Superficially porous materials comprising a substantially nonporous hybrid core having narrow particle size distribution; process for the preparation thereof; and use thereof for chromatographic separations
The present invention provides novel chromatographic materials, e.g., for chromatographic separations, processes for its preparation and separations devices containing the chromatographic material; separations devices, chromatographic columns and kits comprising the same; and methods for the preparation thereof. The chromatographic materials of the invention are chromatographic materials comprising having a narrow particle size distribution.
1. A superficially porous material comprising superficially porous particles, wherein the superficially porous particles comprise an inorganic/organic hybrid core and one or more layers of a porous shell material surrounding the inorganic/organic hybrid core wherein the inorganic/organic hybrid core has a pore volume of less than 0.10 cc/g; and
wherein the inorganic/organic hybrid core has the formula:
(SiO 2 ) d /[R 2 ((R) p (R 1 ) q SiO t ) m ] (I)
wherein,
R and R 1 are each independently C 1 -C 18 alkoxy, C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 5 -C 18 aryloxy, or C 1 -C 18 heteroaryl;
R 2 is C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C 1 -C 18 heterocycloalkyl, C 5 -C 18 aryl, C 1 -C 18 heteroaryl, wherein R 2 is attached to two or more silicon atoms;
R, R 1 and R 2 are optionally substituted;
p and q are each independently 0.0 to 2.0,
t is 0.5, 1.0, or 1.5;
d is 0 to about 30; and
m=2-20,
t
=
(
3
-
(
p
+
q
)
)
2
,
and p+q≤2.
2. The superficially porous material of claim 1 , wherein the superficially porous material has chromatographically enhancing pore geometry.
3. The superficially porous material of claim 1 wherein the porous shell material is a porous inorganic/organic hybrid material.
4. The superficially porous material of claim 1 wherein the porous shell material is a porous silica.
5. The superficially porous material of claim 1 wherein the porous shell material is a porous composite material.
6. The superficially porous material of claim 1 , wherein the superficially porous particles comprise an inorganic/organic hybrid core and more than one layer of a porous shell material wherein each layer of the porous shell material is independently selected from a porous inorganic/organic hybrid material of formula (I) according to claim 1 , a porous silica, a porous composite material, or mixtures thereof.
7. The superficially porous material of claim 1 wherein the superficially porous material has a spherical core morphology, a rod shaped core morphology, a bent-rod shaped core morphology, a toroid shaped core morphology, or a dumbbell shaped core morphology.
8. The superficially porous material of claim 1 , wherein the inorganic/organic hybrid core has a particle size of 0.5-10 μm.
9. The superficially porous material of claim 1 , wherein the superficially porous particles comprise an inorganic/organic hybrid core and more than one layer of a porous shell material, wherein each layer of porous shell material is independently from 0.05 μm to 5 μm in thickness as measured perpendicular to an outer surface of the inorganic/organic hybrid core.
10. The superficially porous material of claim 1 , wherein the superficially porous material has an average particle size between 0.8-10.0 μm.
11. The superficially porous material of claim 1 , wherein the superficially porous material has an average pore diameter of about 25-600 Å.
12. The superficially porous material of claim 1 , wherein the superficially porous material has an average pore volume of about 0.11-0.50 cm 3 /g.
13. The superficially porous material of claim 1 , wherein pore surface area is between about 10 m 2 /g and 400 m 2 /g.
14. The superficially porous material of claim 1 , which has been further surface modified.
15. The superficially porous material of claim 1 , which has been further surface modified by:
coating with a polymer;
by coating with a polymer by a combination of organic group and silanol group modification;
a combination of organic group modification and coating with a polymer;
a combination of silanol group modification and coating with a polymer;
formation of an organic covalent bond between an organic group of the material and a modifying reagent; or
a combination of organic group modification, silanol group modification and coating with a polymer.
16. A separations device having a stationary phase comprising the superficially porous material of claim 1 .
17. A chromatographic column, comprising
a) a column having a cylindrical interior for accepting a packing material and
b) a packed chromatographic bed comprising the superficially porous material of claim 1 .
18. A chromatographic device, comprising
a) an interior channel for accepting a packing material and
b) a packed chromatographic bed comprising the superficially porous material of claim 1 .
19. A kit comprising the superficially porous material of claim 1 , and instructions for use.
20. The superficially porous material of claim 1 , wherein the superficially porous particles comprise an inorganic/organic hybrid core and one or more layer of a porous shell material; and wherein each layer of the porous shell material is independently selected from a porous inorganic/organic hybrid material of formula (I) according to claim 1 .