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

• US 9,976,008 B2
• Filed: 12/14/2015
• Issued: 05/22/2018
• Est. Priority Date: 10/30/2002
• Status: Active Grant

• Current Assignee: Waters Technologies Corporation (Waters Corporation)
• Original Assignee: Waters Technologies Corporation (Waters Corporation)
• Inventors: Jiang, Zhiping, O'Gara, John E., Fisk, Raymond P., Wyndham, Kevin D., Brousmiche, Darryl W.
• Primary Examiner(s): Moore, Margaret G
• Application Number:
  US14/967,647
• Publication Number:
  US 20160096943A1
• Time in Patent Office: 890 Days
• CPC Class Codes: B01J 20/26 Synthetic macromolecular compounds
• CPC Class Codes: B01J 20/265 modified or post-treated polymers polymer carriers or substrates subjected to further impregnating or coating B01J20/3208
• CPC Class Codes: B01J 20/28019 Spherical, ellipsoidal or cylindrical
• CPC Class Codes: B01J 20/28042 Shaped bodies; Monolithic structures
• CPC Class Codes: B01J 20/285 based on polymers
• CPC Class Codes: B01J 20/286 Phases chemically bonded to a substrate, e.g. to silica or to polymers
• CPC Class Codes: B01J 2220/82 Shaped bodies, e.g. monoliths, plugs, tubes, continuous beds
• CPC Class Codes: C08F 230/085 the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
• CPC Class Codes: C08G 77/442 containing vinyl polymer sequences
• CPC Class Codes: C08J 2329/04 Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• CPC Class Codes: C08J 2383/06 containing silicon bound to oxygen-containing groups C08J2383/12 takes precedence
• CPC Class Codes: C08J 9/35 Composite foams, i.e. continuous macromolecular foams containing discontinuous cellular particles or fragments
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 53/005 Modified block copolymers
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

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.

Claims

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,

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.