US4950634A — Method for producing dual zone materials by use o…

Claim 1

Independent Claim 333 words

A method of silylating a porous material to form a silylated porous material having an external zone which comprises the external surfaces of the porous material and having an internal zone which comprises the internal surfaces of the porous material, comprising: (a) providing a hydroxyl-bearing porous support selected from the group consisting of porous metalloid oxides, porous metallic oxides, and mixtures thereof, (b) providing an organosilane mixture of (i) an amount less than or equal to two-thirds of a stoichiometric equivalent, based on the reactable hydroxyl content of said porous support, of a first organosilane having first organosilyl groups and having a leaving group which is capable of rapidly reacting with the hydroxyls on the external surfaces faster than said first organosilane can migrate into the interior of said porous support, and (ii) more than 0.05 molecules per square nanometer of surface area of said porous support of a second organosilane having second organosilyl groups and a leaving group that will react slowly with the hydroxyls on the internal surfaces of said porous support but that will not substantially exchange with the leaving group of said first organosilane, said second organosilane being capable of diffusing into the interior of said porous support, (c) forming a porous support suspension by mixing said porous support with a solvent, (d) adding said organosilane mixture to said porous support suspension at a rate which is rapid with respect to the reaction rate of said second organosilane but slow with respect to the rate of mixing said suspension with said organosilane mixture, (e) maintaining contact between said porous support and said organosilane mixture for a time sufficient to permit rapid formation of said first organosilyl groups predominantly on the external surfaces of said porous support to form said external zone and said slow formation of said second organosilyl groups predominantly on the internal surfaces of said porous support to form said internal zone, and (f) subsequently isolating the so-treated porous support and thereby providing said silylated porous material.

Claim 2

Independent Claim 333 words

A method of silylating a porous material to form a silylated porous material having an external zone which comprises the external surfaces of the porous material and having an internal zone which comprises the internal surfaces of the porous material, comprising: (a) providing a hydroxyl-bearing porous support selected from the group consisting of porous metalloid oxides, porous metallic oxides, and mixtures thereof, (b) providing an organosilane mixture of (i) an amount less than or equal to two-thirds of a stoichiometric equivalent, based on the reactable hydroxyl content of said porous support, of a first organosilane having first organosilyl groups and having a leaving group which is capable of rapidly reacting with the hydroxyls on the external surfaces faster than said first organosilane can migrate into the interior of said porous support, and (ii) more than 0.05 molecules per square nanometer of surface area of said porous support of a second organosilane having second organosilyl groups and a leaving group that will react slowly with the hydroxyls on the internal surfaces of said porous support but that will not substantially exchange with the leaving group of said first organosilane, said second organosilane being capable of diffusing into the interior of said porous support, (c) forming a porous support suspension by mixing said porous support with a solvent, (d) adding said organosilane mixture to said porous support suspension at a rate which is rapid with respect to the reaction rate of said second organosilane but slow with respect to the rate of mixing said suspension with said organosilane mixture, (e) maintaining contact between said porous support and said organosilane mixture for a time sufficient to permit rapid formation of said first organosilyl groups predominantly on the external surfaces of said porous support to form said external zone and said slow formation of said second organosilyl groups predominantly on the internal surfaces of said porous support to form said internal zone, and (f) subsequently isolating the so-treated porous support and thereby providing said silylated porous material.

Claim 3

Dependent Claim 12 words

The method of claim 1 wherein said porous support is particulate silica.

Claim 4

Dependent Claim 12 words

The method of claim 2 wherein said solvent is an aprotic solvent.

Claim 5

Dependent Claim 12 words

The method of claim 2 wherein said solvent is a non-polar solvent.

Claim 6

Dependent Claim 22 words

The method of claim 2 wherein said solvent is selected from the group consisting of hexane, octane, decane, toluene and mixtures thereof.

Claim 7

Dependent Claim 34 words

The method of claim 1 wherein said leaving group of said first organosilane is selected from the group consisting of alkyl or aryl sulfide, a catalyzed non-fluorine halogen, disubstituted amino, and substituted amido groups.

Claim 8

Dependent Claim 27 words

The method of claim 6 wherein said leaving group of said second organosilane is selected from the group consisting of alkoxy, siloxy, carboxy, and uncatalyzed halogen groups.

Claim 9

Dependent Claim 21 words

The method of claim 7 wherein said first organosilyl groups are selected from the group consisting of haloalkylsilyl, vinylalkylsilyl, and aminoalkylsilyl.

Claim 10

Dependent Claim 16 words

The method of claim 6 wherein said second organosilyl groups are trimethylsilyl or dimethyl alkyl groups.

Claim 11

Dependent Claim 17 words

The method of claim 2 wherein said leaving group of said first organosilane is an N-methylacetamido group.

Claim 12

Dependent Claim 17 words

The method of claim 10 wherein said leaving group of said second organosilane is an acetoxy group.

Claim 13

Dependent Claim 13 words

The method of claim 2 wherein said organosilane mixture is a solvent-based mixture.

Claim 14

Dependent Claim 12 words

The method of claim 12 wherein said solvent is an aprotic solvent.

Claim 15

Dependent Claim 22 words

The method of claim 12 wherein said solvent is selected from the group consisting of hexane, octane, decane, toluene, and mixtures thereof.

Claim 16

Dependent Claim 37 words

The method of claim 1 wherein said external zone comprises approximately 5-50% of the total surface area of said porous material and said internal zone comprises approximately 50-95% of the total surface area of said porous material.

Claim 17

Dependent Claim 84 words

The method of claim 1 wherein said dual zone porous material has conditions selected from one of the following: ##EQU3## wherein Γ 1 (E) is the external surface density in Molecules/nM 2 as inferred by Electron Spectroscopy Chemical Analysis, and wherein Γ 1 (A) and Γ 2 (A) are like measurements of average surface density as measured by bulk analysis, and wherein subscripts 1 and 2 refer to said organosilyl groups of said first type and said organosilyl groups of said second type, respectively.

Claim 18

Dependent Claim 249 words

The method of claim 1 wherein said first organosilane has the formula L.sub.m Si(R").sub.3-m R wherein L is a catalyzed non-fluorine halogen, or NR 2 IV or an R IV -substituted sulfide or amido group wherein R IV is methyl, ethyl, phenyl, Si(R") 3-m R, or when L is NR 2 IV , a cyclic amino group, m is 1-3, R" is methyl, ethyl, or phenyl, and R is selected from hydrogen, allyl, vinyl, and Q wherein Q is (a) alkyl groups having less than twenty carbon atoms, (b) aryl groups having less than twenty carbon atoms, (c) CH 2 CH 2 C n F 2n+1 wherein n is 1 or more, (d) --CH 2 C p H 2p CH 2 SR', (e) --CH 2 C p H 2p CH 2 NR' 2 , (f) --CH 2 C p H 2p CH 2 N(R') (CH 2 ) 2 N(R') 2 , (g) --CH 2 C p H 2p CH 2 OCH 2 CHCH 2 , ##STR5## (i) --CH 2 C p H 2p CH 2 OC(O)C(CH 3 )═CH 2 ##STR6## (k) --CH 2 C p H 2p CH 2 O) a Z wherein a is 0-10 and Z is an alkyl or aryl hydrocarbon having less than seven carbon atoms or is acetyl or is the group ##STR7## wherein Me is methyl, or (1) --CH 2 c p H 2p CH 2 X wherein X is a halogen, R'is methyl, ethyl or phenyl and p is 1 or 2.

Claim 19

Dependent Claim 11 words

The method of claim 1 wherein said first organosilane is ##STR8##

Claim 20

Dependent Claim 169 words

The method of claim 17 wherein said second organosilane is an organosilane different from said first organosilane and has the formula L.sub.m Si (R").sub.3-m R wherein L is alkoxy, carboxy, or halogen, R" is methyl ethyl or phenyl, m is 1-3, and R is selected from hydrogen, allyl, vinyl and Q wherein Q is (a) alkyl groups having less than twenty carbon atoms, (b) aryl groups having less than twenty carbon atoms, (c) CH 2 CH 2 C n F 2n+1 wherein n is 1 or more, (d) --CH 2 C p H 2p CH 2 SR', (e) --CH 2 C p H 2p CH 2 NR' 2 , (f) --CH 2 C p H 2p CH 2 N(R') (CH 2 ) 2 N(R') 2 , ##STR9## (i) --CH 2 C p H 2p CH 2 OC(O)C(CH 3 )═CH 2 or ##STR10## (k) --CH 2 C p H 2p CH 2 X wherein X is a halogen, R' is methyl, ethyl or phenyl and p is 1 or 2.

Claim 21

Independent Claim 369 words

A method of silylating a porous material to form a silylated porous material having an external zone of external surfaces ranging from 0.5% to 50% of the surface area of the porous material and having an internal zone of internal surfaces ranging from 50-99.5% of the surface area of the porous material, comprising: (a) providing a hydroxyl-bearing porous support selected from the group consisting of porous metalloid oxides, porous metallic oxides, and mixtures thereof, (b) providing an organosilane mixture of (i) 0.05 to 2.0 molecules per square nanometer of surface area of said porous support of a first organosilane having first organosilyl groups and having a leaving group which is selected from the group consisting of alkyl or aryl sulfide, disubstituted amino, and substituted amino groups and which is capable of reacting with the hydroxyls on the external surfaces faster than said first organosilane can migrate into the interior of said porous support, and (ii) more than 0.05 molecules per square nanometer of the surface area of said porous support of a second organosilane having second organosilyl groups and a leaving group which is selected from the group consisting of alkoxy, carboxy, and halogen groups and which will react slowly with the hydroxyls on the internal surfaces of said porous support but will not substantially exchange with the leaving group of said first organosilane said second organosilane being capable of diffusing into the interior of said porous support, (c) forming a porous support suspension by mixing said porous support with a solvent, (d) adding said organosilane mixture to said porous support suspension at a rate which is rapid with respect to the reaction rate of said second organosilane but slow with respect to the rate of mixing said suspension with said organosilane mixture, (e) maintaining contact between said porous support and said organosilane mixture for a time sufficient to permit rapid formation of said first organosilyl groups predominantly on the external surfaces of said porous support to form said external zone and said slow formation of said second organosilyl groups predominantly on the internal surfaces of said porous support to form said internal zone, and (f) subsequently isolating the so-treated porous support and thereby providing said silylated porous material.

Claim 22

Independent Claim 369 words

A method of silylating a porous material to form a silylated porous material having an external zone of external surfaces ranging from 0.5% to 50% of the surface area of the porous material and having an internal zone of internal surfaces ranging from 50-99.5% of the surface area of the porous material, comprising: (a) providing a hydroxyl-bearing porous support selected from the group consisting of porous metalloid oxides, porous metallic oxides, and mixtures thereof, (b) providing an organosilane mixture of (i) 0.05 to 2.0 molecules per square nanometer of surface area of said porous support of a first organosilane having first organosilyl groups and having a leaving group which is selected from the group consisting of alkyl or aryl sulfide, disubstituted amino, and substituted amino groups and which is capable of reacting with the hydroxyls on the external surfaces faster than said first organosilane can migrate into the interior of said porous support, and (ii) more than 0.05 molecules per square nanometer of the surface area of said porous support of a second organosilane having second organosilyl groups and a leaving group which is selected from the group consisting of alkoxy, carboxy, and halogen groups and which will react slowly with the hydroxyls on the internal surfaces of said porous support but will not substantially exchange with the leaving group of said first organosilane said second organosilane being capable of diffusing into the interior of said porous support, (c) forming a porous support suspension by mixing said porous support with a solvent, (d) adding said organosilane mixture to said porous support suspension at a rate which is rapid with respect to the reaction rate of said second organosilane but slow with respect to the rate of mixing said suspension with said organosilane mixture, (e) maintaining contact between said porous support and said organosilane mixture for a time sufficient to permit rapid formation of said first organosilyl groups predominantly on the external surfaces of said porous support to form said external zone and said slow formation of said second organosilyl groups predominantly on the internal surfaces of said porous support to form said internal zone, and (f) subsequently isolating the so-treated porous support and thereby providing said silylated porous material.

Claim 23

Dependent Claim 29 words

The method of claim 20 wherein said porous support is particulate silica and said solvent is selected from the group consisting of hexane, octane, decane, toluene and mixtures thereof.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1993-08-20	1994-02-19	1994-08-21	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1997-08-20	1998-02-19	1998-08-21	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2001-08-20	2002-02-19	2002-08-21	$7700.00	Window Closed / Lapsed

Method for producing dual zone materials by use of an organosilane mixture

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