Porous Inorganic/Organic Hybrid Materials With Ordered Domains for Chromatographic Separations and Processes for Their Preparation

• US 20080269368A1
• Filed: 07/15/2005
• Published: 10/30/2008
• Est. Priority Date: 07/30/2004
• Status: Active Grant

• Current Assignee: Waters Technologies Corporation (Waters Corporation)
• Original Assignee: Waters Investments Limited (Waters Corporation)
• Inventors: Wyndham, Kevin D., O'Gara, John E.
• Granted Patent: US 8,658,277 B2
• Time in Patent Office: Days
• US Class Current: 521/154
• CPC Class Codes: B01J 20/28095 Shape or type of pores, voids, channels, ducts
• CPC Class Codes: B01J 20/285 based on polymers
• CPC Class Codes: B01J 20/3057 Use of a templating or imprinting material molecularly imprinted polymers B01J20/268; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
• CPC Class Codes: B01J 2220/46 Materials comprising a mixture of inorganic and organic materials materials coated or impregnated on a carrier B01J20/32
• CPC Class Codes: B29C 67/20 for porous or cellular articles, e.g. of foam plastics, coarse-pored chemical aspects of working up macro-molecular substances to porous or cellular articles C08J9/00
• CPC Class Codes: C08G 83/001 Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
• CPC Class Codes: C08J 9/36 After-treatment C08J9/22 takes precedence
• CPC Class Codes: Y10T 428/249953 Composite having voids in a component [e.g., porous, cellular, etc.]
• CPC Class Codes: Y10T 428/24996 With internal element bridging layers, nonplanar interface between layers, or intermediate layer of commingled adjacent foam layers
• CPC Class Codes: Y10T 428/249967 Inorganic matrix in void-containing component
• CPC Class Codes: Y10T 428/249969 Of silicon-containing material [e.g., glass, etc.]
• CPC Class Codes: Y10T 428/249975 Void shape specified [e.g., crushed, flat, round, etc.]
• CPC Class Codes: Y10T 428/249981 Plural void-containing components

Abstract

Porous hybrid inorganic/organic materials comprising ordered domains are disclosed. Methods of making the materials and use of the materials for chromatographic are also disclosed.

Claims

1. A porous hybrid inorganic/organic material comprising ordered domains and having a chromatographically-enhancing pore geometry.

3. The hybrid material of claim 1, wherein diffraction peak maxima observed for said material exhibit a 2θ

position that excludes diffraction peaks resulting from atomic-range order that are associated with amorphous material.

4. The hybrid material of claim 3, wherein the excluded diffraction peak ranges from about 20°

to about 23°

2θ

.

5. The hybrid material of claim 1, wherein said inorganic portion of said hybrid material is selected from the group consisting of alumina, silica, titanium or zirconium oxides, and ceramic materials.

6. The hybrid material of claim 5 wherein said inorganic portion of said hybrid material is silica.

7. The hybrid material of claim 1, wherein the percentage by mass of ordered domains of said material ranges from about 1% to about 100%.

8. The hybrid material of claim 1, wherein pores of a diameter of less than about 34 Å

contribute less than about 110 m²/g to less than about 50 m²/g to the specific surface area of the material.

9. The hybrid material of claim 1 or, wherein said material comprises porous inorganic/organic hybrid particles.

10. The hybrid material of claim 1, wherein said material comprises a monolith.

11. The hybrid material of claim 10, wherein said monolith comprises coalesced porous inorganic/organic hybrid particles.

12. The hybrid material of claim 9, wherein said particles are essentially spherical.

13. The hybrid material of claim 9, wherein said particles have a specific surface area of about 50 to 800 m²/g, said particles have specific pore volumes of about 0.25 to 1.5 cm³/g, and said particles have an average pore diameter of about 50 to 500 Å

.

14. The hybrid material of claim 13, wherein said particles have a specific surface area of about 100 to 700 m²/g.

15. The hybrid material of claim 13, wherein said particles have a specific surface area of about 300 to 600 m²/g.

16. The hybrid material of claim 13, wherein said particles have specific pore volumes of about 0.7 to 1.3 cm³/g.

17. The hybrid material of claim 13, wherein said particles have an average pore diameter of about 50 to 300 Å

.

18. The hybrid material of claim 1, wherein said material comprises porous hybrid inorganic/organic particles that have a micropore surface area of less than about 110 m²/g.

19. The hybrid material of claim 18, wherein said particles have a micropore surface area of less than about 105 m²/g.

20. The hybrid material of claim 18, wherein said particles have a micropore surface area of less than about 80 m²/g.

21. The hybrid material of claim 18, wherein said particles have a micropore surface area of less than about 50 m²/g.

22. The hybrid material of claim 9, wherein said particles have been surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.

23. The hybrid material of claim 22, wherein said hybrid particles have been surface modified with a surface modifier having the formula Z_a(R′

)_bSi—

R, where Z=Cl, Br, I, C₁-C₅ alkoxy, dialkylamino or trifluoromethanesulfonate;

a and b are each an integer from 0 to 3 provided that a+b=3;

R′

is a C₁-C₆ straight, cyclic or branched alkyl group, and R is a functionalizing group.

24. The hybrid material of claim 23, wherein R′

is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl and cyclohexyl.

25. The hybrid material of claim 23, wherein the functionalizing group R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cyano, amino, diol, nitro, ester, a cation or anion exchange group, or an alkyl or aryl group containing an embedded polar functionality.

26. The hybrid material of claim 25, wherein said functionalizing group R is a C₁-C₃₀ alkyl group.

27. The hybrid material of claim 25, wherein said functionalizing group R is a C₁-C₂₀ alkyl group.

28. The hybrid material of claim 22, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane, and octadecyldimethylchlorosilane.

29. The hybrid material of claim 28, wherein said surface modifier is octyltrichlorosilane or octadecyltrichlorosilane.

30. The hybrid material of claim 22, wherein said particles have been surface modified by coating with a polymer.

31. The hybrid material of claim 22, wherein said particles have been surface modified by a combination of an organic group surface modifier and a silanol group surface modifier.

32. The hybrid material of claim 22, wherein said particles have been surface modified by a combination of an organic group surface modifier and a polymeric coating surface modifier.

33. The hybrid material of claim 22, wherein said particles have been surface modified by a combination of a silanol group surface modifier and a polymeric coating surface modifier.

34. The hybrid material of claim 22, wherein said particles have been surface modified via formation of an organic covalent bond between an organic group of the particle and a surface modifier.

35. The hybrid material of claim 22, wherein said particles have been surface modified by a combination of an organic group surface modifier, a silanol group surface modifier, and a polymeric coating surface modifier.

36. The hybrid material of claim 22, wherein said particles have been surface modified by a silanol group surface modifier.

37. The hybrid material of claim 1 having the formula SiO₂/(R²_pR⁴_qSiO_t)_n or SiO₂/[R⁶(R²_rSiO_t)_m]_n wherein R² and R⁴ are independently C₁-C₁₈ aliphatic or aromatic moieties optionally substituted with alkyl, aryl, cyano, amino, hydroxyl, diol, nitro, ester, ion exchange or embedded polar functionalities, R⁶ is a substituted or unsubstituted C₁-C₁₈ alkylene, alkenylene, alkynylene or arylene moiety bridging two or more silicon atoms, p and q are 0, 1 or 2, provided that p+q=1 or 2, and that when p+q=1, t=1.5, and when p+q=2, t=1;

r is 0 or 1, provided that when r=0, t=1.5, and when r=1, t=1;

m is an integer greater than or equal to 2, and n is a number from 0.03 to 1.5.

38. The hybrid material of claim 37, wherein n is a number from 0.1 to 1.0.

39. The hybrid material of claim 37, wherein n is a number from 0.2 to 0.5.

56. A method of preparing a porous hybrid inorganic/organic material comprising ordered domains of claim 1, comprising the steps of:

(a) forming a pore restructuring template;

(b) restructuring the pores of a porous hybrid inorganic/organic material by contacting the pores of the porous hybrid inorganic/organic material with the pore restructuring template, to thereby restructure the pores into ordered domains; and

(c) removing the pore restructuring template from the restructured pores;

to thereby prepare a porous hybrid inorganic/organic material comprising ordered domains.

57. The method of claim 56, wherein the restructuring of step (b) comprises admixing the porous hybrid inorganic/organic material with an aqueous solution containing a base and a pore restructuring template, and heating the admixture at a temperature and for a period of time sufficient to form ordered domains.

80. The method of claim 56, further comprising modifying the pore structure of the porous hybrid inorganic/organic material to thereby form a chromatographically-enhancing pore geometry, to thereby prepare a porous hybrid inorganic/organic material comprising ordered domains and having a chromatographically-enhancing pore geometry.

98. A separations device comprising a porous hybrid inorganic/organic hybrid material of claim 1.

99. A separations device of claim 98 selected from the group consisting of chromatographic columns, thin layer chromatographic (TLC) plates, filtration membranes, microtiter plates, scavenger resins, and solid phase organic synthesis supports.

100. A chromatographic column comprising

a) a column having a cylindrical interior for accepting porous hybrid inorganic/organic material, and

b) a chromatographic bed comprising a porous hybrid inorganic/organic material of claim 1.

101. A porous hybrid inorganic/organic material of claim 1, prepared by a process comprising the steps of:

(a) forming a pore restructuring template;

(b) restructuring the pores of a porous hybrid inorganic/organic material by contacting the pores of the porous hybrid inorganic/organic material with the pore restructuring template, to thereby restructure the pores into ordered domains; and

(c) removing the pore restructuring template from the restructured pores.

102. The hybrid material of claim 101, wherein the restructuring of step (b) comprises admixing the porous hybrid inorganic/organic material with an aqueous solution containing a base and a pore restructuring template, and heating the admixture at a temperature and for a period of time sufficient to form ordered domains.

116. The hybrid material of claim 101, wherein the process further comprises modifying the pore structure of the porous hybrid inorganic/organic material to thereby form a chromatographically-enhancing pore geometry, to thereby prepare a porous hybrid inorganic/organic material comprising ordered domains and having a chromatographically-enhancing pore geometry.

2. A porous hybrid inorganic/organic material comprising ordered domains having formula I, II or III below:

(A)_x(B)_y(C)_z 

 

(Formula I)

wherein the order of repeat units A, B, and C may be random, block, or a combination of random and block;

A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;

B is an organosiloxane repeat unit which is bonded to one or more repeat units B or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;

C is an inorganic repeat unit which is bonded to one or more repeat units B or C via an inorganic bond; and

x, y are positive numbers and z is a non negative number, wherein

when z=0, then 0.002≦

x/y≦

210, and when z≠

0, then

0.0003≦

y/z≦

500 and 0.002≦

z/(y+z)≦

210;

(A)_x(B)_y(B*)_y*(C)_z 

 

(Formula II)

wherein the order of repeat units A, B, B*, and C may be random, block, or a combination of random and block;

A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;

B is an organosiloxane repeat units which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;

B* is an organosiloxane repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond, wherein B* is an organosiloxane repeat unit that does not have reactive (i.e., polymerizable) organic components and may further have a protected functional group that may be deprotected after polymerization;

C is an inorganic repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic bond; and

x, y are positive numbers and z is a non negative number, wherein

when z=0, then 0.002≦

x/(y+y*)≦

210, and when z≠

0, then

0.0003≦

(y+y*)/z≦

00 and 0.002≦

x/(y+y*+z)≦

210;

or

[A]_y[B]_x 

 

(Formula III),

wherein x and y are whole number integers and A is

SiO₂/(R¹_pR²_qSiO_t)_n or SiO₂/[R³(R¹_rSiO_t)_m]_n;

wherein R¹ and R² are independently a substituted or unsubstituted C₁ to C₇ alkyl group, or a substituted or unsubstituted aryl group, R³ is a substituted or unsubstituted C₁ to C₇ alkylene, alkenylene, alkynylene, or arylene group bridging two or more silicon atoms, p and q are 0, 1, or 2, provided that p+q=1 or 2, and that when p+q=1, t=1.5, and when p+q=2, t=1;

r is 0 or 1, provided that when r=0, t=1.5, and when r=1, t=1;

m is an integer greater than or equal to 2; and

n is a number from 0.01 to 100;

B is;

SiO₂/(R⁴_vSiO_t)_n

wherein R⁴ is hydroxyl, fluorine, alkoxy, aryloxy, substituted siloxane, protein, peptide, carbohydrate, nucleic acid, or combinations thereof, R⁴ is not R¹, R², or R³;

v is 1 or 2, provided that when v=1, t=1.5, and when v=2, t=1; and

n is a number from 0.01 to 100;

wherein the material of formula III has an interior area and an exterior surface, and said interior area of said material has a composition represented by A;

said exterior surface of said material has a composition represented by A and B, and wherein said exterior composition is between about 1 and about 99% of the composition of B and the remainder comprising A.

40. The hybrid material of Formula II according to claim 2, wherein B is bonded to one or more repeat units B or C via an inorganic siloxane bond and is bonded to one or more repeat units A or B via an organic bond.

41. The hybrid material of Formula I or II according to claim 2, wherein 0.003≦

y/z≦

50 and 0.02≦

x/(y+z)≦

21.

42. The hybrid material of Formula I or II according to claim 2, wherein 0.03≦

y/z≦

5 and 0.2≦

x/(y+z)≦

2.1.

43. The hybrid material of Formula I or II according to claim 2, wherein A is a substituted ethylene group, B is a oxysilyl-substituted alkylene group, and C is a oxysilyl group.

44. The hybrid material of Formula I or II according to claim 2, wherein A is selected from the group consisting of

45. The hybrid material according to claim 44, wherein each R is independently hydrogen, methyl, ethyl, or propyl.

46. The hybrid material of Formula I or II according to claim 2, wherein B is selected from the group consisting of

47. The hybrid material of Formula I or II according to claim 2, wherein C is

48. The hybrid material of Formula III of claim 2, wherein said exterior surface has a composition that is between about 50 and about 90% of composition B, with the remainder comprising composition A.

49. The hybrid material of claim 48 wherein said exterior surface has a composition that is between about 70 and about 90% of composition B, with the remainder comprising composition A.

50. The hybrid material of Formula III of claim 2, wherein R⁴ is hydroxyl.

51. The hybrid material of Formula III of claim 2, wherein R⁴ is fluorine.

52. The hybrid material of Formula III of claim 2, wherein R⁴ is methoxy.

53. The hybrid material of Formula III of claim 2, wherein R⁴ is

—

OSi(R⁵)₂—

R⁶

wherein R⁵ is a C₁ to C₆ straight, cyclic, or branched alkyl, aryl, or alkoxy group, a hydroxyl group, or a siloxane group, and R⁶ is a C₁ to C₃₆ straight, cyclic, or branched alkyl, aryl, or alkoxy group, wherein R⁶ is unsubstituted or substituted with one or more moieties selected from the group consisting of halogen, cyano, amino, diol, nitro, ether, carbonyl, epoxide, sulfonyl, cation exchanger, anion exchanger, carbamate, amide, urea, peptide, protein, carbohydrate, nucleic acid functionalities, and combinations thereof.

54. The hybrid material of claim 53, wherein R⁶ is a C₁₈ group.

55. The material of claim 53, wherein R⁶ is a cyanopropyl group.

58-79. -79. (canceled)

81-97. -97. (canceled)

103-115. -115. (canceled)

117-133. -133. (canceled)