Porous inorganic/organic homogenous copolymeric hybrid materials for chromatographic separations and process for the preparation thereof

A porous inorganic/organic homogenous copolymeric hybrid material of the formula:

• (A)x(B)y(C)z
• wherein the order of repeat units A, B, and C may be random, block, or a combination of random and block;
• A is selected from the group consisting of
• wherein each R is independently H or a C1-C10 alkyl group;
• m is an integer of from 1 to 20;
• n is an integer of from 0 to 10;
• and Q is hydrogen, N(C1-6alkyl)3, N(C1-6alkyl)2(C1-6alkylene-SO3), or C(C1-6hydroxyalkyl)3;
• B is an organosiloxane repeat unit selected from the group consisting of:
• an organosiloxane repeat unit derived from a monomer selected from the group consisting of:
• ethacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (3-acryloxypropyl)trimethoxysilane, O-(methacryloxyethyl)-N-(triethoxysilylpropyl)urethane, N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyltris(methoxyethoxy)silane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride, 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;
• wherein the porous inorganic/organic homogenous copolymeric hybrid material has specific pore volumes of about 0.25 to 2.5 cm3/g and an average pore diameter of about 50 to 300 Å.

A porous inorganic/organic homogenous copolymeric hybrid material of the formula:

• (A)x(B)y(B*)y*(C)z
• wherein the order of repeat units A, B, B*, and C may be random, block, or a combination of random and block;
• A is selected from the group consisting of
• wherein each R is independently H or a C1-C10 alkyl group;
• m is an integer of from 1 to 20;
• n is an integer of from 0 to 10;
• and Q is hydrogen, N(C1-6alkyl)3, N(C1-6alkyl)2(C1-6alkylene-SO3), or C(C1-6hydroxyalkyl)3;
• B is an organosiloxane repeat unit selected from the group consisting of:
• an organosiloxane repeat unit derived from a monomer selected from the group consisting of:
• ethacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (3-acryloxypropyl)trimethoxysilane, O-(methacryloxyethyl)-N-(triethoxysilylpropyl)urethane, N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyltris(methoxyethoxy)silane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride, 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≦500 and 0.002≦x/(y+y*+z)≦210;
• wherein the porous inorganic/organic homogenous copolymeric hybrid material has specific pore volumes of about 0.25 to 2.5 cm3/g and an average pore diameter of about to 300 Å.