyl (C≤12) , or a substituted version of any of these groups.
14. The method of claim 12 , wherein the polybenzimidazole has the formula:
wherein:
z is 1-200;
R 6 and R 7 are each independently selected from hydrogen, halo, hydroxy, amino, cyano, carboxy, nitro, alkyl (C≤12) , substituted alkyl (C≤12) , alkoxy (C≤12) , or substituted alkoxy (C≤12) , alkylamino (C≤12) , substituted alkylamino (C≤12) , dialkylamino (C≤12) , substituted dialkylamino (C≤12) ;
R 8 is hydrogen, halo, hydroxy, amino, cyano, carboxy, nitro, alkyl (C≤12) , substituted alkyl (C≤12) , aryl (C≤12) , substituted aryl (C≤12) , alkoxy (C≤12) , or substituted alkoxy (C≤12) ; and
n 2 is 0, 1, 2, 3, or 4.
15. The method of claim 12 , wherein the polyimide has the formula:
wherein:
x is 1-500; wherein each repeating unit can have different substituents at R 1 , R 2 , R 3 , R 4 , R 5 , and n 1 ;
R 1 and R 2 are each independent selected from alkyl (C≤12) , substituted alkyl (C≤12) , aryl (C≤12) , or substituted aryl (C≤12) ;
R 3 and R 4 are each independently selected from hydrogen, halo, hydroxy, amino, cyano, carboxy, nitro, alkyl (C≤12) , substituted alkyl (C≤12) , alkoxy (C≤12) , or substituted alkoxy (C≤12) ;
R 5 is hydrogen, halo, hydroxy, amino, cyano, carboxy, nitro, alkyl (C≤12) , substituted alkyl (C≤12) , aryl (C≤12) , substituted aryl (C≤12) , alkoxy (C≤12) , or substituted alkoxy (C≤12) ; and
n 1 is 0, 1, 2, 3, or 4.
16. The method of claim 15 , wherein the polyimide is further defined as:
wherein:
y and y′ are each independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, provided that the sum of y and y′ is greater than 1 and less than 10 and the product of x and the sum of y and y′ is less than 500;
R 1 , R 2 , R 1 ′, and R 2 ′ are each independent selected from alkyl (C≤12) , substituted alkyl (C≤12) , aryl (C≤12) , or substituted aryl (C≤12) ;
R 3 , R 4 , R 3 ′ and R 4 ′ are each independently selected from hydrogen, halo, hydroxy, amino, cyano, carboxy, nitro, alkyl (C≤12) , substituted alkyl (C≤12) , alkoxy (C≤12) , or substituted alkoxy (C≤12) ;
R 5 and R 5 ′ are each independently selected from hydrogen, halo, hydroxy, amino, cyano, carboxy, nitro, alkyl (C≤12) , substituted alkyl (C≤12) , aryl (C≤12) , substituted aryl (C≤12) , alkoxy (C≤12) , or substituted alkoxy (C≤12) ; and
n 1 and n 1 ′ are each independently selected from 0, 1, 2, 3, or 4.
17. A method of preparing a carbon molecular sieve membrane comprising:
(A) obtaining a membrane from the composition of claim 12 ; and
(B) heating the membrane to a temperature from about 400° C. to about 1000° C.
18. A method of using a composition of claim 1 to separate one gas from a mixture of two or more gases comprising:
A) exposing the mixture of two or more gases to the composition, wherein one or more gases is absorbed to the composition to a greater extent than the other one or more gases;
B) separating the one or more non-absorbed gases from the one or more absorbed gases.
19. The method of claim 18 , wherein the gas mixture is hydrogen and carbon dioxide.
20. A carbon molecular sieve membrane formed from the composition of claim 1 .
21. The composition of claim 20 , wherein the carbon molecular sieve membrane comprises a matrix-droplet type morphology.