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

Patent metadata

Field	Value
Publication number	US-9976008-B2
Application number	US-201514967647-A
Country	US
Kind code	B2
Filing date	Dec 14, 2015
Priority date	Oct 30, 2002
Publication date	May 22, 2018
Grant date	May 22, 2018

Abstract

The present invention relates to porous inorganic/organic homogenous copolymeric hybrid material materials, including particulates and monoliths, methods for their manufacture, and uses thereof, e.g., as chromatographic separations materials.

First claim

What is claimed is:

1. A method of preparing a porous inorganic/organic homogenous copolymeric hybrid material, comprising the steps of
(a) hydrolytically condensing an alkenyl-functionalized organosilane with a tetraalkoxysilane,
(b) copolymerizing the product of step (a) with an organic olefin monomer, and
(c) further hydrolytically condensing the product of step (b) to thereby prepare a porous inorganic/organic homogenous copolymeric hybrid material;
wherein said copolymerizing step is free radical-initiated and wherein said hydrolytically condensing step is an base-catalyzed;
and wherein said base is selected from the group consisting of ammonium hydroxide, hydroxide salts of the group I and group II metals, carbonate and hydrogencarbonate salts of the group I metals, and alkoxide salts of the group I and group II metals.

2. The method according to claim 1 , wherein said steps (a) and (b) are performed in a solvent selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, pentanol, hexanol, cyclohexanol, hexafluoroisopropanol, cyclohexane, petroleum ethers, diethyl ether, dialkyl ethers, tetrahydrofuran, acetonitrile, ethyl acetate, pentane, hexane, heptane, benzene, toluene, xylene, N,N-dimethylformamide, dimethyl sulfoxide, 1-methyl-2-pyrrolidinone, methylene chloride, chloroform, and combinations thereof.

3. The method according to claim 1 , wherein either of said steps (a) and (b) further comprises addition of a porogen.

4. The method according to claim 3 , wherein said porogen is selected from the group consisting of cyclohexanol, toluene, 2-ethylhexanoic acid, dibutylphthalate, 1-methyl-2-pyrrolidinone, 1-dodecanol, and a surfactant.

5. The method according to claim 1 , wherein said organic olefin monomer is selected from the group consisting of divinylbenzene, styrene, ethylene glycol dimethacrylate, 1-vinyl-2-pyrrolidinone and tert-butylmethacrylate, acrylamide, methacrylamide, N,N′-(1,2-dihydroxyethylene)bisacrylamide, N,N′-ethylenebisacrylamide, N,N′-methylenebisacrylamide, butyl acrylate, ethyl acrylate, methyl acrylate, 2-(acryloxy)-2-hydroxypropyl methacrylate, 3-(acryloxy)-2-hydroxypropyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxylate triacrylate, tris[(2-acryloyloxy)ethyl] isocyanurate, acrylonitrile, methacrylonitrile, itaconic acid, methacrylic acid, trimethylsilylmethacrylate, N-[tris(hydroxymethyl)methyl]acrylamide, (3-acrylamidopropyl)trimethylammonium chloride, [3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxide inner salt,

6. The method according to claim 1 , wherein said alkenyl-functionalized organosiloxane is selected from the group consisting of methacryloxypropyltrimethoxysilane, 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,

wherein each R is independently H or a C1-C10 alkyl group and wherein R′ is independently H or a C1-C10 alkyl group.

7. The method according to claim 1 , wherein said tetraalkoxysilane is selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane.

8. The method of claim 7 , wherein said tetraalkoxysilane is tetramethoxysilane or tetraethoxysilane.

9. The method according to claim 1 , further comprising adding a free radical polymerization initiator.

10. The method according to claim 9 , wherein said free radical polymerization initiator is selected from the group consisting of 2,2′-azobis-[2-(imidazolin-2-yl)propane] dihydrochloride, 2,2′-azobisisobutyronitrile, 4,4′-azobis(4-cyanovaleric acid), 1,1′-azobis(cyclohexanecarbonitrile), 2,2′-azobis(2-propionamidine) dihydrochloride, 2,2′azobis(2,4-dimethylpentanenitrile), 2,2′-azobis(2-methylbutanenitrile), benzoyl peroxide, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)butane,-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-hexyne, bis(1-(tert-butylperoxy)-1-methyethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxy isopropyl carbonate, cumene peroxide, cyclohexanone hydroperoxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid, and potassium persulfate.

11. The method according to claim 9 , further comprising heating following the addition of the free radical polymerization initiator.

12. The method according to claim 1 , wherein step (b) further comprises adding a surfactant or stabilizer.

Assignees

• Waters Technologies Corp

Inventors

• Jiang Zhiping
• O'Gara John E
• Fisk Raymond P
• Wyndham Kevin D
• Brousmiche Darryl W

Classifications

• C08L53/005

  Modified block copolymers · CPC title

• B01J20/28019

  Spherical, ellipsoidal or cylindrical · CPC title

• B01J20/265

  modified or post-treated polymers (polymer carriers or substrates subjected to further impregnating or coating B01J20/3208) · CPC title

• B01J2220/82

  Shaped bodies, e.g. monoliths, plugs, tubes, continuous beds · CPC title

• C08F230/08

  containing silicon · CPC title