Patent US2409367A successfully refreshed from Google Patents.
Patent US4376641A successfully refreshed from Google Patents.
US4376641A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Coated capillary chromatographic column
Assignee: Dow Chemical Co
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Filing: 1981-12-14
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Granted: 1983-03-15
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Expires: 2001-12-14
Abstract
Abstract In the production of a wall coated open tubular capillary chromatographic column, improved deactivation of the inner surface of a glass or fused silica capillary tube prior to coating with stationary phase is obtained by a multi-step process whereby siloxane polymer molecules are chemically bonded to the capillary inner surface. The process comprises multiple cycles of successive reactions with silicon tetrachloride and a diorganodichlorosilane vapor with intermediate hydrolyses and a final capping reaction with a triorganochlorosilane. The deactivated surface is adapted to coating with an apolar liquid stationary phase.
Inventors
- 👤 Terry J. Nestrick
- 👤 Thomas L. Peters
- 👤 Lester L. Lamparski
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 20:39
CPC Classifications
B; B01; B01J; B01J20/00; B01J20/281; B01J20/286; B01D; B01D15/00; B01D15/08; B01D15/10; B01D15/20; B01D15/206; C; C03; C03C; C03C17/00; C03C17/28; C03C17/30; C03C17/34; C03C17/3405; B01J2220/00; B01J2220/50; B01J2220/54; B01J2220/80; B01J2220/86; G; G01; G01N; G01N30/00; G01N30/02; G01N30/60; G01N30/6052; G01N30/6073; G01N30/6078
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
234 words
In the process of preparing a chromatographic column using a glass capillary tube, the inner surface of which is etched and acid-activated, or fused silica capillary tube, the inner surface of which is acid-activated, the improved method of deactivating, the inner surface of the capillary which comprises: (a) contacting the etched and/or acid-activated surface with SiCl 4 vapor thereby causing substantial chlorosilylation of said surface, (b) contacting the chlorosilylated surface with water vapor until essentially all of the chlorosilyl groups have been hydrolyzed to hydroxysilyl groups, (c) contacting the hydrolyzed surface with excess of a diorganodichlorosilane vapor of the formula RR'SiCl 2 where RR' each represent a methyl, ethyl, vinyl, or allyl radical, or a mono-chlorinated derivative thereof, to react at least the major portion of the hydroxysilyl groups to form corresponding diorganochlorosilyl groups, (d) contacting the reacted surface from step (c) with water vapor until essentially all of the diorganochlorosilyl groups have been hydrolyzed to diorganohydroxysilyl groups, (e) contacting the hydrolyzed surface of step (d) with SiCl 4 vapor to react substantially all of said diorganohydroxysilyl groups to form diorganosilyloxychlorosilyl groups, (f) repeating steps b-d not less than once, and (g) contacting the final hydrolyzed surface from step (f) with a triorganochlorosilane vapor of the formula RR'R"SiCl where RR'R" each represent a methyl, ethyl, vinyl or allyl radical, or a mono-chlorinated derivative thereof, to convert substantially all diorganohydroxysilyl groups to corresponding triorganosilyloxydiorganosilyl groups.
Claim 2
Dependent Claim
234 words
In the process of preparing a chromatographic column using a glass capillary tube, the inner surface of which is etched and acid-activated, or fused silica capillary tube, the inner surface of which is acid-activated, the improved method of deactivating, the inner surface of the capillary which comprises: (a) contacting the etched and/or acid-activated surface with SiCl 4 vapor thereby causing substantial chlorosilylation of said surface, (b) contacting the chlorosilylated surface with water vapor until essentially all of the chlorosilyl groups have been hydrolyzed to hydroxysilyl groups, (c) contacting the hydrolyzed surface with excess of a diorganodichlorosilane vapor of the formula RR'SiCl 2 where RR' each represent a methyl, ethyl, vinyl, or allyl radical, or a mono-chlorinated derivative thereof, to react at least the major portion of the hydroxysilyl groups to form corresponding diorganochlorosilyl groups, (d) contacting the reacted surface from step (c) with water vapor until essentially all of the diorganochlorosilyl groups have been hydrolyzed to diorganohydroxysilyl groups, (e) contacting the hydrolyzed surface of step (d) with SiCl 4 vapor to react substantially all of said diorganohydroxysilyl groups to form diorganosilyloxychlorosilyl groups, (f) repeating steps b-d not less than once, and (g) contacting the final hydrolyzed surface from step (f) with a triorganochlorosilane vapor of the formula RR'R"SiCl where RR'R" each represent a methyl, ethyl, vinyl or allyl radical, or a mono-chlorinated derivative thereof, to convert substantially all diorganohydroxysilyl groups to corresponding triorganosilyloxydiorganosilyl groups.
Claim 3
Dependent Claim
30 words
The process of claim 1 wherein the deactivated column surface is coated with a film of at least about 80 percent by weight apolar liquid polymer as a stationary phase.
Claim 4
Dependent Claim
13 words
The process of claim 2 wherein the apolar polymer is a methyl silicone.
Claim 5
Dependent Claim
11 words
The deactivated capillary column product of the process of claim 1.
Claim 6
Dependent Claim
39 words
An improved process for making a chromatographic separation comprising mixing the vapor of a substance having multiple components with an inert carrier gas and passing the gaseous mixture through the chromatographic column product of the process of claim 2.
Claim 7
Dependent Claim
18 words
The process of claim 5 wherein the chromatographic column is the product of the process of claim 3.
Claim 8
Dependent Claim
47 words
In an apparatus for use in chromatographic separations comprising a capillary glass or fused silica tube having a thin film of a stationary liquid phase supported by the inner surface of the tube, the improvement wherein the column is the product of the process of claim 2.
Claim 9
Dependent Claim
19 words
The apparatus of claim 7, the improvement wherein the column is the product of the process of claim 3.
Claim 10
Dependent Claim
226 words
In the process of preparing a chromatographic column of a glass capillary tube, the inner surface of which is etched and acid-activated or fused silica capillary tube, the inner surface of which is acid-activated, the improved method of deactivating the inner surface of the capillary which comprises: (a) contacting the etched and/or acid-activated surface with SiCl 4 vapor at about 0°-300° C., thereby causing substantial chlorosilylation of said surface, (b) contacting the chlorosilylated surface with water vapor at about 0°-300° C. until essentially all of the chlorosilyl groups have been hydrolyzed to hydroxysilyl groups, (c) contacting the hydrolyzed surface with excess dimethyldichlorosilane vapor at about 0°-300° C. for a time sufficient to react at least the major portion of the hydroxysilyl groups to form corresponding dimethylchlorosilyl groups, (d) contacting the reacted surface from step (c) with water vapor at about 0°-300° C. until essentially all of the dimethylchlorosilyl groups have been hydrolyzed to dimethylhydroxysilyl groups, (e) contacting the hydrolyzed surface from step (d) with SiCl 4 vapor at about 0°-300° C. for a time sufficient to react substantially all of said dimethylhydroxysilyl groups to form dimethylsilyloxychlorisilyl groups, (f) repeating steps b-d not less than once, and (g) contacting the final hydrolyzed surface from step (f) with trimethylchlorosilane vapor at about 0°-300° C. for a time sufficient to convert substantially all dimethylhydroxysilyl groups to corresponding trimethylsilyloxydimethylsilyl groups.
Claim 11
Dependent Claim
226 words
In the process of preparing a chromatographic column of a glass capillary tube, the inner surface of which is etched and acid-activated or fused silica capillary tube, the inner surface of which is acid-activated, the improved method of deactivating the inner surface of the capillary which comprises: (a) contacting the etched and/or acid-activated surface with SiCl 4 vapor at about 0°-300° C., thereby causing substantial chlorosilylation of said surface, (b) contacting the chlorosilylated surface with water vapor at about 0°-300° C. until essentially all of the chlorosilyl groups have been hydrolyzed to hydroxysilyl groups, (c) contacting the hydrolyzed surface with excess dimethyldichlorosilane vapor at about 0°-300° C. for a time sufficient to react at least the major portion of the hydroxysilyl groups to form corresponding dimethylchlorosilyl groups, (d) contacting the reacted surface from step (c) with water vapor at about 0°-300° C. until essentially all of the dimethylchlorosilyl groups have been hydrolyzed to dimethylhydroxysilyl groups, (e) contacting the hydrolyzed surface from step (d) with SiCl 4 vapor at about 0°-300° C. for a time sufficient to react substantially all of said dimethylhydroxysilyl groups to form dimethylsilyloxychlorisilyl groups, (f) repeating steps b-d not less than once, and (g) contacting the final hydrolyzed surface from step (f) with trimethylchlorosilane vapor at about 0°-300° C. for a time sufficient to convert substantially all dimethylhydroxysilyl groups to corresponding trimethylsilyloxydimethylsilyl groups.
Claim 12
Dependent Claim
32 words
The process of claim 9 wherein the deactivated column surface is coated with a film of at least about 80 percent by weight of an apolar liquid polymer as a stationary phase.
Claim 13
Dependent Claim
14 words
The process of claim 10 wherein the apolar polymer is a methyl silicone polymer.
Claim 14
Dependent Claim
11 words
The deactivated capillary column product of the process of claim 9.
Claim 15
Dependent Claim
39 words
An improved process for making a chromatographic separation comprising mixing the vapor of a substance having multiple components with an inert carrier gas and passing the gaseous mixture through the chromatographic column product of the process of claim 10.
Claim 16
Dependent Claim
18 words
The process of claim 13 wherein the chromatographic column is the product of the process of claim 11.
Claim 17
Dependent Claim
47 words
In an apparatus for use in chromatographic separations comprising a capillary glass or fused silica tube having a thin film of a stationary liquid phase supported by the inner surface of the tube, the improvement wherein the column is the product of the process of claim 10.
Claim 18
Dependent Claim
19 words
The apparatus of claim 15, the improvement wherein the column is the product of the process of claim 11.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-03-14 | 1986-09-13 | 1987-03-15 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-03-14 | 1990-09-13 | 1991-03-15 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-03-14 | 1994-09-13 | 1995-03-15 | $7700.00 | Window Closed / Lapsed |