Adsorption medium and method of preparing same

An adsorption medium that includes a finely divided substrate provided on at least a portion of its surface with the polymerization product of a silane that includes (a) two or three olefinic groups having the formula --(CH.sub.2).sub.m CH.dbd.CH.sub.2, where m is between 0 and 3, inclusive, and (b) at least one ligand selected to interact with a substance brought into contact with the adsorption medium to adsorb at least a portion of the substance on the surface of the adsorption medium.

FIELD OF THE INVENTION 
This invention relates to adsorbing one or more substances on the surface 
of a finely divided substrate. 
DESCRIPTION OF RELATED ART 
Finely divided oxides (e.g., Al.sub.2 O.sub.3, SiO.sub.2, TiO.sub.2, and 
ZrO.sub.2) have been used as adsorption media, including chromatographic 
support materials. The silanization of the surfaces of these materials 
provides a convenient way of introducing a variety of ligands onto the 
oxide surface. Such ligands interact with substances applied to the 
adsorption medium to cause selective adsorption. 
One problem with the treated surfaces is that the bonded phase produced by 
silanization is stabilized by siloxane linkages. These linkages are 
susceptible to hydrolysis, particularly under strongly acidic or basic 
conditions, resulting in release of silane from the oxide surface and 
concurrent loss of adsorptive ability. 
SUMMARY OF THE INVENTION 
In a first aspect, the invention features an adsorption medium that 
includes a finely divided substrate provided on at least a portion of its 
surface with the polymerization product of a silane that includes (a) two 
or three olefinic groups having the formula --(CH.sub.2).sub.m 
CH.dbd.CH.sub.2, where m is between 0 and 3, inclusive, and (b) at least 
one ligand selected to interact with a substance brought into contact with 
the adsorption medium to adsorb at least a portion of the substance on the 
surface of the adsorption medium. 
In preferred embodiments, the adsorption medium is in the form of a 
chromatographic support material and the ligand is a chromatographically 
useful ligand. The polymerization product preferably has a carbosilane 
backbone that is essentially free of siloxane linkages. 
The polymerization product may be the homopolymerization product of the 
silane monomer or it may be a copolymer of the silane monomer and one or 
more co-monomers, e.g., a trihydrosilane. In some preferred embodiments, 
the polymerization product is covalently bonded to at least a portion of 
the surface of the substrate, whereas in other preferred embodiments, the 
polymerization product is physically deposited on at least a portion of 
the surface of the substrate. Examples of preferred substrates include 
Al.sub.2 O.sub.3, SiO.sub.2, TiO.sub.2, and ZrO.sub.2, and combinations 
thereof. 
Preferred silanes feature three olefinic groups having the formula 
--(CH.sub.2).sub.m CH.dbd.CH.sub.2, where m is between 0 and 3, inclusive. 
Particularly preferred are olefinic groups having the formula --CH.sub.2 
CH.dbd.CH.sub.2 (m.dbd.1) and --CH.dbd.CH.sub.2 (m.dbd.0). Examples of 
preferred ligands include hydrogen, a halogen (e.g., F, Cl, Br, or I), an 
alkoxy group (e.g., having between 1 and 3 carbon atoms, inclusive, such 
as a methoxy or ethoxy group), an aryl group (e.g., a phenyl or naphthyl 
group), a derivatized aryl group (e.g., an aminoaryl, haloaryl, 
hydroxyaryl, mercaptoaryl, cyanoaryl, phosphonoaryl, or carboxyaryl group 
having between 1 and 18 carbon atoms, inclusive), an alkyl group (e.g., 
having between 1 and 22 carbon atoms, inclusive, such as an octyl or 
octadecyl group), or a derivatized alkyl group (e.g., an aminoalkyl, 
haloalkyl, hydroxyalkyl, mercaptoalkyl, cyanoalkyl, phosphonoalkyl, or 
carboxyalkyl group having between 1 and 18 carbon atoms, inclusive). Other 
examples of derivatized alkyl and aryl groups include alkyl or aryl-bound 
cyclodextrans, crown ethers, and chiral molecules. Specific examples of 
preferred silanes include triallyloctadecylsilane, 
trivinyloctadecylsilane, triallyoctylsilane, and trivinyloctylsilane. 
In a second aspect, the invention features a method of preparing the 
above-described adsorption media that includes the steps of contacting a 
finely divided substrate with the above-described silanes and polymerizing 
the silane on at least a portion of the surface of the substrate. 
In one preferred embodiment of this method, the substrate is contacted with 
the silane and a trihydrosilane, and the two are copolymerized with each 
other on at least a portion of the surface of the substrate. In yet 
another preferred embodiment, the surface of the substrate is pre-treated 
to create surface-bonded groups that can react with the silane. 
The invention also features a chromatography apparatus (e.g., a column or 
bed) that includes a chromatographic support material as the stationary 
phase, in which the support material includes a finely divided substrate 
provided on at least a portion of its surface with the polymerization 
product of a silane that includes (a) two or three olefinic groups having 
the formula --(CH.sub.2).sub.m CH.dbd.CH.sub.2, where m is between 0 and 
3, inclusive, and (b) at least one chromatographically useful ligand. 
In this application: 
A "finely divided substrate" refers to a particulate material in which the 
particle size is selected to yield an overall surface area sufficient to 
enable the material to function as an adsorbent medium on a practical 
scale. Particle diameters typically range from about 0.1 to about 500 
micrometers, although particles having diameters less than 0.1 micrometer 
and greater than 500 micrometers can be used as well. 
A "silane" refers to a compound in which a central silicon atom is bonded 
to four substituents, none of which are oxygen. 
A "siloxane linkage" refers to a silicon-oxygen (Si--O) bond. 
A "ligand" refers to a functional group bonded to the central silicon atom 
of the silane that does not participate in the polymerization reaction, 
but rather remains available as a pendent group following polymerization 
for interacting with a substance applied to the adsorption medium. A 
"chromatographically useful ligand" is a ligand that interacts with 
substances applied to a chromatography apparatus (e.g., a column or bed) 
to cause selective adsorption (and thus separation of the material or 
materials of interest). 
A "derivatized alkyl group" refers to an alkyl group in which one or more 
of the hydrogen atoms are replaced with a different functional group. 
Examples of common functional groups include amino, halogen, hydroxyl, 
mercaptyl, cyano, phosphonyl, and carboxyl groups. 
A "derivatized aryl group" refers to an aryl group in which one or more of 
the hydrogen atoms are replaced with different functional groups. Examples 
of common functional groups include amino, halogen, hydroxyl, mercaptyl, 
cyano, phosphonyl, and carboxyl groups. 
"Essentially free of siloxane linkages" refers to the polymerization 
product of a silane monomer (and, optionally, one or more co-monomers) in 
which the number of Si-O linkages in the carbosilane (i.e., --C--Si--) 
backbone of the polymer (as opposed to pendent groups attached to the 
carbosilane backbone) is sufficiently low such that the hydrolyric 
stability of the resulting polymer is not substantially impaired. 
The invention provides silane-derivatized, finely divided support materials 
useful as adsorption media, e.g., chromatographic columns and beds. 
Reacting silanes having two or three olefinic groups improves the 
hydrolytic stability of the materials, particularly upon exposure to 
strongly acidic or basic conditions, because the resulting polymerization 
product is essentially free of siloxane linkages in its backbone: such 
linkages are particularly susceptible to hydrolysis.

DESCRIPTION OF PREFERRED EMBODIMENTS 
The invention features an adsorbent medium in which a finely divided 
substrate contains on at least a portion of its surface the polymerization 
product of (a) one or more silane monomers and (optionally) (b) one or 
more non-silane monomers. The substrate particles preferably are 
substantially spherical particles. Both porous and non-porous particles 
can be used, with porous particles being preferred. The average pore 
diameter of the porous particles (as measured by nitrogen adsorption) 
ranges from about 20 .ANG. to about 4000 .ANG., preferably from about 50 
.ANG. to about 1000 .ANG., and more preferably from about 60 .ANG. to 
about 500 .ANG.. In addition, the porosity of the individual particles 
preferably ranges from about 10-90%, more preferably from about 20-80%, 
and even more preferably from about 30-70%. 
Particle diameters typically range from about 0.1 micrometer to about 500 
micrometers. In the case of non-porous particles, the particle diameters 
preferably range from about 0.1 micrometer to about 20 micrometers, more 
preferably from about 0.5 micrometer to about 10 micrometers, and even 
more preferably from about 1 micrometer to about 3 micrometers. For porous 
particles, the preferred particle diameters are in the range of about 1 
micrometer to about 25 micrometers, and more preferably in the range of 
about 3 micrometers to about 6 micrometers. 
Suitable materials for the finely divided substrate are well-known and 
include both organic and inorganic materials. Preferably, however, the 
finely divided substrate is selected from oxides and mixed oxides of 
silicon, aluminum, titanium, and/or zirconium. These materials may further 
include minor proportions of additives such as stabilizers and processing 
aids, or other oxides (e.g., oxides of boron, cerium, hafnium, or 
yttrium). Particularly preferred are silica (SiO.sub.2), zirconia 
(ZrO.sub.2), and admixtures thereof. Also suitable are the materials 
described in the following patents, all of which are incorporated by 
reference: Cart et al., U.S. Pat. No. 5,015,373 (polymer clad materials); 
Carr et al., U.S. Pat. No. 5,141,634 (phosphate-coated materials); and 
Funkenbusch et al., U.S. Pat. No. 5,108,597 (carbon-clad particles). 
The silane monomer contains four substituents bonded to a central silicon 
atom. Two or three of those substituents (with three being preferred) are 
olefinic substituents having the formula --(CH.sub.2).sub.m 
CH.dbd.CH.sub.2, where m is between 0 and 3, inclusive. Examples of 
preferred groups are vinyl groups (m.dbd.0) and allyl groups (m.dbd.1). 
The olefinic groups may be the same as, or different from, each other. 
Polymerization proceeds through the double bond of the olefinic 
substituent, resulting in a polymer having a carbosilane backbone that is 
essentially free of siloxane linkages. 
At least one of the remaining substituents bonded to the central silicon 
atom is a ligand designed to impart selective adsorptive capabilities to 
the polymerized product. A wide variety of ligands may be used, with the 
particular choice of ligand being a function of the use to which the 
adsorbent medium will be put (i.e., the type of material that the medium 
is designed to adsorb). Suitable ligands are well-known and include those 
described in the Summary of the Invention, above. 
The silane monomers are generally prepared by reacting an olefinic 
organometallic reagent with an appropriate n-alkyl tri- or di-halo silane. 
Suitable organometallic reagents include olefinic Grignard reagents and 
olefinic lithium reagents. 
Polymerization of the silane monomers is carried out in the presence of the 
finely divided substrate material and an initiator according to known 
polymerization techniques, including thermal-, ultraviolet-, gamma ray-, 
ionic-, or coordination ionic- initiated polymerization. Suitable 
initiators are described in the aforementioned Carr and Funkenbush 
patents, and include peroxides (e.g., benzoyl peroxide and dicumyl 
peroxide), ultraviolet sensitizers (e.g., 2,2'-dimethoxy-2-phenyl 
acetophenone), and platinum catalysts (e.g., chloroplatinic acid and 
bis(divinyltetramethyldisiloxane Pt). 
The silane monomer may be copolymerized with one or more co-monomers, 
including both silane and non-silane co-monomers. Examples of useful 
co-monomers include alkyl trihydrosilanes, alkenyl trihalosilanes (e.g., 
allyl trichlorosilane), vinyl phosphonate, 1,2-epoxy hexene, and allyl 
glycidyl ether. Particularly preferred co-monomers are alkyl 
trihydrosilanes such as octadecyl trihydrosilane. 
The silane monomer(s) and, optionally, non-silane monomers can be 
polymerized directly onto the surface of the substrate, in which case the 
polymerization product is not chemically bonded to the substrate surface. 
The substrate surface may also be pre-treated to introduce 
surface-functional groups, e.g., vinyl groups, that can react with the 
silane monomer(s) during the polymerization reaction to create side chains 
that covalently bond the final polymer to the substrate surface. These 
side chains may include siloxane linkages bonding the side chains to the 
substrate surface. The presence of such linkages does not substantially 
impair the overall hydrolyric stability of the product so long as the 
carbosilane polymer backbone itself is essentially free of such linkages. 
The final product is useful as an adsorbent medium in a variety of 
settings. It is particularly useful as a chromatographic support material 
forming the stationary phase of a normal or reversed phase high 
performance liquid chromatography (HPLC) column or bed, as well as an 
ion-exchange HPLC column or bed. It may also be combined with a binder and 
used to coat a glass or plastic plate for use in thin layer 
chromatography. In addition, it may be used to immobilize biologically 
active materials (e.g., enzymes or antibodies) for a variety of purposes, 
including catalysis, analysis, affinity chromatography, synthetic 
transformations, and remediation. 
Objects and advantages of this invention are further illustrated by the 
following examples, but the particular materials and amounts thereof 
recited in these examples, as well as other conditions and details, should 
not be construed to limit this invention. All parts and percentages are by 
weight unless otherwise indicated. 
EXAMPLES 
Examples 1-15 describe the preparation of silane monomers. Structures of 
the silane monomers described in these Examples are summarized in Table 1, 
below. 
TABLE 1 
__________________________________________________________________________ 
Triolefinic: 
Silane structure Name: Abbreviation 
Formula: 
FW: Example 
__________________________________________________________________________ 
##STR1## trivinyl octadecyl silane 
TVOdS C.sub.24 H.sub.46 Si 
362.72 
1 
##STR2## trially octadecyl silane 
TAOdS C.sub.27 H.sub.52 Si 
404.80 
2 
##STR3## tributenyl octadecyl silane 
TBOdS C.sub.30 H.sub.58 Si 
446.88 
3 
##STR4## trivinyl octyl silane 
TVOcS C.sub.14 H.sub.26 Si 
222.45 
4 
##STR5## triallyl octyl silane 
TAOcS C.sub.17 H.sub.32 Si 
264.51 
5 
##STR6## triallyl (3- chloropropyl) silane 
TACPS C.sub.12 H.sub.21 SiCl 
228.84 
6 
##STR7## triallyl (3- bromopropyl) silane 
TABPS C.sub.12 H.sub.21 SiBr 
273.39 
7 
##STR8## triallyl (3- iodopropyl) silane 
TAIPS C.sub.12 H.sub.21 SiI 
320.29 
8 
##STR9## triallyl N,N- (diethyl- aminopropyl) 
TADEAPS 
C.sub.16 H.sub.31 NSi 
265.52 
9 
##STR10## triallyl-(propyl phosphonic) acid silane 
TAPPS C.sub.12 H.sub.23 O.sub.2 
258.37 
10 
##STR11## triallyl-(3- glyceryl-propyl) silane 
TAGlPS 
C.sub.15 H.sub.28 O.sub.3 
284.47 
11 
##STR12## triallyl-(3- hydroxy propyl) silane 
TAHPS C.sub.12 H.sub.22 OSi 
209.5 
12 
##STR13## triallyl fluoroalkyl silane 
FATAS C.sub.17 H.sub.19 F.sub.13 
498.40 
13 
##STR14## trivinyl methoxy silane 
TVMS C.sub.7 H.sub.11 OSi 
140.26 
14 
##STR15## triallyl methoxy silane 
TAMS C.sub.10 H.sub.18 OSi 
182.34 
15 
__________________________________________________________________________ 
Example 1 
Example 1 describes the preparation of trivinyl octadecyl silane. 
A two liter, three-necked round bottom flask was oven dried and equipped 
with an inert (polytetrafluoroethylene) paddle mechanical stirrer, a 250 
ml pressure equalizing addition funnel with inert stopcock, a reflux 
condenser and a gas inlet. The apparatus was flushed with dry nitrogen. A 
0.42 mole (250 ml) sample of 15% vinyl magnesium chloride in 
tetrahydrofuran (available from Janssen Chimica of Geel, Belgium) was 
transferred to this flask via a double ended cannula; this solution is 
known as a Grignard reagent. It was further diluted with 600 ml of 
anhydrous cyclohexane (available as Omnisolve reagent grade from E. Merck, 
Gibbstown, N.J.). The diluted solution was then stirred. 
Next, the addition funnel was replaced with a similar 100 ml funnel 
containing 0.136 mole (52.7 grams) of octadecyl trichlorosilane (available 
from United Chemical Technologies of Bristol, Pa.) which was added to the 
solution dropwise. The addition funnel was then rinsed with 
tetrahydrofuran into the reaction flask. Magnesium chloride precipitate 
formed as the silane was added to the Grignard solution. The resulting 
suspension was stirred for 4 hours under the flow of nitrogen gas. Silica 
gel (commercially available as Merck grade 9385, 230-400 mesh (38-63 
micrometers) from Aldrich Chemical Co. of Milwaukee, Wis.) was washed with 
water and was then added to the slurry to quench remaining reagents. The 
silica gel and magnesium halide precipitate were removed by filtration 
through a bed of filtration enhancer (commercially available as Celite 
from Aldrich Chemical Co.) on a Buchner funnel. The bed was washed with 
three 100 ml portions of cyclohexane which were added to the filtrate, 
which was subsequently concentrated on a rotary evaporator. The remaining 
liquid was vacuum distilled at 168.degree. C.-169.degree. C. and 0.6 mm to 
yield the silane monomer. 
The final distilled product was 95% pure as determined by capillary gas 
chromatography with flame ionization detection (GC/FID) using a 30 meter 
5% phenyl methyl silicone column (commercially available as a DB-5 column 
from J&W Scientific of Folsom, Calif.). Spectroscopic evaluation using 
mass spectrometry, Fourier transform infrared spectroscopy (FTIR), and 
nuclear magnetic resonance spectroscopy (NMR) was consistent with 
octadecyl trivinyl silane. 
Example 2 
Example 2 describes the preparation of triallyl octadecyl silane. 
Triallyl octadecyl silane was prepared as described in Example 1 except 
that 0.31 mole (155 ml) of 2M allyl magnesium chloride in tetrahydrofuran 
(commercially available from Aldrich Chemical Co. of Milwaukee, Wis.) was 
used in place of the vinyl magnesium bromide reagent to react with a 0.10 
mole (38 grams) sample of octadecyl trichlorosilane (commercially 
available from United Chemical Technologies of Bristol, Pa.). The final 
triallyl octadecyl silane product was obtained by vacuum distillation at 
191.degree. C.-192.degree. C. and 0.5 mm. It was 95% pure as determined by 
capillary GC/FID using a 30 meter DB-5 column. Spectroscopic evaluation 
using mass spectrometry, FTIR and NMR was consistent with octadecyl 
triallyl silane. 
Example 3 
Example 3 describes the preparation of tributenyl octadecyl silane. 
A two liter, three-necked round bottom flask was oven dried and equipped 
with an inert (polytetrafluoroethylene) paddle mechanical stirrer, a 250 
ml pressure equalizing addition funnel with inert stopcock, a reflux 
condenser and a gas inlet. The apparatus was flushed with dry nitrogen. A 
3.96 gram sample of magnesium turnings (commercially available from 
Aldrich Chemical Co. of Milwaukee, Wis., 162 millimoles) was added to the 
flask and was warmed while flushing with dry nitrogen, after which 20 ml 
of dry tetrahydrofuran (commercially available from Burdick and Jackson of 
Muskeegon, Mich.) were added. A 22.0 gram sample of 4-bromo-1-butene 
(commercially available from Aldrich Chemical Co., 162 millimoles) was 
dissolved in an equal volume of dry tetrahydrofuran, and was added 
dropwise to the flask via the addition funnel. 
Upon addition of the bromobutene, the flask was heated to maintain a reflux 
condition. An additional 50 ml of dry tetrahydrofuran was then used to 
rinse the funnel into the flask and the sample was refluxed for an 
additional hour. Next, 15.8 grams of octadecyltrichlorosilane 
(commercially available from Aldrich Chemical Co., 40.7 millimoles) was 
dissolved in 180 ml of cyclohexane (commercially available from Burdick 
and Jackson) and was transferred to the addition funnel via double ended 
cannula. The reaction flask was immersed in a water bath and the silane 
solution was added slowly over 2 hours, after which the addition funnel 
was rinsed with an additional 200 ml of cyclohexane. The reaction was 
stirred for 72 hours. The excess reagents were quenched by addition of 
silica gel, and the silica gel and magnesium halide precipitates were 
removed by filtration as described in Example 1. The filtrate was 
subsequently concentrated on a rotary evaporator to provide 21 grams of 
crude product. This material contained 23% tributenyl octadecylsilane. 
The crude product was chromatographed on 100 grams of silica gel 
(commercially available from Aldrich Chemical Co.) using cyclohexane 
eluent to provide 5.2 grams of an oil consisting of 70% (as determined by 
capillary GC/FID) of tributenyl octadecylsilane. Spectroscopic evaluation 
using mass spectrometry, FTIR and NMR was consistent with tributenyl 
octadecylsilane. 
Example 4 
Example 4 describes the preparation of trivinyl octyl silane. 
Trivinyl octyl silane was prepared as described in Example 1 except that 
0.31 mole (298 ml) of 15% vinyl magnesium chloride in tetrahydrofuran 
(commercially available from Janssen Chimica, Geel, Belgium) was reacted 
with 0.16 mole (40 grams) of n-octyl trichlorosilane (commercially 
available from United Chemical Technologies of Bristol, Pa.) in place of 
the n-octadecyl trichlorosilane reagent used in Example 1. The final 
trivinyl octyl silane reagent was obtained by vacuum distillation at 
75.degree. C. and 1 mm. It was 98% pure as determined by capillary GC/FID 
using a 30 meter DB-5 column. Spectroscopic evaluation using mass 
spectrometry, FTIR and NMR was consistent with trivinyl octyl silane. 
Example 5 
Example 5 describes the preparation of triallyl octyl silane. 
Triallyl octyl silane was prepared as described in Example 1 except that 
0.60 mole (300 ml) of 2.0M vinyl magnesium chloride in tetrahydrofuran 
(commercially available from Aldrich Chemical Co. of Milwaukee, Wis.) was 
reacted with 0.19 mole (48 grams) of n-octyl trichlorosilane (commercially 
available from United Chemical Technologies of Bristol, Pa.) in place of 
the n-octadecyl trichlorosilane reagent used in Example 1. The final 
triallyl octyl silane reagent was obtained by vacuum distillation at 
98.degree. C. and 0.5 mm. It was 99% pure as determined by capillary 
GC/FID using a 30 meter DB-5 column. Spectroscopic evaluation using mass 
spectrometry, FTIR and NMR was consistent with triallyl octyl silane. 
Example 6 
Example 6 describes the preparation of triallyl-3-chloropropyl silane. 
Triallyl chloropropyl silane was prepared using the equipment described in 
Example 1 except that a 3 L flask was used. The apparatus was flushed with 
nitrogen and was charged with 100 grams (0.47 mole) of trichloro 
(3-chloropropyl) silane (commercially available from Lancaster Synthesis 
Inc., Windham, N.H.). The silane reagent was diluted with 1200 ml of 
cyclohexane (commercially available as Omnisolve from E. Merck, Gibbstown, 
N.J.). The reaction flask was cooled in an ice bath while 732 ml (1.46 
mole) of a 2M solution of allyl magnesium chloride in tetrahydrofuran 
(commercially available from Aldrich Chemical Co. of Milwaukee, Wis.) was 
added slowly through the addition funnel. The addition funnel was then 
rinsed with tetrahydrofuran. Magnesium chloride precipitate formed as the 
Grignard reagent was added to the silane solution. 
The resulting suspension was stirred for 1 hour following addition of the 
Grignard reagent, at which point the ice bath was removed and the slurry 
was allowed to warm to room temperature. The slurry was then stirred 
overnight. Residual active reagents were quenched and the product 
collected by filtration as described in Example 1. The bed was washed with 
three 100 ml portions of cyclohexane which were added to the filtrate, 
which was subsequently concentrated on a rotary evaporator. The remaining 
liquid was vacuum distilled using a short path still at 0.6 mm. Tetra 
allyl silane impurities distilled off at about 78.degree. C.-80.degree. 
C., while the triallyl chloropropyl silane product distilled at 86.degree. 
C. and 0.6 mm. Preparations for use as synthetic intermediates were 
obtained by pooling distillation fractions from 78.degree. C.-86.degree. 
C. since tetraallyl silane impurities were removed more readily in later 
synthetic steps. 
The final distilled product was 98% pure as determined by capillary GC/FID 
using a 30 meter DB-5 column. This preparation contained 1-2% tetraallyl 
silane impurity. Spectroscopic evaluation using mass spectrometry, FTIR 
and NMR was consistent with triallyl chloropropyl silane. 
Example 7 
Example 7 describes the preparation of triallyl (3-bromopropyl) silane. 
Triallyl bromopropyl silane was prepared using the apparatus described in 
Example 6. The nitrogen purged reaction flask was charged with 50 grams 
(0.20 mole) of trichloro (3-bromopropyl) silane (commercially available 
from Lancaster Synthesis Inc. of Windham, N.H.). The silane reagent was 
diluted with 800 ml of cyclohexane (commercially available as Omnisolve 
from E. Merck, Gibbstown, N.J.). The reaction flask was cooled in an ice 
bath while 303 ml (0.60 mole) of a 2M solution of allyl magnesium chloride 
in tetrahydrofuran (commercially available from Aldrich Chemical Co. of 
Milwaukee, Wis.) was added dropwise through the addition funnel over two 
hours. The addition funnel was then rinsed with tetrahydrofuran. Magnesium 
chloride precipitate formed as the Grignard reagent was added to the 
silane solution. 
The resulting suspension was stirred for 1 hour following addition of the 
Grignard reagent, at which point the ice bath was removed and the slurry 
was allowed to warm to room temperature. The slurry was then stirred 
overnight. Residual active reagents were quenched and the product 
collected by filtration as described in Example 1. The bed was washed with 
three 100 ml portions of cyclohexane which were added to the filtrate, 
which was subsequently concentrated on a rotary evaporator. The remaining 
liquid was vacuum distilled using a short path still at 0.6 mm. Tetraallyl 
silane rich impurities distilled off at about 78.degree. C.-80.degree. C., 
while the triallyl bromopropyl silane product distilled at 94.degree. C. 
and 0.6 mm. Preparations for use as synthetic intermediates were obtained 
by pooling distillation fractions from 78.degree. C.-94.degree. C. since 
tetraallyl silane impurities were removed more readily in later synthetic 
steps. 
The final distilled product was 95% pure as determined by capillary GC/FID 
using a 30 meter DB-5 column. This preparation contained low levels of 
tetraallyl silane impurity. Spectroscopic evaluation using mass 
spectrometry, FTIR and NMR was consistent with triallyl bromopropyl 
silane. 
Example 8 
Example 8 describes the preparation of triallyl 3-iodopropyl silane. 
Triallyl 3-iodopropyl silane was prepared by the Finkelstein 
transhalogenation reaction from chloropropyl silane prepared in Example 6. 
A 250 ml flask equipped with a stir bar and a reflux condenser was charged 
with 20 grams (90 millimoles) of triallyl (3-chloropropyl) silane 
(prepared as described in Example 6) and 100 ml of acetone (available 
commercially as Omnisolve Reagent grade from E. Merck, Gibbstown, N.J.). 
The silane solution was refluxed under positive nitrogen pressure with 40 
grams (270 millimoles) of sodium iodide (available commercially from 
Aldrich Chemical Co. of Milwaukee, Wis.) for 18 hours. After cooling, the 
acetone solution was decanted from the insoluble iodide salts and was 
concentrated on a rotary evaporator to yield triallyl 3-iodopropyl silane, 
which was used without further purification. 
Example 9 
Example 9 describes the preparation of triallyl 3-(N,N-diethylaminopropyl) 
silane. 
Triallyl 3-(N,N-diethylaminopropyl) silane was prepared from the triallyl 
(3-iodopropyl)silane intermediate prepared in Example 8. A 100 ml flask 
equipped with stir bar and reflux condenser was charged with 15 grams (44 
millimoles) of triallyl (3-iodopropyl)silane (prepared as described in 
Example 8) and 50 ml of anhydrous acetonitrile (available commercially as 
Omnisolve from E. Merck of Gibbstown, N.J.). Diethyl amine (available 
commercially from Aldrich Chemical Co. of Milwaukee, Wis.) was added in 
about a five-fold excess (22.5 ml, 218 millimoles). The solution was 
stirred under positive nitrogen pressure for 5 hours. 
Next, solvent was removed in vacuo, and the residue was taken up in 30 ml 
of cyclohexane (commercially available as Omnisolve from E. Merck). 
Aqueous 2M HCl (commercially available from J. T. Baker of Phillipsburg, 
N.J.) was added to adjust the pH of the aqueous layer to 4. The organic 
layer was then discarded and the aqueous layer partitioned with two 
additional 30 ml portions of cyclohexane. The final aqueous phase was 
adjusted to pH 12 through the addition of concentrated ammonium hydroxide 
(commercially available from J. T. Baker). The alkaline aqueous sample was 
then extracted with three 50 ml portions of methyl-t-butyl ether 
(commercially available from Burdick and Jackson of Muskeegon, Mich.) 
which were pooled and washed with two equal volumes of saturated aqueous 
solution of sodium chloride. After washing, the ether phase was dried over 
anhydrous sodium sulfate (commercially available from J. T. Baker) and was 
concentrated to dryness in vacuo. The product was vacuum distilled at 
100.degree. C. and 0.6 mm Hg. 
The final product was 96% pure by GC/FID analysis using a 30 meter DB-5 
column (J&W Scientific, Folsom, Calif.). Spectroscopic analysis using mass 
spectrometry, FTIR and NMR was consistent with 
triallyl-3-(N,N-diethylaminopropyl) silane. 
Example 10 
Example 10 describes the preparation of triallyl-3(diethylphosphonopropyl) 
silane and triallyl silyl-(3-propylphosphonic acid). 
Triallyl silyl-3-propylphosphonic acid was prepared from the triallyl 
bromopropyl silane prepared as in Example 7 via the diethyl phosphonate 
ester intermediate. A 100 ml flask equipped with stir bar and reflux 
condenser was charged with 17.6 grams (60 millimoles) of 93% triallyl 
bromopropyl silane (prepared as described in Example 7) and 30.4 grams 
(180 millimoles) of triethyl phosphite (commercially available from 
Aldrich Chemical Co. of Milwaukee, Wis.). The solution was stirred under 
positive nitrogen pressure while the sample was refluxed at 165.degree. C. 
in an oil bath overnight. Unreacted phosphite reagents were removed using 
a rotary evaporator at 80.degree. C. The majority of the remaining 
reagents and impurities were removed by vacuum distillation at 50.degree. 
C.-150.degree. C. and 1 mm Hg to yield triallyl-3(diethylphosphonopropyl) 
silane, which was 98% pure as measured using capillary GC/FID with a 30 
meter DB-5 column. Spectroscopic analysis using mass spectrometry, FTIR 
and NMR was consistent with triallyl-3(diethylphosphopropyl) silane. 
The free phosphonic acid product was prepared by hydrolysis of the 
triallyl-3-(diethylphosphonopropyl) silane in acidic aqueous solution. 
Example 11 
Example 11 describes the preparation of triallyl glycerylpropyl silane. 
Triallyl glycerylpropyl silane was prepared from triallyl bromopropyl 
silane prepared in Example 7 via glycerol acetonide intermediate. A 250 ml 
flask equipped with a stir bar was charged with 22.9 grams of 74% triallyl 
bromopropyl silane reagent (17.0 grams, 62 millimoles of triallyl 
bromopropyl silane prepared as described in Example 7). The silane was 
diluted with 175 ml of tetrahydrofuran (commercially available from 
Aldrich Chemical Co. of Milwaukee, Wis.) containing 1.1 grams (3.2 
millimoles) tetrabutylammonium hydrogen sulfate (commercially available 
from Aldrich Chemical Co.). The reaction vessel was then cooled in an ice 
bath and purged with nitrogen. 
Next, the reaction vessel was charged with 16.86 grams (128 millimoles) of 
freshly distilled solketal (the acetone ketal of glycerine, commercially 
available from Aldrich Chemical Co.) and the solution was stirred rapidly 
while 32 grams of chilled 50% sodium hydroxide (commercially available 
from Aldrich Chemical Co.) solution were added. The bath was allowed to 
warm to room temperature. The solution was then stirred for 48 hours while 
the sample was purged with nitrogen. The organic phase was then decanted 
and saved. The aqueous phase was diluted four-fold with water and 
extracted with two 50 ml portions of methyl-t-butyl ether (commercially 
available from Burdick and Jackson of Muskeegon, Mich.). The organic 
phases were then combined and rotoevaporated to remove the ether. The 
remaining sample was separated by Flash Chromatography on a 25 gram bed of 
Merck 230-400 mesh (38-63 micrometers) silica (commercially available from 
Aldrich Chemical Co.) using 25/75 v/v methyl-t-butyl ether/cyclohexane 
(commercially available from E. Merck of Gibbstown, N.J.) to remove 
quaternary ammonium salts, the tetraallyl silane and most of the solketal 
and triallyl bromopropyl silane reagents. The sample was then vacuum 
distilled, with the triallyl glycerylpropyl silane acetonide collected at 
125.degree. C. and 0.06 mm Mg. 
The triallyl glycerylpropyl silane acetonide prepared in this way was 
90%-92% pure. A sample was then purified further to yield product that was 
98% pure. 
A 0.75 gram sample of the 98% pure acetonide product prepared as above was 
converted to the diol by overnight hydrolysis in 2 ml of a 10% acetic acid 
(Aldrich Chemical Co.) in water and 1 ml of n-butanol (commercially 
available from Aldrich Chemical Co.) at 50.degree. C. The solvents were 
removed by rotoevaporation and the diol was purified by liquid 
chromatography on silica using an increasing gradient of methyl-t-butyl 
ether versus hexane (Burdick and Jackson). The chromatographic faction was 
then re-concentrated by rotary evaporation to provide a pure preparation 
of triallyl-(3-glycerylpropyl)silane. Spectroscopic analysis using mass 
spectrometry, FTIR and NMR was consistent with 
triallyl-(3-glycerylpropyl)silane. 
Example 12 
Example 12 describes the preparation of triallyl(3-hydroxypropyl)silane. 
Triallyl(3-hydroxylpropyl)silane was prepared from triallyl-3-bromopropyl 
silane prepared in Example 7 via the formyloxypropyl intermediate. A 100 
ml flask equipped with stir bar and reflux condenser was charged with 10.0 
grams (36 millimoles) of triallyl 3-bromopropyl silane (prepared as 
described in Example 7), 4.90 grams (72 millimoles) sodium formate 
(commercially available from Aldrich Chemical Co. of Milwaukee, Wis.) and 
0.60 grams of tetrabutyl ammonium bromide (commercially available from 
Aldrich Chemical Co.). The suspension was stirred at 110.degree. C. for 
two days. The solution was then filtered and combined with equal volumes 
of deionized water and cyclohexane (commercially available as Omnisolve 
from E. Merck of Gibbstown, N.J.). The organic extract was flash 
chromatographed on silica using first cyclohexane, followed by 80/20 
cyclohexane/acetone to collect the triallyl formyloxypropyl silane 
intermediate. 
The triallyl formyloxypropyl silane intermediate was converted to the 
hydroxylpropyl product by charging 5.0 grams of the intermediate, together 
with 50 ml of methanol (commercially available from Burdick and Jackson of 
Muskeegon, Mich.) and 10 ml of deionized water, in a 250 ml flask with 
stir bar. 1.0 gram (10 millimoles) of potassium hydrogen carbonate 
(commercially available from Aldrich Chemical Co.) was added to the 
solution, which was then stirred at 50.degree. C. for five hours. The 
solution was filtered and was concentrated in vacuo. The sample was then 
taken up in cyclohexane and was washed with saturated aqueous sodium 
chloride before drying over anhydrous sodium sulfate (commercially 
available from Aldrich Chemical Co.). The sample was then purified using 
flash chromatography on silica with 99/1 cyclohexane/acetone eluent 
initially, followed by 80/20 cyclohexane/acetone. The recovered fractions 
were concentrated in vacuo to yield triallyl 3-hydroxypropyl silane, as 
shown by capillary GC/FID analysis using a 30 meter DB-5 column. 
Spectroscopic analysis using mass spectrometry, FTIR and NMR was 
consistent with triallyl-3-hydroxypropyl silane. 
Example 13 
Example 13 describes the preparation of triallyl 
tridecafluorotetrahydrooctyl silane. 
Triallyl tridecafluorotetrahydrooctyl silane was prepared from its 
trichloro silane analogue using allyl Grignard reagents. A 125 ml flask, 
equipped with stirring bar and a delivery funnel with 
polytetrafluoroethylene stopcock, was charged with 7.78 grams (16 
millimoles) of (tridecafluoro-1,1,2,2-tetrahydrooctyl)-1-trichlorosilane 
(United Chemical Technologies, Piscataway, N.J.) under nitrogen purge 
conditions. The silane was diluted with 50 ml of tetrahydrofuran (Burdick 
and Jackson, Muskeegon, Mich.). A 25.0 ml (50 millimoles) portion of a 2M 
solution of allyl magnesium chloride in tetrahydrofuran (Aldrich Chemical 
Co.) was then added dropwise to the stirred solution, forming magnesium 
chloride precipitate in an initially strongly exothermic reaction. 
After 1 hour had elapsed, an additional 1 ml of the allyl magnesium 
chloride reagent was added to the sample, which was then stirred overnight 
at room temperature and under nitrogen purging. Excess Grignard reagent 
was consumed by the addition of 10 ml of methanol (Burdick and Jackson), 
after which the slurry was stirred for another hour. The magnesium 
chloride precipitate was collected by filtration through filter paper and 
the precipitate was washed with two 10 ml portions of tetrahydrofuran. The 
filtrate and the wash solutions were then combined to yield a reagent 
solution. This sample was evaluated by capillary GC/FID and GC/MS using a 
30 meter DB-5 column. Based on these results, the solution contained about 
10 weight percent of a 95% pure component. Spectroscopic analysis using 
gas chromatography and mass spectrometry were consistent with triallyl 
tridecafluorotetrahydrooctyl silane. 
Example 14 
Example 14 describes the preparation of trivinyl methoxy silane. 
Trivinyl methoxy silane was prepared from trichlorosilane via a trivinyl 
hydrosilane intermediate. A 2 L two necked flask, equipped with a 
mechanical stirrer, a 100 ml pressure equalizing additional funnel with 
inert stopcock, a cold finger condenser and a nitrogen purge inlet, was 
charged with 800 ml (1.34 mole) of a 15% solution of vinyl magnesium 
chloride in tetrahydrofuran (commercially available from Janssen Chimica 
of Geel, Belgium). The addition funnel was charged with a solution 
consisting of 43.9 ml (0.435 mole) of trichlorosilane (commercially 
available from Aldrich Chemical Co. of Milwaukee, Wis.) and 43.9 ml of 
decahydronaphthaiene (commercially available from Burdick and Jackson of 
Muskeegon, Mich.). The reaction flask was cooled in an ice bath and the 
trichlorosilane solution was added dropwise with stirring. Addition of the 
silane resulted in formation of magnesium chloride precipitate. 
After addition of the silane reagent was complete, the sample was kept cold 
for 30 minutes, after which the slurry was stirred at room temperature for 
4 hours. Excess Grignard reagent was quenched by the addition of saturated 
ammonium chloride solution. The precipitates were removed by filtration as 
described in Example 1 and the bed was washed with two 100 ml portions of 
decahydronaphthalene, which were then added to the flitrate. The organic 
fraction was then distilled and the fractions from 50.degree. 
C.-150.degree. C. collected. 
The resulting product consisted of 8% trivinyl hydrosilane in 
tetrahydrofuran/decahydroanphthalene solvent. This preparation can be 
converted directly to the alkoxy derivative, or can be purified further by 
washing twice each with equal volumes of 3% aq sodium chloride, 2.5% aq 
sodium chloride and water in order to remove tetrahydrofuran. The 
resulting organic fraction is dried over molecular sieves and then 
distilled at 84.degree. C.-87.degree. C. to yield the purified product. 
Trivinyl hydrosilane was converted to trivinyl methoxy silane by combining 
150 ml of the crude solution in tetrahydrofuran/decahydronaphthalene with 
an equal volume of dry methanol (commercially available as Omnisolve from 
Aldrich Chemical Co. of Milwaukee, Wis.) in a 2 L two necked flask 
equipped with stir bar, cold finger condenser and a septum seal. A 
solution of 56 milligrams of sodium methoxide (commercially available from 
Aldrich Chemical Co.) was dissolved in 5 ml of methanol and added dropwise 
to the flask. The reaction flask wag then immersed in a room temperature 
water bath to control the exothermic reaction. After 4 hours, an 
additional 0.5 ml of a fresh solution of sodium methoxide was added to the 
reaction, which was left stirring overnight. The trivinyl methoxy silane 
was recovered by distillation of the product at 119.degree. C.-120.degree. 
C. 
This process yielded 96% trivinyl methoxy silane, as determined by gas 
chromatography and FID analysis on a 30 meter DB-5 column. Spectroscopic 
analysis using mass spectrometry, FTIR and NMR was consistent with 
trivinyl-methoxy silane. 
Example 15 
Example 15 describes the preparation of triallyl methoxy silane. 
Triallyl methoxy silane was prepared from trichlorosilane via the triallyl 
hydrosilane intermediate following the procedure described in Example 14. 
A 500 ml two-necked flask, equipped with a mechanical stirrer, a 100 ml 
pressure equalizing additional funnel with inert stopcock, a cold finger 
condenser and a nitrogen purge inlet, was charged with 197 ml (394 
millimoles) of a 2M solution of allyl magnesium chloride in 
tetrahydrofuran (commercially available from Aldrich Chemical Co. of 
Milwaukee, Wis.). The addition funnel was charged with a solution 
consisting of 12.5 ml (0.124 mole) of trichlorosilane (commercially 
available from Aldrich Chemical Co.) and 12.5 ml of dry pentane 
(commercially available from Aldrich Chemical Co.). The reaction flask was 
cooled in an ice bath and the trichlorosilane solution was added and 
reacted as described in Example 14. After quenching excess Grignard 
reagent with saturated ammonium chloride solution, the sample was filtered 
to remove precipitate and yield triallyl hydrosilane. This material can be 
directly converted to the methoxy derivative (as described below) or 
purified further by vacuum distillation at 55.degree. C.-57.degree. C. and 
20 mm Hg. 
Triallyl hydrosilane was converted to triallyl methoxy silane by combining 
13 grams of triallyl hydrosilane with 50 ml of dry methanol (commercially 
available from Burdick and Jackson, Muskeegon of Mich.) in a 125 ml flask 
equipped with a stir bar and a septum seal. A solution of 250 milligrams 
of sodium methoxide (commercially available from Aldrich Chemical Co.) was 
prepared in 5 ml of methanol and was added to the flask in 100 microliter 
increments. The reaction flask was then immersed in a room temperature 
water bath to control the exothermic reaction. When gas evolution ceased, 
an additional 1 ml of a fresh solution of sodium methoxide was added to 
the reaction, which was then left stirring overnight. The methanol was 
removed by distillation while the triallyl methoxy silane was isolated by 
vacuum distillation of the remaining sample at 65.degree. C. and 10 mm Hg. 
This process yielded 99% triallyl methoxy silane by GC/FID analysis on a 30 
meter DB-5 column. Spectroscopic analysis using mass spectrometry, FTIR 
and NMR was consistent with triallyl-methoxy silane. 
Example 16 
Example 16 describes the preparation of a triallyl octadecylsilyl polymeric 
bonded phase on a zirconia chromatographic support. 
12 grams of a zirconia (ZrO.sub.2) chromatographic support gel. (generally 
described in Carr et al., U.S. Pat. No. 5,015,373, hereby incorporated by 
reference, and characterized as having an average particle diameter of 7 
.mu.m; a surface area of 33 m.sup.2 /gram; an average pore diameter of 165 
.ANG.; and a specific pore volume of 0.14 ml/gram) was washed with 0.1N 
NaOH and then dried at 150.degree. C. for two hours. The gel was then 
transferred into a 100 ml round bottom flask and suspended in 20 grams of 
hexane (available from Burdick and Jackson, Muskeegon, Mich.), which was 
then outgassed with vacuum and ultrasonication. 
The resulting slurry was charged with 0.51 gram of triallyl octadecyl 
silane (prepared as described in Example 2, 1.3 millimoles) and 30 
milligrams of dicumyl peroxide (available from Aldrich Chemical Co., 
Milwaukee, Wis.). The slurry was rotated at 90 rpm for 5 minutes in a room 
temperature water bath before the solvent was removed by rotoevaporation 
over a 10 minute period. The sample was then outgassed with evacuation and 
N.sub.2 purge cycles. After a final evacuation, the sample flask was 
immersed in the 180.degree. C. oil bath where it was cured in vacuo for 3 
hours. After curing, the sample was cooled under vacuum and collected on a 
Buchner funnel, where it was washed to remove unbonded monomer. The washed 
gel was then dried overnight to remove residual solvent. Carbon combustion 
analysis of the final product indicated 2.5% C which corresponds to a 
coverage of 2.5 micromoles octadecyl silane/m.sup.2. 
Example 17 
Example 17 describes the preparation of a trivinyl octylsilyl polymeric 
bonded phase on a zirconia chromatographic support. 
The procedure of Example 16 was followed except that 0.31 gram of trivinyl 
octyl silane (prepared as described in Example 4, 3.9 millimoles) and 51 
milligrams of dicumyl peroxide were used. Carbon combustion analysis of 
the final product indicated 2.0% C which corresponds to a coverage of 3.8 
micromole octyl silane/m.sup.2. 
Example 18 
Example 18 describes the preparation of trivinyl octadecylsilyl polymeric 
bonded phase on a silica chromatographic support. 
The procedure of Example 16 was followed except that the support material 
was a silica (SiO.sub.2) chromatographic support (commercially available 
as "Impaq R60610Si" from the PQ Corporation of Valley Forge, Pa., 
characterized as having an average particle diameter of 10 micrometers; a 
surface area of 579 m.sup.2 /gram; an average pore diameter of 62 .ANG.; 
and a specific pore volume of 0.90 ml/gram). 2.03 grams of the SiO.sub.2 
support material were used. In addition, the polymer was prepared by free 
radical polymerization of trivinyl octadecyl silane (prepared as described 
in Example 1, 1.20 grams, 3.32 millimoles) using, as the initiator, 98 
milligrams of benzoyl peroxide (available from Aldrich Chemical Co., 
Milwaukee, Wis.). Carbon combustion analysis of the final product 
indicated 18.4% C which corresponds to a coverage of 1.14 micromoles 
octadecyl silane/m.sup.2. 
Example 19 
Example 19 describes the preparation of a triallyl octylsilyl polymeric 
bonded phase on a chromatographic alumina support. 
The procedure of Example 16 was followed except that the support material 
was an alumina (Al.sub.2 O.sub.3) chromatographic support (commercially 
available as "Spherisorb Al.sub.2 O.sub.3 " from the Phase Separations 
Inc. of Norwalk, Conn., characterized as having an average particle 
diameter of 10 micrometers; a surface area of 105 m.sup.2 /gram; an 
average pore diameter of 167 .ANG.; and a specific pore volume of 0.44 
ml/gram). 4.31 grams of the Al.sub.2 O.sub.3 support material were used. 
In addition, the polymer was prepared by free radical polymerization of 
triallyl octyl silane (prepared as described in Example 5, 3.4 millimoles, 
0.41 gram) using 49 milligrams of benzoyl peroxide as the initiator. 
Carbon combustion analysis of the final product indicated 3.8% C which 
corresponds to a coverage of 1.9 micromoles octyl silane/m.sup.2. 
Example 20 
Example 20 describes the preparation of a triallyl octadecylsilyl polymeric 
bonded phase on a carbon clad ZrO.sub.2 chromatographic support. 
The procedure of Example 16 was followed except that the support was a 
carbon clad ZrO.sub.2 chromatographic support prepared by treating the 
ZrO.sub.2 chromatographic gel in Example 16 with butanol vapor at 
700.degree. C. under reduced pressures as described in U.S. Pat. No. 
5,108,597. The support was Characterized as having a surface area of 20.1 
m.sup.2 /gram; an average pore diameter of 155 .ANG.; and a specific pore 
volume of 0.11 ml/gram. Carbon combustion analysis of this support yielded 
a carbon content of 1.30%. 
13 grams of the carbon clad ZrO.sub.2 support material was washed with 25 
ml each of 0.1N potassium hydroxide in methanol, acetonitrile and hexane, 
and then dried for 30 minutes at 110.degree. C. Next, a 100 ml round 
bottom flask was charged with 12.42 grams of the washed and dried carbon 
clad ZrO.sub.2, which was slurried in 15 grams of hexane and 5 grams of 
unstabilized tetrahydrofuran (available from Burdick and Jackson, 
Muskeegon, Mich.) and then outgassed with vacuum and ultrasonication. To 
the slurry was added 0.59 gram of triallyl octadecyl silane reagent 
(prepared as described in Example 2, 1.5 millimoles) and 70 milligrams of 
dicumyl peroxide. The procedure of Example 16 was then followed to yield 
the final product. Carbon combustion analysis of the final product 
indicated 3.13% C, which represents an increase of 1.83% C, or a coverage 
of 2.0 micromoles octadecyl silane/m.sup.2. 
Example 21 
Example 21 describes the preparation of a tributenyl octadecylsilyl 
dimercaptan copolymeric bonded phase on a zirconia chromatographic 
support. 
An octadecyl functionalized polymeric carbosilane bonded phase was prepared 
on the zirconia (ZrO.sub.2) chromatographic support used in Example 16 by 
photoinitiated copolymerization of tributenyl octadecyl silane and 
ethylene glycol bis (mercaptoethyl ether) on the support as follows. 15 
grams of the ZrO.sub.2 gel was weighed into a 100 ml round bottom flask 
and suspended in 30 grams of cyclohexane (commercially available from 
Burdick and Jackson, Muskeegon, Mich.), after which it was outgassed with 
vacuum and ultrasonication. Next, the slurry was charged with 0.225 gram 
of 70% tributenyl octadecyl silane reagent (prepared as described in 
Example 3, 0.35 millimoles), 0.134 gram of 1,8-dimercapto-3,6-dioxaoctane 
(commercially available from Itochu Specialty Chemical Co of White Plains, 
N.Y., 0.73 millimole) and 90 milligrams of 2,2'-dimethoxy-2-phenyl 
acetophenone photoinitiator (commercially available from Aldrich Chemical 
Co.). The slurry was rotated at 90 rpm for 5 minutes in a room temperature 
water bath before the solvent was removed by rotoevaporation over a 15 
minute period. While under vacuum, the sample was exposed to UV radiation 
(350 nm) for 150 seconds, one third time at an intensity of 1.0 
mW/cm.sup.2 and the remaining two thirds time at an intensity of 2.2 
mW/cm.sup.2 (as measured by a UVIMAP VR 365CH3 radiometer). After curing, 
the sample was collected on a Buchner funnel, where it was washed to 
remove unbonded monomer. The washed gel was then dried overnight to remove 
residual solvent. Carbon and sulfur combustion analysis of the final 
product indicated 1.3% C and 0.3% S which corresponds to coverages of 1.4 
micromoles octadecyl silane/m.sup.2 and 0.8 micromole mercaptan/m.sup.2. 
Example 22 
Example 22 describes the preparation of a triallyl 
octadecylsilyl--epoxyhexenyl copolymeric bonded phase on a zirconia 
chromatographic support. 
An octadecyl functionalized polymeric carbosilane bonded phase, covalently 
bound to the gel surface, was prepared on the ZrO.sub.2 chromatographic 
support (described in Example 16) by free radical copolymerization of 
triallyl octadecyl silane and epoxy hexene on the support according to the 
procedure described in Example 16 except that 0.15 gram of 1,2-epoxy 
hexene (available from Aldrich Chemical Co., Milwaukee, Mich.) was added 
to the ZrO.sub.2 slurry in hexane prior to addition of the triallyl 
octadecyl silane and dicumyl peroxide. Under these conditions, the epoxy 
reagent reacted with surface hydroxyls to yield a hexene-substituted 
ZrO.sub.2 surface which was then copolymerized with the triallyl silane. 
Carbon combustion analysis of the final product indicated 3.0% C which 
corresponds to a coverage of 1.7 micromoles/m.sup.2 epoxy hexene and 2.5 
micromoles/m.sup.2 octadecyl silane. 
Example 23 
Example 23 describes the preparation of a triallyl octadecylsilyl--allyl 
glycidyl ether copolymeric bonded phase on a zirconia chromatographic 
support. 
An octadecyl functionalized polymeric carbosilane bonded phase, covalently 
bound to the surface of a zirconia chromatographic support, was prepared 
according to the procedure of Example 16 except that 10.7 grams of the 
support material was used. The polymer was prepared by free radical 
copolymerization of triallyl octadecyl silane (prepared as described in 
Example 2, 1.7 millimoles, 0.70 gram) and allyl glycidyl ether (available 
from Aldrich Chemical Co., Milwaukee, Wis., 2.1 millimoles, 0.24 gram) on 
the support using, as the initiator, 50 milligrams of dicumyl peroxide. 
Carbon combustion analysis of the final product indicated 5.4% C which 
corresponds to a coverage of 1.4 micromoles/m.sup.2 allyl glycidyl ether 
and 2.6 micromoles/m.sup.2 octadecyl silane. 
Example 24 
Example 24 illustrates the preparation of a trivinyl octadecylsilyl 
polymeric bonded phase on a vinyl phosphonate treated zirconia 
chromatographic support. 
The procedure of Example 16 was followed except that the support was a 
vinyl phosphonate treated zirconia support prepared by suspending 12.70 
grams of ZrO.sub.2 (described in Example 16) in 50 ml of water, and then 
outgassing with ultrasonication and vacuum. 0.40 gram of vinyl phosphonate 
(available from Aldrich Chemical Co., Milwaukee, Wis., 3.7 millimoles) was 
added to the slurry and the pH was adjusted to 7.4 using ammonium 
hydroxide, after which the sample was equilibrated for 15 minutes. The 
vinyl phosphonate treated ZrO.sub.2 gel was recovered by filtration and 
was washed with 10 ml each of deionized water and acetonitrile, and then 
dried for two hours at 110.degree. C. Carbon combustion analysis of the 
vinyl phosphonated product indicated 0.25% C which corresponds to a vinyl 
phosphonate coverage of 3.2 micromoles/m.sup.2. 
A 100 ml round bottom flask wash charged with 11.04 grams of the dried 
vinyl phosphonate treated ZrO.sub.2, which was suspended in 20 grams of 
hexane (available from Burdick and Jackson, Muskeegon, Mich.) and was 
outgassed with vacuum and ultrasonication. To the slurry was added 0.53 
gram of trivinyl octadecyl silane (prepared as described in Example 1, 1.5 
millimoles) together with 30 milligrams of dicumyl peroxide and 25 
milligrams of benzoyl peroxide (available from Aldrich Chemical Co.). The 
procedure of Example 16 was followed to yield the final product. Carbon 
combustion analysis of the final product indicated 4.0% C which 
corresponds to a coverage of 4.1 micromoles/m.sup.2 octadecyl silane. 
Example 25 
Example 25 describes the preparation of a triallyl (3-glycerylpropyl)silyl 
polymeric bonded phase on a zirconia chromatographic support. 
11.2 grams of the ZrO.sub.2 gel described in Example 16 was washed with 25 
ml of 0.1N NaOH and unstabilized tetrahydrofuran (available from Burdick 
and Jackson, Muskeegon, Mich.). A 100 ml round bottom flask was charged 
with 12.9 grams of the alkaline, water rich gel, which was suspended in 20 
grams of tetrahydrofuran and then outgassed with vacuum and 
ultrasonication. To the slurry was added 0.75 gram of triallyl 
(3-glycerylpropyl)silane acetonide (prepared as described in Example 11, 
2.3 millimoles) and 88 milligrams of dicumyl peroxide (available from 
Aldrich Chemical Co.). The slurry was rotated at 90 rpm for 10 minutes in 
a 40.degree. C. water bath before the solvent was removed by 
rotoevaporation over a 10 minute period while the sample was heated to 
60.degree. C. The sample was then outgassed with evacuation and N.sub.2 
purge cycles. After a final evacuation, the sample flask was immersed in 
the 180.degree. C. oil bath where it was cured in vacuo for 3 hours. After 
curing, the sample was cooled under vacuum and resuspended in 50 ml of 1:1 
methanol/1N HCl, and outgassed with vacuum and ultrasonication. 
The sample was heated overnight at 70.degree. C. to hydrolyze the acetonide 
to the diol form. The hydrolyzed sample was recovered on a Buchner funnel, 
where it was washed to remove unbonded monomer. The washed gel was then 
dried overnight to remove residual solvent. Carbon combustion analysis of 
the final product indicated 3.8% C which corresponds to a coverage of 6.9 
micromoles/m.sup.2 of diol silane. 
Example 26 
Example 26 describes the preparation of a triallyl (aminopropylsilyl) allyl 
glycidyl ether copolymeric bonded phase on a zirconia chromatographic 
support. 
The procedure of Example 16 was followed except that 13 grams of the 
ZrO.sub.2 gel was washed with of 0.1N NaOH, water and acetonitrile, and 
then dried at 110.degree. C. for two hours. A 100 ml round bottom flask 
wash charged with 12.78 grams of the washed and dried gel, which was 
suspended in 20 grams of hexane and then outgassed with vacuum and 
ultrasonication. To the resulting slurry was added 0.29 gram of allyl 
glycidyl ether (available from Aldrich Chemical Co., 2.6 millimoles) and 
0.56 gram of triallyl(N,N-diethyl-3-aminopropyl)silane (prepared as 
described in Example 9, 2.1 millimoles), and, as the initiator, 73 
milligrams of dicumyl peroxide. The procedure of Example 16 was then 
followed to yield the final product. Carbon and nitrogen combustion 
analysis of the final product indicated 2.8% C and 0.2% N which 
corresponds to a coverage of 3.6 micromoles/m.sup.2 of amino silane. 
Example 27 
Example 27 describes the preparation of a triallyl (phosphonopropyl)silyl 
polymeric bonded phase on a zirconia chromatographic support. 
10 grams of the ZrO.sub.2 gel described in Example 16 was washed with 0.1N 
NaOH, water and acetonitrile, and then dried at 110.degree. C. for two 
hours. A 100 ml round bottom flask was charged with 9.06 grams of the 
washed and dried gel, which was suspended in 20 grams of hexane and then 
outgassed with vacuum and ultrasonication. To the slurry was added 0.59 
gram of triallyl 3-phosphonopropyl silane diethyl ester (prepared as 
described in Example 10, 1.9 millimoles). After 3.5 hours, 92 milligrams 
of dicumyl peroxide (available from Aldrich Chemical Co.) was added to the 
slurry, which was then rotated at 90 rpm for 5 minutes in a room 
temperature water bath before the solvent was removed by rotoevaporation 
over a 15 minute period. The sample was then outgassed with evacuation and 
N.sub.2 purge cycles. After a final evacuation, the sample flask was 
immersed in the 180.degree. C. oil bath where it was cured in vacuo for 3 
hours. 
After curing, the sample was cooled under vacuum and was resuspended in 50 
ml of 1:1 acetonitrile/1N HCl, and then outgassed with vacuum. Next, the 
sample was heated overnight to hydrolyze the esters to the free acid 
forms. The hydrolyzed sample was recovered on a Buchner funnel, where it 
was washed to remove unbonded monomer. The washed gel was then dried 
overnight to remove residual solvent. Carbon combustion analysis of the 
final product indicated 1.6% C which corresponds to a coverage of 3.4 
micromoles/m.sup.2 of alkyl phosphonic acid silane. 
Example 28 
Example 28 describes the preparation of a trivinyl 
octadecylsilyl--octadecylsilyl copolymeric bonded phase on an allyl 
silane-treated zirconia chromatographic support. 
Allyl silanized ZrO.sub.2 was prepared by suspending 15.2 grams of the 
ZrO.sub.2 support material described in Example 16 in 25 ml of toluene in 
a 125 ml flask, and outgassing with ultrasonication and vacuum. 0.76 gram 
of allyl triethoxy silane (available from Aldrich Chemical Co., Milwaukee, 
Wis., 3.7 millimoles) was added to the slurry. The sample was heated at 
100.degree. C. for 40 hours, after which the allyl silanized ZrO.sub.2 gel 
was recovered by filtration and was washed to remove unbonded silane. 
Carbon combustion analysis of the allyl silanized product indicated 0.65% 
C which corresponds to a polymeric allyl silane coverage of 5.6 
micromoles/m.sup.2. 
A 125 ml iodine flask was charged with 7.05 grams of allyl silanized 
ZrO.sub.2 suspended in 15 grams of hexane (available from Burdick and 
Jackson, Muskeegon, Mich.) and then outgassed with vacuum and 
ultrasonication. The slurry was charged with 0.41 gram of trivinyl 
octadecyl silane (prepared as described in Example 1, 1.1 millimoles) and 
0.33 gram of octadecyl silane (available from United Chemical Technologies 
of Bristol, Pa., 1.2 millimoles). An 80 milligram sample of chloroplatinic 
acid (available from Aldrich Chemical Co., 0.2 millimole) was dissolved in 
2 ml of unstabilized tetrahydrofuran (available from Burdick and Jackson) 
and was added to the slurry. The flask was purged with nitrogen and 
stoppered with a pressure-sealing polytetrafluoroethylene stopper, and 
then heated at 100.degree. C. for 20 hours. The sample was then allowed to 
sit at room temperature for 24 hours. The sample was recovered on a 
Buchner funnel, where it was washed to remove unbound reagents. The washed 
gel was then dried overnight to remove residual solvent. Carbon combustion 
analysis of the final product indicated 1.6% C. 
Example 29 
Example 29 describes the preparation of a trivinyl 
octadecylsilyl--octadecylsilyl copolymeric bonded phase on a zirconia 
chromatographic support. 
11 grams of the ZrO.sub.2 gel described in Example 16 was washed with 0.1N 
NaOH, water and acetonitrile, and then dried overnight at 110.degree. C. A 
100 ml round bottom flask was charged with 10.53 grams of the washed and 
dried ZrO.sub.2, which was suspended in 15 grams of hexane and 15 grams of 
unstabilized tetrahydrofuran (available from Burdick and Jackson, 
Muskeegon, Mich.) and then outgassed with vacuum and ultrasonication. To 
the slurry was added 0.38 gram of trivinyl octadecyl silane (prepared as 
described in Example 1, 1.1 millimoles) together with 0.11 gram of 
octadecyl silane (available from United Chemical Technologies of Bristol, 
Pa., 0.38 millimole) and 27 milligrams of 
2,2'-azobis(2-methylpropionitrile) (available from Eastman Fine Chemicals 
of Rochester, N.Y., 0.16 millimole). The flask was purged with nitrogen 
and stoppered with a pressure-sealing polytetrafluoroethylene stopper, and 
then heated at 100.degree. C. for 5 hours. 
Next, the sample was spiked with 20 milligrams of dicumyl peroxide 
(available from Aldrich Chemical Co., Milwaukee, Wis.). The procedure of 
Example 16 was then followed to yield the final product. Carbon combustion 
analysis of the final product indicated 3.32% C. 
Example 30 
Example 30 describes the preparation of a triallyl 
methoxysilyl--octadecylsilyl copolymeric bonded phase on a zirconia 
chromatographic support. 
An octadecyl-functionalized polymeric carbosilane bonded phase, covalently 
bound to the gel surface, was prepared on the ZrO.sub.2 chromatographic 
support described in Example 16 according to the procedure described in 
Example 16 except that 11.5 grams of the ZrO.sub.2 gel was washed with 
0.1N NaOH, water and acetonitrile, and then dried overnight at 110.degree. 
C. A 100 ml round bottom flask was charged with 11.05 grams of the washed 
and dried ZrO.sub.2, which was suspended in 20 grams of hexane and then 
outgassed with vacuum and ultrasonication. To the slurry was added 0.39 
gram of triallyl methoxy silane (prepared as described in Example 15, 2.2 
millimoles) together with 0.43 gram of octadecyl silane (available from 
United Chemical Technologies of Bristol, Pa., 1.5 millimoles) and 70 
milligrams of dicumyl peroxide (available from Aldrich Chemical Co., 
Milwaukee, Wis., 0.26 millimole). The procedure of Example 16 was then 
followed to yield the final product. Carbon combustion analysis of the 
final product indicated 4.56% C. 
Various modifications and alterations of this invention will become 
apparent to those skilled in the art without departing from the scope and 
spirit of this invention, and it should be understood that this invention 
is not to be limited to the illustrative embodiments set forth herein.