Porous inorganic/organic hybrid materials with ordered domains for chromatographic separations and processes for their preparation

• US 8,658,277 B2
• Filed: 07/15/2005
• Issued: 02/25/2014
• Est. Priority Date: 07/30/2004
• Status: Active Grant

• Current Assignee: Waters Technologies Corporation (Waters Corporation)
• Original Assignee: Waters Technologies Corporation (Waters Corporation)
• Inventors: Wyndham, Kevin D., O'Gara, John E.
• Primary Examiner(s): Krylova, Irina
• Application Number:
  US11/631,341
• Publication Number:
  US 20080269368A1
• Time in Patent Office: 3,147 Days
• Field of Search: 526/279
• US Class Current: 428/314.2
• 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 particle or monolith comprising ordered domains and having a chromatographically-enhancing pore geometry, prepared by a method comprising the steps of:

(a) forming a pore restructuring template;

(b) restructuring the pores of the porous hybrid inorganic/organic particle or monolith by contacting the pores of the porous hybrid inorganic/organic particle or monolith 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 the porous hybrid inorganic/organic particle or monolith comprising ordered domains;

wherein the pores of a diameter of 34 Å

or less contribute less than about 110 m²/g to the specific surface area of the particle or monolith and the ratio of the micropore surface area to the specific surface area is from 0.036 to 0.273,

wherein the particle or monolith has a specific pore volume of about 0.25 to 1.5 cm³/g and an average pore diameter of about 50 to 500 Å

,

and wherein diffraction peaks are present for said ordered domains in the range of 0.8 to 20°

2θ

,

and wherein the diffraction peak maxima observed for said particle or monolith exhibit a 2θ

position that excludes diffraction peaks ranging from about 20°

to about 23°

2θ

resulting from atomic-range order that are associated with amorphous material.

2. The inorganic/organic hybrid particle or monolith of claim 1, wherein said inorganic portion of said hybrid particle or monolith is selected from the group consisting of alumina, silica, titanium oxide, zirconium oxide, and ceramic materials.

3. The inorganic/organic hybrid particle or monolith of claim 2 wherein said inorganic portion of said hybrid particle or monolith is silica.

4. The inorganic/organic hybrid particle or monolith of claim 1, which is a porous inorganic/organic hybrid particle.

5. The inorganic/organic hybrid particle or monolith of claim 1, which is a monolith.

6. The inorganic/organic hybrid monolith of claim 5, wherein said monolith comprises coalesced porous inorganic/organic hybrid particles.

7. The inorganic/organic hybrid particle of claim 4, wherein said particle is essentially spherical.

8. The inorganic/organic hybrid particle of claim 4, wherein said particle has a specific surface area of about 50 to 800 m²/g.

9. The inorganic/organic hybrid particle of claim 8, wherein said particle has a specific surface area of about 100 to 700 m²/g.

10. The inorganic/organic hybrid particle of claim 8, wherein said particle has a specific surface area of about 300 to 600 m²/g.

11. The inorganic/organic hybrid particle of claim 8, wherein said particle has specific pore volumes of about 0.7 to 1.3 cm³/g.

12. The inorganic/organic hybrid particle of claim 8, wherein said particle has an average pore diameter of about 50 to 300 Å

.

13. The inorganic/organic hybrid particle or monolith of claim 1, wherein said particle or monolith has the micropore surface area of less than about 105 m²/g.

14. The inorganic/organic hybrid particle or monolith of claim 13, wherein said particle or monolith has the micropore surface area of less than about 80 m²/g.

15. The inorganic/organic hybrid particle or monolith of claim 14, wherein said particle or monolith has the micropore surface area of less than about 50 m²/g.

16. The inorganic/organic hybrid particle of claim 4, wherein said particle has 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.

17. The inorganic/organic hybrid particle of claim 16, wherein said hybrid particle has 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.

18. The inorganic/organic hybrid particle of claim 17, wherein R′

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

19. The inorganic/organic hybrid particle of claim 17, wherein the functionalizing group R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cyano, amino, diol, nitro, ester, a cation exchange group, anion exchange group, an alkyl group containing an embedded polar functionality, and aryl group containing an embedded polar functionality.

20. The inorganic/organic hybrid particle of claim 19, wherein said functionalizing group R is a C₁-C₃₀ alkyl group.

21. The inorganic/organic hybrid particle of claim 19, wherein said functionalizing group R is a C₁-C₂₀ alkyl group.

22. The inorganic/organic hybrid particle of claim 16, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane, and octadecyldimethylchlorosilane.

23. The inorganic/organic hybrid particle of claim 22, wherein said surface modifier is octyltrichlorosilane or octadecyltrichlorosilane.

24. The inorganic/organic hybrid particle of claim 16, wherein said particle has been surface modified by coating with a polymer.

25. The inorganic/organic hybrid particle of claim 16, wherein said particle has been surface modified by a combination of an organic group surface modifier and a silanol group surface modifier.

26. The inorganic/organic hybrid of claim 16, wherein said particle has been surface modified by a combination of an organic group surface modifier and a polymeric coating surface modifier.

27. The inorganic/organic hybrid particle of claim 16, wherein said particle has been surface modified by a combination of a silanol group surface modifier and a polymeric coating surface modifier.

28. The inorganic/organic hybrid particle of claim 16, wherein said particle has been surface modified via formation of an organic covalent bond between an organic group of the particle and a surface modifier.

29. The inorganic/organic hybrid particle of claim 16, wherein said particle has been surface modified by a combination of an organic group surface modifier, a silanol group surface modifier, and a polymeric coating surface modifier.

30. The inorganic/organic hybrid particle of claim 16, wherein said particle has been surface modified by a silanol group surface modifier.

31. The inorganic/organic hybrid particle or monolith 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 x=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.

32. The inorganic/organic hybrid particle or monolith of claim 31, wherein n is a number from 0.1 to 1.0.

33. The inorganic/organic hybrid particle or monolith of claim 31, wherein n is a number from 0.2 to 0.5.

34. A porous hybrid inorganic/organic particle or monolith comprising ordered domains and having a chromatographically-enhancing pore geometry and 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 is 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≦

x/(y+z)≦

210;

or

(A)_x(B)_y(B*)_y*(C)_z 

 

(Formula II)

wherein the order of repeat units A, B, B*, and C is 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, 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, B*, or C via an inorganic siloxane bond, wherein the B* organosiloxane repeat unit does not have reactive 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, 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≦

500 and 0.002≦

x/(y+y*+z)≦

210;

[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 t=1; and

n is a number from 0.01 to 100;

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

said exterior surface of said particle or monolith has a composition represented by A and B, and wherein said exterior composition is between 1 and 99% of the composition of B and the remainder comprising A,

wherein said particle or monolith is prepared by a method comprising the steps of;

(a) forming a pore restructuring template;

(b) restructuring the pores of the porous hybrid inorganic/organic particle or monolith by contacting the pores of the porous hybrid inorganic/organic article or monolith 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 the porous hybrid inorganic/organic particle or monolith comprising ordered domains;

wherein the pores of a diameter of 34 Å

or less contribute less than about 110 m²/g to the specific surface area of the particle or monolith and the ratio of the micropore surface area to the specific surface area is from 0.036 to 0.273,

wherein the particle or monolith has a specific pore volume of about 0.25 to 1.5 cm³/g and an average pore diameter of about 50 to 500 Å

,

and wherein diffraction peaks are present for said ordered domains in the range of 0.8 to 20°

2θ

,

and wherein the diffraction peak maxima observed for said particle or monolith exhibit a 2θ

position that excludes diffraction peaks ranging from about 20°

to about 23°

2θ

resulting from atomic-range order that are associated with amorphous material.

35. The inorganic/organic hybrid particle or monolith of Formula II according to claim 34, 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.

36. The inorganic/organic hybrid particle or monolith of Formula I or II according to claim 34, wherein 0.003≦

y/z≦

50 and 0.02≦

x/(y+z)≦

21.

37. The inorganic/organic hybrid particle or monolith of Formula I or II according to claim 34, wherein 0.03≦

y/z≦

5 and 0.2≦

x/(y+z)≦

2.1.

38. The inorganic/organic hybrid particle or monolith of Formula I or II according to claim 34, wherein A is a substituted ethylene group, B is a oxysilyl-substituted alkylene group, and C is a oxysilyl group.

39. The inorganic/organic hybrid particle or monolith of Formula I or II according to claim 34, wherein A is selected from the group consisting of

40. The inorganic/organic hybrid particle or monolith according to claim 39, wherein each R is independently hydrogen, methyl, ethyl, or propyl.

41. The inorganic/organic hybrid particle or monolith of Formula I or II according to claim 34, wherein B is selected the group consisting of

42. The inorganic/organic hybrid particle or monolith of Formula I or II according to claim 34, wherein C is

43. The inorganic/organic hybrid particle or monolith of Formula III of claim 34, wherein said exterior surface has a composition that is between about 50 and about 90% of composition B, with the remainder comprising composition A.

44. The inorganic/organic hybrid particle or monolith of claim 43 wherein said exterior surface has a composition that is between about 70 and about 90% of composition B, with the remainder comprising composition A.

45. The inorganic/organic hybrid particle or monolith of Formula III of claim 34, wherein R⁴ is hydroxyl.

46. The inorganic/organic hybrid particle or monolith of Formula III of claim 34, wherein R⁴ is fluorine.

47. The inorganic/organic hybrid particle or monolith of Formula III of claim 34, wherein R⁴ is methoxy.

48. The inorganic/organic hybrid particle or monolith of Formula III of claim 34, 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, dial, nitro, ether, carbonyl, epoxide, sulfonyl, cation exchanger, anion exchanger, carbamate, amide, urea, peptide, protein, carbohydrate, nucleic acid functionalities, and combinations thereof.

49. The inorganic/organic hybrid particle or monolith of claim 48, wherein R⁶ is a C₁₈ group.

50. The inorganic/organic hybrid particle or monolith of claim 48, wherein R⁶ is a cyanopropyl group.