JPS62110746A - Packing material for liquid chromatography - Google Patents

Abstract

PURPOSE:To obtain a packing material having resistance to acid and alkali by using a packing material for liquid chromatography encapsulated in resin to reduce the influence of residual Si-OH group by enclosing Si-OH groups with the resin capsule. CONSTITUTION:A silicone compd. expressed by the general formula: (R<1>HSiO)a(R<2>R<3>SiO)b(R<4>R<5>R<6>SiO1/2)c (wherein R<1>, R<2>, and R<3> are 1-10C hydrocarbon groups substituted with halogen atoms; R<4>, R<5> and R<6> are H tom or similar hydrocarbon groups substituted with halogen atoms; a and b are zero or integers; c=0 or 2; a+b+c=3-300) is allowed to contact with powder to cause polymn. of the compd. on the whole surface of the powder, and unreacted Si-H groups are crosslinked in the presence of a catalyst. Thus, powder body having silicone polymer film on the whole surface is obtd. When the powder is used as packing material for liquid chromatography, the influence of residual Si-OH groups is reduced and a packing material having sharp polarity and high resistance to acid and alkali is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a liquid chromatography packing material comprising a powder carrying a silicone polymer film on its surface.

[Conventional technology] At present, analysis and preparative purification technology using high-performance liquid chromatography has progressed significantly, and some companies are using even larger liquid chromatography plants for purification. ing. Under these circumstances, it goes without saying that the quality of the packing material used to fill the column is important in analysis and preparative purification.

Currently, about 80% of analysis and preparative purification by high-performance liquid chromatography is performed by reversed-phase liquid chromatography. Among them, the silanol group (S
Many application examples have been reported using ODS-silica gel (C1s type) filler in which dimethyloctadecylchlorosilane is chemically bonded to (t-OH group). In addition, packing materials for reversed phase liquid chromatography include:
Type C, 1 type in which dimethyloctachlorosilane is chemically bonded to the silanol group of silica gel, Type 04 in which dimethylbutylchlorosilane is chemically bonded, Type 01 in which trimethylchlorosilane is chemically bonded, Type C is chemically bonded to triphenylchlorosilane. Phenyl type etc. are known.

[Problem that the invention seeks to solve]

However, in the conventional chemically bonded packing material for reversed-phase liquid chromatography described above, the reaction between the Si-OH (silanol) group and the alkylchlorosilane is not completed and 10 to 20% of s+-0114,V remains. ing. It is said that the number of residual Si-011 groups increases in the order of larger molecules, ie, CPS type>CB type>C4 type<C, type, which is a major problem in reversed phase liquid chromatography. That is, the residual S
When the i-Oll group exists, strong interaction with polar substances occurs, and therefore, the peak of the polar compound becomes broad in analysis or preparative separation, and furthermore, a tailing phenomenon occurs.

Furthermore, the remaining Si--OH groups cause irreversible adsorption with highly polar compounds, which accelerates the deterioration of the packed column. Furthermore, due to the presence of residual Si-OH groups and the hydrophilic surface of silica gel, acid resistance and alkali resistance are weak, and the pH range of mobile phase solvents that can be used is limited to pH 2 to 7 in the case of conventional packed columns. There are many problems such as For this reason, some conventional packed columns are treated with trimethylchlorosilane (TMS) or the like again to block the remaining St -OH groups after the reaction with dimethyloctadecylchlorosilane or dimethyloctylchlorosilane. Some did. However, even by trimethylsilylation treatment, residual Si-OR groups cannot be completely eliminated.

That is, a high-quality reverse phase liquid chromatography moonlight agent that does not contain any residual Si--OH groups has not yet existed.

Furthermore, trimethylsilylation completely removes Si-01 from Si-01.
Even if one group can be blocked, the exposed hydrophilic surface of silica gel still exists, so the problem of weak acid and alkali resistance cannot be solved.

As a result of extensive research, the present inventors have found that the influence of residual Si -OR groups can be minimized by using a resin capsule type photonic agent, which is essentially different from conventional chemically bonded type photonic agents. It has been found that it is possible to make a material with high acid resistance and alkali resistance. Therefore,
The purpose of the present invention is to completely eliminate the influence of the 5l-OH group,
Our objective is to provide a column packing material for liquid chromatography that has sharp peaks for polar compounds, has excellent acid resistance and alkalinity, and can be used for a long period of time.

[Means for solving problems]

The purpose is to: (a) have the general formula % () where R1, R2 and R3 are, independently of each other, 1 to 10 carbon atoms which may be substituted with at least one halogen atom; is a hydrocarbon group, and R4, R
5 and R6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with at least one halogen atom, and a is an integer of 0 or 1 or more. , b is an integer of 0 or 1 or more, C is 0 or 2, and the sum of a, b, and C is 3 to 300). (b) crosslinking unreacted Si-H groups in the presence of a catalyst;
And depending on the case, (c) a small amount of Si − generated during the step (b)
0■ (silanol) group is trimethylsilylated using a trimethylsilylating agent, and is made of a powder that carries a silicone polymer film on substantially the entire surface. achieved.

Furthermore, the said object is (a) general formula % formula % (1) (wherein R1, R2, R3, R4, R5, R6, a, b
(b) bringing the powder into contact with at least one silicone compound represented by (and C has the same meaning as above) and polymerizing the silicone compound on substantially the entire surface of the powder; adding a vinyl compound of up to 40 carbon atoms to the unreacted S i -I+ group, and optionally (c)
The remaining unreacted Si-If groups are crosslinked in the presence of a catalyst, and optionally (d) the Si-If groups slightly formed during step (c) above are
This is achieved by using a liquid chroma powder filler made of a powder with a silicone polymer film on substantially the entire surface, which is produced by a process consisting of trimethylsilylating OH groups with a trimethylsilylating agent. .

The present invention will be explained in more detail below.

In this specification, it is referred to as "powder", and 11, average particle size is 3 μm.
~1000μm, specific surface area 1()■ζ/g ~10
00rr+/g means a porous body with 30 to 1000 pores. Any powder commonly used as a carrier for liquid chromatography may be used in the present invention, such as silica gel, alumina, glass beads (eg porous glass), zeolite, hydroxyapatite or graphite.

Furthermore, composite powders, ie, powders of synthetic resins such as polyamides, acrylic resins, or polyvinyl alcohols whose surfaces are coated with fine inorganic powders such as silica gel, titanium dioxide, or hydroxyapatite, can also be used. Preferred powders have pores of 50 to 500, especially 60 to 300, and a specific surface area of 50 to 600.
%/g, it is a spherical or crushed silica gel with a particle size of 3 μm to 500 μm.

The present inventor brought the powder into contact with a silicone compound having an Si-H group, surface-polymerized it, and then cross-linked it or added a vinyl compound to the powder, thereby removing an organic solvent such as hexane, benzene, chloroform, etc. It has been found that it is possible to form a uniform silicone polymer film that does not dissolve in acetone, methanol, acetonitrile, water, or the like.

In the present invention, the general formula % formula % (1) (In the formula, R', R2, R', R', R5, Rh.

A silicone compound represented by (a, b and C have the same meanings as above) is brought into contact with the powder either alone or in the form of a mixture thereof.

The "hydrocarbon group" of the group R1 to R6 above refers to a straight-chain or branched anobar group, particularly a lower alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group or n-butyl groups; cycloalkyl groups such as cyclohexyl groups; cycloalkenyl groups such as cyclohexenyl groups; aryl groups, especially phenyl or naphthyl groups;
It means an aryl-substituted alkyl group such as a phenylmethyl group or a phenylethyl group; an alkyl-substituted aryl group such as a methylphenyl group.

A halogen substituent is a chlorine, bromine, iodine or fluorine atom.

The silicone compounds represented by the general formula (I) are comprised of two groups. The first group includes c in the general formula (I).
=Q, and the general formula (R'HSiO)a'
(R2R"SiO)b' (V) (wherein, R1, R2 and R3 have the same meanings as above, and a'
and b' have the same meaning as a and b, respectively,
However, the sum of a' and b' is 3 to 300.) It is a cyclic silicone compound represented by:

In the present invention, in the general formula (V), R1,
R2 and R'' independently represent a lower alkyl group, particularly a methyl group,
Preference is given to using cyclic silicone compounds which are ethyl, n-propyl or n-butyl groups, or aryl groups, especially phenyl groups, and in which the sum of a' and b' is from 3 to 100. R1, R2 and R3 can be different groups but are preferably the same group.

Particularly preferred cyclic silicone compounds have the general formula (wherein R
1 has the same meaning as above, and a" is an integer of 3 to 300. In the general formula (Vl), R1
is a methyl group or ethylno, (, and a# is 3 to 10
Particularly preferred are compounds in which 0.

Appropriate cyclic Siri:! Examples of the compound include tetrahydrotetramethylcyclotetrasiloxane, tetrahydrotetraethylcyclotetrasiloxane, tetrahydrotetraphenylcyclotetrasiloxane, tetrahydro-1 decamedylcyclooctasiloxane, tetrahy-I-lotylcyclotetrasiloxane, and the like. can be mentioned.

Furthermore, in the present invention, mixtures of cyclic silicone compounds containing different numbers of repeating units (eg, 30 to 50, 80 to 1()0, etc.) may be used.

The second group of silicone compounds has the general formula (+)
corresponds to the case where C=2 in the general formula (R'HSiO
)a"'(R2R3SiO)b"'(R'R'R6
SiO1)z (■) (wherein, R1, R2, R3, R
4, R5 and R6 have the same meanings as above, a''' and b''' have the same meanings as a and b, respectively,
provided that a''+b''+2 is 3 to 300).

In the present invention, in the general formula (■), R1,
R2, R3, R4, R5 and R6 are independently lower alkyl groups, especially methyl, ethyl, n-propyl or n-butyl groups, or aryl groups, especially phenyl groups, and a'' and b'' Preferably, linear silicone compounds having a sum of 3 to 100 are used. R1-R6 can be different groups, but are preferably the same group.

Suitable linear silicone compounds include, for example, 1,
1. R2,3,4,4,4-octamethyltetrasiloxane, LLI, 2,3,4,5,5.5-nonamethylpentasiloxane, and 1,1,1,2,3,4,5,
Mention may be made of 6,6,6-zocamethylhexasiloxane.

The silicone compound represented by the general formula (1) is brought into contact with the powder in a gas phase or liquid phase.

Contact between the silicone compound in the gas phase and the powder (vapor phase treatment) is carried out as follows.

1 part by weight of a powder (for example, silica gel) and 0.01 to 1 part by weight of a solid or liquid silicone compound are placed in separate small containers, and then placed in a closed container with a capacity of 5 to 500 times the volume of the powder. (For example, a desiccator, a closed type constant temperature bath), and after sealing the container, heat it at 50 to 200°C for 2 hours or more. At this time, the powder may be left stationary, but it is preferable to stir it. Therefore, it is preferable to use a closed container with a stirring function, or a container with a function of vibrating or rotating the container itself to fluidize the powder inside.

When processing a large amount of powder (for example, 51nr or more), it is possible to carry out the process using, for example, an apparatus including a heat-insulating jacket toy, a one-rotation heating reaction tank, and a stock solution supply tank with a heat-insulating jacket connected thereto. can. A large amount of powder was placed in a heating reaction tank, the system was depressurized with a vacuum pump, and the
Heat above ℃. The raw solution supply tank, which has been heated in advance at the same temperature, is opened and closed, and the silicone compound gas is supplied into the reaction tank and brought into contact with the powder. At this time, it is preferable to periodically rotate the reaction tank to fluidize the powder inside.

After depressurizing the system as described above, the same operation can also be carried out after the system has been purged with an inert gas, such as nitrogen gas.

Furthermore, a reaction vessel with a separate small vessel inside can be used. A solid or liquid silicone compound is placed in the small container and heated under reduced pressure or normal pressure to vaporize the silicone compound and bring it into contact with the powder.

Furthermore, it is also possible to make the system an open system and to supply the silicone compound gas into the reaction tank by passing a carrier gas such as nitrogen gas into the stock solution supply tank.

Examples of silicone compounds suitable for the above-mentioned gas phase treatment include tetraethylcyclotetrasiloxane and tetrahydrotetramethylcyclotetrasiloxane.

Volatile solvents that can dissolve silicone compounds, such as benzene, dichloromethane or chloroform, especially in hexane? It is also possible to bring the silicone compound in a container into contact with the powder (liquid phase treatment). A solution containing 1 to 50% by weight of a silicone compound is prepared, and the silicone compound solution is added to the powder while stirring so that the silicone compound is 0.01 to 1 part by weight per 1 part by weight of the powder. In the case of liquid phase treatment, it is preferred to evaporate the solvent before carrying out the surface polymerization.

The silicone compounds used in liquid phase processing are generally cyclic or linear silicone compounds containing 10 or more repeating units.

Surface polymerization of the silicone compound on the surface of the powder can be carried out by leaving the powder after the above-mentioned contact treatment at a temperature of 50 to 200 DEG C. for 2 hours or more or stirring the powder every time.

This surface polymerization is promoted by the action of the surface active sites of the powder itself, so there is no need to add any particular catalyst. here"
"Active site" is a site that can catalyze the polymerization of a silicone compound having a siloxane bond (Si-0-3i) or a Si-H (hydrosilyl) group, such as an acid site, a base site, an oxidation site, or a reduction site. means a point. Surface polymerization is carried out until the active sites on the powder surface are covered with a film of silicone polymer. If the activity of the powder itself is very weak, an alkali catalyst such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide or calcium hydroxide, or an alkyl metal may be added to the powder before or after the contact treatment. Polymerization may be carried out after appropriately adding a catalyst such as dibutyltin.

There are two types of polymerization of the silicone compound on the powder surface: when the powder and the silicone compound are brought into contact in the gas phase and heated, or when the powder and the silicone compound are brought into contact in the liquid phase and heated in a constant temperature bath. be. One of them is S i -I
This is cross-linking polymerization between t groups and forms a network structure on the powder surface. That is, it proceeds as shown in (wherein R is a hydrocarbon group R1 to R6).

The degree of progress of crosslinking polymerization between Si-H groups is determined by FT-IR
It can be easily grasped by measuring the diffuse reflection spectrum using a Fourier transform infrared spectroscopy device (Fourier transform infrared spectroscopy l1l). That is, as crosslinking progresses, Si-
Since the H group disappears, it can be understood by determining the intensity of absorption based on the Si-H stretching vibration appearing at 2160el11-'. In addition, the network structure produced by crosslinking polymerization can be confirmed from this point, since only the peaks of methane, ethane, and other alkanes are observed in the pyrogram obtained by pyrolysis gas chromatography. No matter how the reaction conditions (temperature, catalyst, etc.) are strengthened, this crosslinking polymerization cannot be increased to 80% or more due to steric hindrance.

Another mode of polymerization is the macrocyclization of cyclic silicone compounds and the macrolinearization of linear silicone compounds through siloxane bonds. These polymerization modes are, for example, the following reaction formula or (in each of the above formulas, R has the same meaning as above, m is the sum of a and b, and m' is an integer larger than m). can be expressed.

This polymerization is promoted by the surface active sites (particularly Brønsted acid sites) of the powder. The progress of this polymerization is FT-
2 in measuring diffuse reflection spectra using an IR device
The intensity of absorption based on the Si-II stretching vibration at 160 cm' does not decrease, and furthermore, cyclic or linear silicone with a distribution of m r = 4 to 30 appears in 11 grams of pi by pyrolysis gas chromatography. 4' (141).

Depending on the type of powder and reaction conditions (temperature, catalyst, etc.), the above two different types of polymerization may proceed independently, or both types may proceed simultaneously. The degree of polymerization also varies.

As described above, in the present invention, since a low molecular weight silicone compound is brought into contact with the powder, the silicone compound penetrates into the pores of the powder and adheres or adsorbs onto substantially the entire surface of the powder. As the powder is polymerized, a very thin film (3 to 30 films) of silicone polymer is formed on the powder surface, and the porosity of the powder remains substantially intact. This porosity is not substantially impaired by subsequent crosslinking, vinyl compound addition, and trimethylsilylation.

The molecular weight (weight average molecular weight) of the silicone polymer formed on the powder surface by the above polymerization reaction is 150,000 or more. Although it can be confirmed that the above molecular weight is 150,000 or more, there is no means to determine the molecular weight in more detail. In other words, in the case of silicone compounds, as they become polymerized through polymerization, they become less soluble in water and organic solvents, making it impossible to extract the polymer and measure its molecular weight. It is also not possible to measure the molecular weight of a polymer in its present state.

Therefore, the inventor indirectly determined the molecular weight (weight average molecular weight)
In order to estimate, the polymer at each stage during polymerization was extracted into chloroform, each extract was analyzed by GPC (gel vermation chromatography), and the molecular weight of the extracted polymer was determined by polystyrene conversion.
It was possible to detect the presence of a polymer with a maximum molecular weight of 150,000. Therefore, it can be said that the molecular weight (weight average molecular weight) of poly-7-, which has been sufficiently polymerized to the point where it is not extracted by chloroform, is 150,000 or more.

The powder coated with the silicone polymer formed by the above-mentioned surface polymerization can be used as a reversible liquid chromatography filler even if it is packed into a column as it is. For example, in the general formula (I), the group R1-group R
The filler of the present invention, which is made of a powder treated with a silicone compound in which all of the groups R1 to iFR' are methyl groups, has a retention comparable to that of the conventional CI type in which trimethylchlorosilane is chemically bonded to silica gel. It has power. However, although it can be used stably when using a solvent that is inert to Si-H groups (such as acetonitrile), when an alcohol-based mobile phase solvent is passed through the column, residual Si Since there are many -H groups, it reacts with alcohol to generate hydrogen, and the column gradually deteriorates. The inability to use alcohol-based mobile phase solvents is a fatal flaw for column packings.

The present inventors have discovered that in the powder after the surface polymerization treatment,
By crosslinking unreacted Si-H groups present in silicone polymers in the presence of a catalyst, it is possible to obtain a filler that can be stably used even when alcohol-based mobile phase solvents are used. I found it. As a crosslinking catalyst, an alkali catalyst such as hydroxide 1-
lithium, potassium hydroxide, calcium hydroxide, ammonium hydroxide, lithium hydroxide or thorium carbonate,
Alkyl metal catalysts such as dibutyltin, ii; or avalylamine catalysts such as tributylamine can be used. In an aqueous solution, alcohol solution, or other organic solution (e.g., acetone or acetonyl-lyl) containing about 0.01 to 10% by weight of these catalysts, the powder after the surface polymerization treatment is heated at 1 to 40% by weight. When left at room temperature or under heating, or heated under reflux, residual Si
-If group crosslinks as shown in reaction formula 4.

The amount of silicone compound coated on the powder surface is 1 to 50% by weight, preferably 10 to 3% by weight, based on the weight of the powder.
0% by weight army. If the amount of the silicone compound exceeds 50% by weight, the amount of the silicone compound that is simply attached to the surface of the powder without being sufficiently polymerized will increase, making it undesirable as a filler. If the amount of the silicone compound is less than 1% by weight, the entire surface of the powder cannot be covered with a silicone polymer film, which is not preferable because the holding power as a filler becomes weak. The amount of silicone compound, reaction conditions, etc. used to coat the powder with a desired amount of silicone compound can be easily determined by pilot tests.

The filler of the present invention made of the powder thus obtained has approximately the same holding power as a conventional chemically bonded optical filler. For example, in the general formula (I), the group R1-group R3 (
Alternatively, the filler of the present invention, which is made of a powder treated with a silicone compound in which all of the groups R1 to R6) are methyl groups, is a filler of the conventional C.

Comparable to other types of fillers.

The present invention further provides the general formula % formula % () (wherein R1 has the same meaning as above, t is an integer making the weight average molecular weight 150,000 or more, and
and y is a number that satisfies the relationship of x + y = l and 0.6≦X≦1) A liquid consisting of powder carrying a silicone polymer skin 11 on substantially the entire surface. Capture and provide chromatography moonlight agent. This filler is produced by, for example, contacting the powder with a cyclic silicone compound represented by the general formula (wherein R1 and a" have the same meanings as above), so that substantially all of the powder is It can be produced by polymerizing the silicone compound on the surface and crosslinking the unreacted Si-H groups in the presence of the catalyst.

It can be estimated by the same method as above that the silicone polymer represented by the general formula (11) has a molecular weight of 150,000 or more. Furthermore, the ratio of X and y is F
It can be determined by measuring an infrared diffuse reflection spectrum using a T-IR device. In this method, the Si-H group of the cyclic silicone compound undergoes crosslinking polymerization as shown in the following formula (XI) to become Si-O-8i, and Si-H
The principle is that the number of groups decreases.

-A i' -H-! l. ``'. Knee 4 + -0-j
3 i -(XI, that is, in the infrared diffuse reflection spectrum, a peak based on the stretching vibration of the Si-H group appears at 2160 cm-', and this absorption intensity decreases as crosslinking polymerization progresses. Therefore, The ratio of X and y can be determined by determining the Si-H peak intensity ratio of the sample before polymerization and the sample after polymerization.

Preparation of the sample before polymerization can be carried out by determining the silicone compound coverage of the sample after polymerization from the weight increase, and adding and mixing the same weight part of the cyclic silicone compound to the silica gel under non-polymerization conditions. . To measure the diffuse reflection spectrum, 1 part by weight of the sample and 9 parts by weight of KBr (potassium bromide) powder were stirred and mixed, and then ^II was added to the cell.
Place the sample on the sample stand and perform the measurement. The peak intensity of the Si-It group is determined at 2160 cm-' of the obtained spectrum, and calculated using the following four formulas (XTI).

X=1.0-yy=Y/X (XTI) In the above calculation formula, X is the Si-It peak intensity of the sample before polymerization, and Y is the Sill peak intensity of the sample after polymerization.

The relationship with x,:y is 0.6≦X≦1 with x ]y=l
However, it is preferred that 0.7≦X≦0.9, and it is particularly preferred that X is about 0.8 (and therefore y is about 0.2).

When the powder surface-polymerized with the silicone compound represented by the general formula (1) is crosslinked in the presence of the catalyst,
During the crosslinking process, silanol (Si-OH) groups may be slightly chemically converted. A packing material containing silanol groups (:r) causes irreversible adsorption with highly polar compounds, resulting in column deterioration.

The present inventors discovered that after the crosslinking step, the Si-01
By blocking one group by trimethylsilylation, S
It has been found that it is possible to obtain a high-quality reversed-phase liquid chromatography chromatography agent that is significantly less affected by the i-011 group.

Trimethylsilylation is carried out by bringing the crosslinked powder into contact with a trimethylsilylating agent in a gaseous or liquid phase. For example, 0.5 to 3 parts by weight (especially about 1 part by weight) of trimethylchlorosilane, 1 to 6 parts by weight (especially about 2 parts by weight) of hexamethyldisilazane, and 1 to 8.5 parts by weight (especially about 2 parts by weight) of pyridine. The powder is heated under reflux under stirring for 2 to 24 hours in a mixture with about 7 parts by weight). Alternatively, trimethylchlorosilane, hexamethyldisilazane, trimethylmethoxysilane or trimethylethoxysilane, each alone, is heated to about 40°C to 150°C with the powder in a closed container.

In this way, a column packing material can be obtained that can handle even highly polar compounds that cannot be handled with conventional chemically bonded column packing materials.

By the way, especially in reversed-phase liquid chromatography, in most cases a packing material with stronger retention than the above-mentioned C1 type packing material [for example, C11 type (ODS-silica gel), C8 type, or phenyl type] is used. occupy The present inventor has developed a liquid chromatography packing that can be stably used without generating hydrogen even when an alcohol-based mobile phase solvent is used, and has a retention power comparable to that of the conventional C11l type packing. As a result of intensive testing and testing to further develop the agent, we were able to complete the following invention.

That is, the present inventor brought the silicone compound represented by the general formula (1) into contact with the powder and surface-polymerized it in the same manner as described above, and then added a vinyl compound to the remaining Si-It group. It has been found that it is possible to obtain a filler capable of achieving the above-mentioned objectives.

The above-mentioned vinyl compound is, for example, a compound having the general formula % () (wherein R8 and R9 are each independently a hydrogen atom,
An aryl group that may be substituted with an alkyl group having 1 to 40 carbon atoms, a cycloalkyl group or cycloalkenyl group having 4 to 8 carbon atoms, or an alkyl group having 1 to 20 carbon atoms, and An alkyl group, a cycloalkyl group, a cycloalkenyl group, an alkyl-substituted aryl group, or an aryl group is a halogen atom, a hydroxyl group,
Compounds represented by the following formulas (which may be substituted with a carboxyl group, an amino group, a cyan group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a sulfonic acid group) can be used.

The vinyl compound represented by the general formula (IV) is R8
and ethylene in which R9 are both hydrogen atoms, vinyl compounds in which one of R@ or R9 is a hydrogen atom and the other is a substituent other than a hydrogen atom, such as an α-olefin compound,
It may be either a symmetric vinyl compound in which Re and R9 are the same substituent other than a hydrogen atom, or an asymmetric vinyl compound in which R8 and R9 are different substituents other than a hydrogen atom.

In the preferred vinyl compound, in the general formula (TV), R11 and R9 independently represent a hydrogen atom; an alkyl group having 4 to 20 carbon atoms, such as a 1-hexyl group, a 1-
Octyl group, 1-decyl group, ■-dodecyl group, 1-hexadecyl group, or 1-octadecyl group; cyclohexyl group or cyclohexenyl group; phenyl group or naphthyl group; or lower alcohol group having 1 to 4 carbon atoms It is a vinyl compound which is a phenyl group or a naphthyl group substituted with.

In the general formula (IV), R8 is a hydrogen atom,
Addition of a vinyl compound in which R9 is an ethyl group, hexyl group, hexadecyl group, or phenyl group corresponds to the 04-type, C8-type, Cl8-type, or phenyl type of conventional chemically bonded photostimulants, respectively. can be obtained.

Another preferable vinyl compound is the general formula (IV), in which at least one of R8 and R9 is a functional group (halogen atom, hydroxyl group, carboxyl group, amino group, cyan group, alkoxycarbonyl group, aryloxycarbonyl group, This is a compound in which a group other than a hydrogen atom is substituted with a sulfonic acid group). By adding this vinyl compound, a packing material for normal phase or ion exchange liquid chromatography can be obtained.

On the other hand, when a vinyl compound containing no functional group is added, a reverse phase liquid chromatography supporting agent can be obtained.

As described above, by appropriately selecting the vinyl compound, the properties of the filler can be freely designed and controlled.

The reaction between the vinyl compound and the silicone polymer-coated powder can be carried out using hydrosilylation, which is known per se [for example, A. J. Chalk et al., Journal. of the American Chemical Society (J, 8m, Chew, Soc,), 87.16 (196
See 5)]. The above reaction can be carried out, for example, by contacting in the presence of a solvent at 50 to 300° C. in a gas phase or liquid phase for 2 hours or more.

Suitable catalysts are platinum group catalysts, ie compounds of ruthenium, rhodium, palladium, osmium, iridium or platinum. Palladium compounds and platinum compounds are particularly good. Examples of palladium-based catalysts include palladium chloride (formerly tetraamminepalladium (II) chloride, M ammonium, palladium oxide (■), palladium (II) hydroxide, etc.). Examples of platinum-based catalysts include, for example, platinum chloride ( ■), tetrachloroplatinic acid (■), platinum chloride (■), hexachloroplatinic acid (
■), hexachloroplatinic acid (IV) ammonia, mu, platinum oxide (■), platinum hydroxide (■), platinum dioxide (■),
Platinum oxide (■), platinum disulfide (■), platinum sulfide (■),
Examples include potassium hexachloroplatinate (TV). In addition, 1·'J Cl-s-alkylmethylammonium chloride and tri-C+-me alkylamine were added to these palladium-based or platinum-based compounds, and ion pair extraction was performed in a water/organic solvent system, resulting in an organic solvent layer. You can also use Furthermore, it is also possible to use alkylamines such as tributylamine.

The reaction between the vinyl compound and the Si-H group of the silicone polymer coated powder can be confirmed by measuring the diffuse reflection spectrum using an FT-IR device. That is, the absorption intensity of the Si--H group of 216Qc+a'' is significantly reduced by the addition of the vinyl compound, and in its place, a new absorption based on an alkyl group appears at 2800 cm-1 to 3000 cm-'. Therefore, the reaction rate between the Si--H groups of the silicone polymer coated powder and the vinyl compound can be determined from the following formula.

When the reaction rate is increased to 60% or more, hydrogen is no longer generated even when an alcoholic mobile phase solvent is passed through the column, and it can be stably used.

The amount of silicone polymer coverage after adding the vinyl compound is
10 to 60% by weight, preferably 2% by weight based on the weight of the powder
The amount is from 0 to 40% by weight.

The present invention further provides the following formula: −, and X′,
y' and 2)+'+y'-1-z =], O≦X'≦0.5. 0≦y'≦0.4 and 0.5≦2≦1.0) from a powder carrying a silicone polymer skin V expressed on substantially the entire surface. We provide a liquid chromatography moonlight agent. This filler is produced by, for example, contacting the powder with a cyclic silicone compound represented by the general formula (wherein R1 and a" have the same meanings as above), so that substantially all of the powder is A silicone compound is polymerized on the surface, and the unreacted Si-H groups are treated with the general formula (IV
) can be produced by adding a vinyl compound represented by:

It can be estimated by the same method as above that the silicone polymer represented by the general formula (III) has a molecular weight of 150,000 or more.

The ratio of X', y', and 2 can be determined by measuring the diffuse reflection spectrum using an FT-IR device, as in the case of the general formula (n). That is, for the sample before adding the vinyl compound, calculate the ratio of X (-X') to y using the above trial calculation formula (XII), and then calculate the ratio of the sample before and after adding the vinyl compound. Find the Si-H peak intensity ratio at 2160 cm-',
Calculated using the following trial calculation formula (XIII).

! '-1.0-y y '-(Z/Y) y (Xllll)z=
1.9, r, -y1 In the above trial calculation formula, Y has the same meaning as above, and Z
is the S i -I+ peak intensity after addition of the vinyl compound.

The relationship between X', y' and 2 is x'+y'+z=1 and 0≦
X'≦0.5.0≦y'≦0.4 and 0.5≦2≦1
However, 0.1≦X'≦0.3.0.1≦y'≦0.
3 and 0.5≦2≦0.7 are preferred, and it is particularly preferred that X' is about 0.2, y' is about 0.2 and 2 is about 0.6.

The retention force of the reverse phase liquid chromatography moonlight agent coated with 10 to 15% by weight of the silicone polymer represented by the general formula (Ill) is, for example, when R1 is a methyl group and R? The one with octadecyl group is the conventional C11 type (
ODS)-comparable to silica gel, R1 is a methyl group and R7
The one with octyl group is comparable to the conventional Cll type silica gel, the one where R1 is a methyl group and R7 is a butyl group is comparable to the conventional 04 type silica gel, and the one where R1 is a methyl group and R7 is a substituted phenethyl group is comparable to the conventional 04 type silica gel. Comparable to conventional phenyl type silica gel.

Furthermore, in general, the conventional It is possible to obtain a liquid chromatography moonlight agent that has a wide range of retention power that cannot be obtained with chemically bonded photoreactive agents.

The vinyl compound addition treatment described above leaves some Si-H groups in the silicone polymer due to steric hindrance. S
If the i-H group is present, hydrogen will be generated and the column will deteriorate when an alkaline (pH 8-14) mobile phase solvent is used. Therefore, it is preferable to crosslink the remaining Si-H groups in the same manner as described above. This crosslinking treatment can be carried out in the same manner as described above.

Furthermore, since a small amount of Si-OH group may be generated during the crosslinking treatment, it is preferable to perform trimethylsilylation as well.

As mentioned above, the filler of the present invention made of the powder obtained in this manner has a holding power that is approximately the same as that of the conventional chemically bonded optical filler. Second, the filler of the present invention has excellent resistance to organic solvents, acids and alkalis,
It can be used very stably for a long period of time.

[For production]

The liquid chromatography moonlight packing agent obtained by the present invention is essentially different in type from conventional packing materials, which are characterized by chemical bonding, and is a resin capsule type in which silicone polymer is uniformly coated with powder. A distinctive feature of this product is that there are no chemical bonds between the silicone polymer and the powder. That is, since it is a resin capsule type, a high-quality liquid chromatography moonlight agent can be obtained that is hardly affected by the polar groups (for example, silanol groups of silica gel) of individual powders.

Furthermore, it is possible to use alkaline mobile phase solvents that cannot be used with conventional packing materials, and the range of applicable samples for analysis and preparative separation can be expanded.

Furthermore, by appropriately selecting the side chains of the starting silicone compound and vinyl compound, the properties of the filler can be freely designed and controlled.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
This is not intended to limit the technical scope of the invention. In the following examples, the molecular weight of the silicone polymer is the weight average molecular weight unless otherwise specified.

1 og of spherical silica gel powder with about 100 pores and an average particle size of 5 μm and a cyclic silicone compound [In formula (1), R' = CH3, a = 3 to 5, b = c = Q 2g of 100g) in separate containers, put them in the same desiccator, close them tightly, put them in a constant temperature bath at 80°C, leave them for 7 hours, and convert the cyclic silicone compound into silica gel powder in the gas phase in the desiccator. They were brought into contact and surface polymerized. Subsequently, the silica gel powder container was taken out from the desiccator and heated at 105° C. for 1 hour in a constant temperature bath. After cooling, add 3 powders
The powder was placed in a 00ml beaker, 200rrl of a 0.01N sodium hydroxide/acetonitrile mixture (2:1) was added thereto, the powder was dispersed, and the mixture was heated on a water bath for 2 hours. Next, it is filtered using a glass filter (G-4), and the water/acetonitrile mixture (2:
After washing and filtering in step 1), place in a constant temperature bath at 105°C.
Let dry for an hour.

The silicone polymer powder thus formed is
By measuring the infrared diffuse reflectance spectrum using an FT-IR device, it was found that the molecular weight was 150,000 or more since the loloform soluble matter was 0.001% or less.

Using a backer and a pump, 3 g of the above powder was
, ■ and a stainless steel column with a length of 25 cm were filled by an equilibrium slurry method to prepare a packed column.

Connect the zero column to a high performance liquid chromatograph and use 30% methanol as the mobile phase at 1 m7 per minute! A standard mixture of uracil, methyl benzoate, toluene, and naphthalene was injected and detected using a UV detector at 254 r+m to obtain a chromatogram.

As a result, the retention time and number of theoretical plates for each peak were as follows.

廿-4 10g of crushed silica gel powder with approximately 100 pores and an average particle size of 5μm is 300mJ! Place in a beaker, add 100 m/h of hexane and a cyclic silicone compound [formula (I)
In, RI-CI13, a-80-100, b=c
= Q's] 4G was added, and hexane was vaporized on a water bath while stirring, and then placed in a constant temperature bath at 100°C and heated for 10 hours. After cooling, 0.01N water was added to the powder. Oxidized Litrium J, acetonitrile mixture (2:1)
Add 200 mff, t5) Disperse the body and place on a water bath for 2
heated for an hour. Next, it was filtered using a glass filter (G-4), washed and filtered with a mixture of water and acetonitrile (2:1) until the filtrate became neutral, and then placed in a constant temperature bath at 105°C and dried for 3 hours. Ta. The silicone polymer thus formed had a molecular weight of 150,000 or more and a packed column was prepared from the powder in the same manner as in Example 1.

The column was connected to a high performance liquid chromatograph, and 50% methanol was flowed as the mobile phase at 1 mp/min.
A chromatogram was obtained for the same standard mixture as in Example 1 above. The retention time and number of theoretical plates for each peak were as follows.

Take 10 g of spherical silica gel powder with approximately 100 pores and an average particle size of 5 μm into a 300 m beaker, and add 100 mj of hexane! and a cyclic silicone compound [formula (I), R'=C, l+, a ~20~40°b=
After adding 2 g of c=Q) and volatilizing the hexane on a water bath while stirring, put it in a thermostatic bath at 180°C for 10 minutes.
heated for an hour. After cooling, the powder was treated as in Example 2 above. In this way, a film of a silicone polymer having a molecular weight of 150,000 or more and having the formula % was formed on the powder.

A packed column was prepared in the same manner as in Example 1 from 3 g of the obtained powder and a stainless steel column (inner diameter 6 cm and length 15 cm).

The column was connected to a high performance liquid chromatograph, and 50 methanol was flowed as a mobile phase at a rate of 1 ml per minute.
A chromatogram was obtained for the same standard mixture as in Example 1 above. The retention time and number of theoretical plates for each peak were as follows.

10g of spherical silica gel powder with approximately 100 pores and an average particle size of 10μm for 300mJ! Take a beaker, add 106 mn of hexane and a cyclic silicone compound [formula (1)
In, R' = C4H,, a-3 to 10, b =
After adding 2.5 g of C, = Q) and volatilizing the hexane on a water bath without stirring, the mixture was placed in a constant temperature bath at 100° C. and heated for 10 hours. After cooling, the powder was treated as in Example 2 above. In this way, a film of a silicone polymer having a molecular weight of 150,000 or more and expressed by the formula % was formed on the powder.

A packed column was prepared from the obtained powder in the same manner as in Example 3 above.

The column was connected to a high performance liquid chromatograph, and 70% methanol was flowed as a mobile phase at a rate of 1 ml per minute.
A chromatogram was obtained for the same standard mixture as in Example 1 above. The retention time and number of theoretical plates for each peak were 111 as shown below.

One morning, using the same silica gel powder and cyclic silicone compound as in Example 1, surface polymerization was carried out in a desiccator under the same conditions as in Example 1, and then the container of silica gel powder was removed from the desiccator. , and heated at 105° C. for 1 hour in a constant temperature bath. After cooling, the powder was placed in a 300 rrl eggplant flask, 1 mg of tri-n-octylmethylammonium salt of chloroplatinic acid as a catalyst and 50 mN of 1-octene were added thereto, and the mixture was heated under reflux in a water bath for 5 hours.

Next, it was filtered using a glass filter (G-4), and then 100 m# of chloroform was added, followed by 50 m# of methanol.
After washing and filtering with m#, it was placed in a constant temperature bath at 105°C and dried for 1 hour.

The silicone polymer on the powder thus formed is FT
- By measuring the infrared diffuse reflectance spectrum using a TR device, it was found that the formula% formula% loloform extract was less than 0.001%, so the molecular weight was found to be more than 150,000.

A packed column was prepared from the obtained powder in the same manner as in Example 1, and a chromatogram was obtained in the same manner as in Example 4. The retention time and number of theoretical plates for each peak were as follows.

Using the same silica gel powder and cyclic silicone compound as in Example 1, surface polymerization was carried out in a desiccator under the same conditions as in Example 1, and then the container of silica gel powder was taken out of the desiccator and placed in a constant temperature bath. The mixture was heated at 105° C. for 1 hour. After cooling, the powder was placed in a 300 mε eggplant-shaped flask, and 5 mg of tri-n-octylmethylammonium salt of chloroplatinic acid as a catalyst and 25 m7 of carbon tetrachloride were added thereto. and 25 ml of 1-octadecene were added and heated under reflux in a water bath for 10 hours. Next, the mixture was filtered using a glass filter (G-4), washed and filtered with 100 mff1 of chloroform and then 5 Qm6 of methanol, and then placed in a constant temperature bath at 105°C and dried for 1 hour.

In this way, a film of a silicone polymer having a molecular weight of 150,000 or more and expressed by the formula % was formed on the powder.

A packed column was prepared from the obtained powder in the same manner as in Example 1, and a chromatogram was obtained in the same manner as in Example 4. The retention time and number of theoretical plates for each peak were as follows.

Below, using the same silica gel body and cyclic silicone compound as in Example 1 above, surface polymerization was carried out in a dessicator under the same conditions as in Example 1, and then the container of silica gel powder was removed from the dessicator. It was heated at 105° C. for 1 hour in a constant temperature bath. After 6, 300 mj of powder! of chlorinated platinic acid as a catalyst.
+J -n-octylmethylammonium salt 1 mg
Then, 25 mA of carbon tetrachloride and 25 mJ of styrene were added, and the mixture was heated under reflux in a water bath for 2 hours. Next, filter using a glass filter (G-4), and further remove r111 form 1.
00m7! Subsequently, the mixture was washed and filtered with 50 mβ of methanol, and then placed in a constant temperature bath at 105° C. and dried for 1 hour.

In this way, a film of a silicone polymer having a molecular weight of 150,000 or more and represented by the formula was formed on the powder.

A packed column was prepared from the obtained powder in the same manner as in Example 1 above, and a chromatogram was obtained in the same manner as in Example 2 above.

The retention time and number of theoretical plates for each peak were as follows.

10g of crushed silica gel powder with approximately 50 pores and an average particle size of 1oμm
300mj! Take a beaker and add 100 hexane to it.
m7! and a cyclic silicone compound [formula (1),
R' = CH3, a = 30-50, b = c-0 (
7) Add 13 g of hexane, volatilize the hexane on a water bath while stirring, and then place in a thermostat at 100°C for 10 min.
heated for an hour. After 6, the powder was placed in a 300rrl eggplant-shaped flask, and 2mg of chloroplatinic acid as a catalyst was added thereto.
25 ml of carbon tetrachloride and 25 mj+ of 1-tococene were added and heated under reflux in a 150'C bath for 5 hours. Next, it was filtered using a glass filter (G-4), and further chloroform was added at 100 m/! , followed by 50ml of methanol! After washing and filtering, the mixture was placed in a constant temperature bath at 105°C and dried for 1 hour.

In this way, a film of a silicone resin polymer having a molecular weight of 150,000 or more and represented by the formula was formed on the powder.

A packed column was prepared from the obtained powder in the same manner as in Example 1, and a chromatogram was obtained in the same manner as in Example 4. The retention time and number of theoretical plates for each peak were as follows.

1 kg of crushed silica gel powder having approximately 60 pores and an average particle size of 44 to 63 μm and a cyclic silicone compound [formula (I)
), R' = CII 3 , a = 3-5
, b=c=Q) in separate containers, sealed and placed in a constant temperature bath (30β) that can be heated, sealed and left at 80°C for 7 hours to release the cyclic silicone compound in the gas phase. was brought into contact with silica gel powder to cause surface polymerization. After 6 days, the powder was placed in a 51 round bottom flask, 200 mg of tri-n-octylmethylammonium salt of chloroplatinic acid as a catalyst and 1.51 g of 1-octene were added thereto, and the mixture was heated under reflux using a mantle heater. It was heated at 120°C for 10 hours.

Next, it was filtered using a glass filter (G-3), and further added with 2 l of chloroform, 5 l of methanol! After washing and filtration, it was placed in a constant temperature bath at 105° (:) and dried for 1 hour.

In this way, a film of a silicone polymer having a molecular weight of 150,000 or more and represented by the formula 1 was formed on the powder.

750 g of the obtained powder and a stainless steel column (
A packed column was prepared in the same manner as in Example 1 above from a column having an inner diameter of 5 cm and a length of 50 cn+. The column was connected to a preparative liquid chromatograph, and 85% methanol was flowed as the mobile phase at 100 rn/min, and methyl benzoate was run at 0.00 m/min.
A mixture of 6 g and 1.2 g of toluene was injected into the column,
Detection was performed using a differential refractometer to obtain a chromatogram. As a result, the retention time and number of theoretical plates for each peak were as follows.

Using the same silica gel powder and cyclic silicone compound as in Example 1 above, surface polymerization was carried out in a desiccator under the same conditions as in Example 1, and then the silica gel powder container was removed from the desiccator and kept at a constant temperature. It was heated in a tank at 105° C. for 1 hour. After 6, the powder was taken into a 300 mA eggplant type flask, and treated with chloroplatinic acid as a catalyst.
1 mg of -octylmethylammonium salt and 50 ml of 1-octadecene were added and heated under reflux at 120° C. for 5 hours in an oil bath. Next, a glass filter (G-4
), then 100ml of chloroborum, followed by 50ml of methanol! After washing and filtering at 105℃
It was placed in a constant temperature bath and dried for 1 hour.

Then add 300 ml of dry powder! The mixture was placed in a glue flask, 10 ml of 28% aqueous ammonia and 90 mA of methanol were added thereto, and the mixture was heated under reflux in a water bath for 5 hours.

Next, it was filtered using a glass filter (-G-4), and then washed and filtered with methanol 50m#, and then 105
It was placed in a constant temperature bath □ at ℃ and dried for 3 hours.

Next, the dry powder was placed in a 300 ml eggplant-shaped flask, and 5 g of trimedelchlorosilane, 10 g of hexamethyldisilazane, and 80 ml of pyridine were added thereto, and the mixture was heated under reflux in a water bath for 4 hours. 6, add 100 ml of water, filter using a glass filter -= (G-4), and add 50 ml of methanol! After washing and filtering with
It was placed in a constant temperature bath at 0°C and dried for 3 hours.

A packed column was prepared from the obtained powder in the same manner as in Example 1, and a chromatogram was obtained in the same manner as in Example 4. The retention time and number of theoretical plates for each peak were as follows.

300ml of 10g of spherical silica gel powder with approximately 100 pores and an average particle size of 5μm! Add 100 mj of hexane to a beaker! and a cyclic silicone compound [formula (
In I), R' = CHz, a = 30-50
After adding 32.5 g of ゜b=c=o and volatilizing hexane on a water bath while stirring, the mixture was placed in a constant temperature bath at 100°C and heated for 10 hours. After 6, the powder was 300 m 1
1 m of tri-n-octylmethylammonium salt of chloroplatinic acid as a catalyst.
g and 50 mN of 1-octene were added and heated under reflux in a water bath for 5 hours. Next, it was filtered using a glass filter (G-4), washed and filtered with 100 mff of chloroform and then 59 ml of methanol, and then placed in a constant temperature bath at 105°C and dried for 1 hour.

The dry powder was then crosslinked in the same manner as in Example 10,
This was followed by trimethylsilylation.

A packed column was prepared from the above powder in the same manner as in Example 1,
A chromatogram was obtained in the same manner as in Example 4 above.

The retention time and number of theoretical plates for each peak were as follows.

Example: A spherical silica gel powder Log having approximately 100 pores and an average particle size of 5 μm and 2 g of a cyclic silicone compound [formula %] were placed in separate containers and placed in the same desiccator. The mixture was sealed and placed in a constant temperature bath at 80° C., and left for 7 hours. The cyclic silicone compound was brought into contact with the silica gel powder in a gas phase in a desiccator to cause surface polymerization. Next, remove the silica gel powder container from the desiccator,
It was heated at 105° C. for 1 hour in a constant temperature bath. After 6, 300m7 of powder! 1 mg of tri-n-octylmethylammonium salt of chloroplatinic acid as a catalyst and 5Qmn of 1-octadecene were added thereto, and the mixture was heated under reflux at 120° C. in an oil bath for 5 hours. Next, it was filtered using a glass filter (G-4), and then 100 m of chloroform was added, followed by 50 m of methanol.
After washing and filtering with 1 liter of water, the mixture was placed in a constant temperature bath at 105° C. and dried for 1 hour.

Next, the dry powder was crosslinked in the same manner as in Example 10,
This was followed by trimethylsilylation.

A packed column was prepared from the above powder in the same manner as in Example 1, and a chromatogram was obtained in the same manner as in Example 4. The retention time and number of theoretical plates for each peak were as follows.

10 g of spherical silica gel powder having approximately 100 pores and an average particle size of 5 μm and a linear silicone compound [in formula (I), R1-R4=R5=R6-CH3, a-3-1
0, b=o, and C=2 in separate containers, put them in the same desiccator, seal them, and heat them at 100°C.
The mixture was placed in a constant temperature bath and left to stand for 16 hours, and the linear silicone compound was brought into contact with the silica gel powder in a gas phase in a desiccator to cause surface polymerization. Subsequently, the silica gel powder container was taken out from the desiccator and heated at 105° C. for 1 hour in a constant temperature bath. After 6 days, the powder was placed in a 300 rrl eggplant-shaped flask, and 1 m'g of tri-n-octylmethylammonium salt of chloroplatinic acid as a catalyst and 50 mJ of 1-octadecene were added thereto, and the mixture was heated under reflux in a water bath for 5 hours. . Next, it was filtered using a glass filter (G-4), and 100 ml of chloroform was added! Then, after washing and filtering with 50 methanol of methanol, it was placed in a constant temperature bath at 105 °C.
Let dry for an hour.

The dry powder was then crosslinked in the same manner as in Example 10,
This was followed by trimethylsilylation.

A packed column was prepared from the above powder in the same manner as in Example 1,
A chromatogram was obtained in the same manner as in Example 4 above.

The retention time and number of theoretical plates for each peak were as follows.

Spherical silica gel powder with approximately 100 pores and an average particle size of 51zm Log 300m7! Add 100 m# of hexane and a linear silicone compound [formula (I) to a beaker.
), r? '=I? '=R5=R6=CH3
, a=20-40. . After 6,
300+n7 powder! The mixture was placed in a glue flask, and 1 mg of tri-n-octylmethylammonium salt of chloroplatinic acid as a catalyst and 50 ml of l-octene were added thereto, and the mixture was heated under reflux in a water bath for 5 hours. Next, filter using a glass filter (G-4), and then chloroform
00m/.

Next, methanol 59mJ! After washing and filtering with 105
It was placed in a constant temperature bath at ℃ and dried for 1 hour.

The dry powder was then crosslinked in the same manner as in Example 10,
This was followed by trimethylsilylation.

A packed column was prepared from the powder described above in the same manner as in Example 1, and a chromatogram was obtained in the same manner as in Example 4.

The retention time and number of theoretical plates for each peak were as follows.

10 g of crushed silica gel powder having about 50 pores and an average particle size of 10 μm and a linear silicone compound [in formula (1), R'"R' = CH3, a-1 to 3, b-1
~3, A = 3 ~ 5, C = 2) and 2 g of each in separate containers, put them in the same desiccator, seal them, put them in a thermostat at 100 ° C., leave them for 7 hours, and then put them in a desiccator. - A linear silicone compound was brought into contact with the silica gel powder in the gas phase to cause surface polymerization. Next, take out the silica gel container from the desiccator and place it in a thermostat at 105 ml.
Heated at ℃ for 1 hour. After 6 days, the powder was placed in a 300ml eggplant-shaped flask, and 1mg of tri-n-octylmethylammonium salt of chloroplatinic acid as a catalyst and 1-
5 Qrrl of octadecene was added and heated under reflux in a water bath for 5 hours. Next, it was filtered using a glass filter (G-4), washed and filtered with 100 rrl of chloroform and then 5 QmA of methanol, and then placed in a constant temperature bath at 105°C and dried for 1 hour.

The dry powder was then crosslinked in the same manner as in Example 10,
This was followed by trimethylsilylation.

A packed column was prepared from the above powder in the same manner as in Example 1,
A chromatogram was obtained in the same manner as in Example 4 above.

The retention time and number of theoretical plates for each peak were as follows.

1 kg of crushed silica gel powder with approximately 120 pores and a particle size of 25 to 44 μm and a linear silicone compound [formula (
In 1), RI = R4 = R5 = R6 = CH
,, a-1 to 3, b-1 to 3, a+b=3 to 5, C=2
200g of each sample) were placed in separate containers, placed in the same large desiccator, sealed tightly, placed in a constant temperature bath at 80°C, and left for 16 hours. It was brought into contact with the powder and surface polymerized. Subsequently, the silica gel powder container was taken out from the desiccator and heated at 105° C. for 3 hours in a constant temperature bath.

After 6 hours, the powder was placed in a 51 round bottom flask, and tri-n-octylmethylammonium salt of chloroplatinic acid as a catalyst and 1-octene 21 were added thereto, and the mixture was heated under reflux in a bath for 5 hours. Next, use a glass filter ((, −
4), and then chloroform (5) followed by methanol (17!). After washing and filtering, the mixture was placed in a constant temperature bath at 105°C and dried for 1 hour.

Next, add 57 dry powders! 28% ammonia water 0.2/methanol and methanol 1.81%
In addition, the mixture was heated under reflux in a water bath for 5 hours. Next, filter using a glass filter (G-4), followed by methanol 11
After washing and filtering, the mixture was placed in a constant temperature bath at 105°C and dried for 3 hours.

The dry powder was then taken into a 5 Il round bottom flask and added with too g of trimethylchlorosilane, 200 g of hexamethyldisilazane and 1.8 j of pyridine! was added and heated under reflux in a water bath for 4 hours. After 6 hours, 2j+ of water was added and the mixture was filtered using a glass filter (G-4), washed and filtered with 17.5 methanol, and then placed in a constant temperature bath at 120°C for 3 hours to dry.

750g of the obtained powder and a stainless steel power ram (
A packed column (with an inner diameter of 5 cm and a length of 50 cm) was prepared in the same manner as in Example 1 above. Connect the zero column to a preparative liquid chromatograph and use 85% methanol as the mobile phase at 100ml/min! flushed with water, injected with a standard mixture of methyl benzoate and toluene, and detected at 254 nm using a UV detector.
Detection was performed and a chromatogram was obtained. As a result, the retention time and number of theoretical plates for each peak were as follows.

Take 10 g of crushed silica gel powder with approximately 100 pores and an average particle size of 5 μm in a 300 ml beaker, and add 100 ml of hexane to it! and a linear silicone compound [formula (1
), R1=R4=R5=R6=CH,, a=
80-100, b = O, c = 2] 4
After adding g and volatilizing the hexane on a water bath while stirring, the mixture was placed in a constant temperature bath at 100° C. and heated for 10 hours.

After 6 hours, 200 m# of 0.0 IN sodium hydroxide/acetonitrile mixture (2:1) was added to the powder, the powder was dispersed, and heated on a water bath for 2 hours.

Next, it is filtered using a glass filter (G-4), and the water/acetonitrile mixture (2
: After washing and filtering in step 1), place in a thermostat at 105°C.
Dry for an hour.

The dried powder was then trimethylsilylated in the same manner as in Example 10 above.

A packed column was prepared from the above powder in the same manner as in Example 1,
A chromatogram was obtained in the same manner as in Example 2 above. The retention time and number of theoretical plates for each peak were as follows.

10 g of spherical silica gel powder with approximately 100 pores and an average particle size of 10 μm was placed in a 300 ml beaker, and 100 m of hexane and a linear silicone compound [formula (1)
In, R1=R4=R5=R6-C4H9, a=
3 to 10, b = o, c = 217)] and evaporated hexane on a water bath while stirring,
It was placed in a constant temperature bath at 100°C and heated for 10 hours.

The dry powder was then crosslinked in the same manner as in Example 10,
This was followed by trimethylsilylation.

A packed column was prepared from the above powder in the same manner as in Example 1,
A chromatogram was obtained in the same manner as in Example 2 above. The retention time and number of theoretical plates for each peak were as follows.

〔Effect of the invention〕

The packing material for liquid chromatography obtained by the present invention has various superior properties compared to conventional chemically bonded phase reversible liquid chromatography packing material.

That is, in conventional chemically bonded fillers, as described above, residual Si-01l groups exist in an amount of about 10 to 20%, which greatly affects the elution of polar substances (particularly basic substances). On the other hand, the filler obtained by the present invention is a resin capsule type, and the Si-OH group is completely wrapped inside the capsule, so the influence of the Si-011 group can be substantially eliminated. I can do it.

Furthermore, the tailing phenomenon during elution of polar substances, which is a drawback of conventional chemically bonded packing materials, can be prevented.

In addition, the packing material according to the present invention accounts for about 80% of the usage rate in conventional reversed-phase liquid chromatography columns, and is used in CI8 type and G
Compared to the o type, it shows similar retention and separation power.

In addition, since the silica gel is covered with a uniform silicone polymer film, the Raikō tensile agent has particularly strong alkali resistance.
It can be used for a long time between pH 2 and 12.

Hereinafter, the effects of the filler according to the present invention will be specifically explained using comparative examples, but this is not intended to limit the technical scope of the present invention.

This example compared the retention and separation power of the packing according to the present invention and a conventional CI8 type packing.

The packed column prepared in Example 6 and the packed column prepared in Example 5 were prepared.

A commercially available column from Company N filled with conventional ODS silica gel (C+e type) packing was used as a control.

Each of the above columns was connected to a high-performance liquid chromatograph, flowing 70% methanol as the mobile phase at 1 ml per minute, injecting a standard mixture of uracil, methyl benzoate, toluene, and naphthalene, and using a UV detector at 254 nm. Detection was performed and a chromatogram was obtained. Figure 1 shows the conventional ODS
FIG. 2 shows a chromatogram using the packed column obtained in Example 6 of the present invention, and FIG. 3 shows a chromatogram using the packed column obtained in Example 5 of the present invention. In Figures 1 to 3,
■ indicates the peaks of uracil, ■ indicates the peaks of methyl benzoate, ■ indicates the peaks of toluene, and ■ indicates the peaks of naphthalene. A comparison between FIG. 1 and FIG. 2 shows that the packed column obtained in Example 6 of the present invention has almost the same retention power as the conventional chemically bonded column, and has almost the same separation ability. Further, the packed column of Example 5 shown in FIG. 3 had a slightly lower retention power than the above-mentioned column in the same mobile phase solvent, but it was comparable to the retention power of the chemically bonded CII type.

This example compares the influence of the St-011 group on the resin capsule type photoresist according to the present invention and the conventional chemically bonded filler.

Examples 5, 6, 10, and 1 as fillers of the present invention
2, the fillers prepared in Example 13 and Example 15 were used. As a control, 10 types of commercially available packed columns filled with conventional chemically bonded packing materials were used. For each filler, trimethylsilylation (TM
The results are shown in Table 1 below, together with the presence or absence of S conversion) treatment. As with each commercially available column, 3 g of each packing according to the invention was added to a stainless steel column (4.6 N internal diameter and 25 cm long).
n) by an equilibrium slurry method to prepare a packed column. Each column was connected to a high performance liquid chromatograph, 15% acetonitrile was passed through the column as a mobile phase at a flow rate of 1 ml/min, and a pyridine/phenol test was performed at a chart speed of 5711 tVI min. The pyridine/phenol test is a test in which a mixture of pyridine and phenol is analyzed using high-performance liquid chromatography, and from the respective retention times (T, l), TI (pyridine)/TR
(phenol) value, and the larger the value exceeds 1, the more Si-Oil groups remain, and the greater the influence on polar substances.

At the same time, the degree of tailing of the pyridine elution peak was
The evaluation was divided into 5 grades starting from the largest, and the results are shown in Table 1. In addition, the results of both the pyridine/phenol test and the tailing of the pyridine elution peak were comprehensively evaluated in three stages: 8, B, and C, and are shown in Table 1. As a result, the capsule-type reversed-phase liquid chromatographic filler according to the present invention has very little influence from the Si-〇 group and has excellent performance compared to commercially available chemically bonded fillers. This has been proven.

Margin Table 1 This example compares the alkali resistance of the resin capsule type photoresist according to the present invention and the conventional chemically bonded type photoresist.

The fillers prepared in Examples 10, 12, 13, and 15 were used as the fillers of the present invention. As a control, six types of commercially available 0DS-silica gel packed columns filled with conventional chemically bonded photoresistants were used. As with each commercially available column, 3 g of each packing according to the invention was added to a stainless steel column (inner diameter 4.
6 ms and length 25 cm) by the balanced slurry method to create a packed column. Each column was connected to a fully automatic high-performance liquid chromatograph, 70% methanol adjusted to pHlo with a Britton-Robinson bathophore was flowed at 1 mJ/min as a mobile phase, and a naphthalene standard was injected to obtain a chromatogram. This operation was repeated fully automatically to determine the continuous operation time at which the retention time of the naphthalene chromatogram peak was 2 minutes faster. It is said that when a commercially available chemically bonded photo(8I) column is run for a certain period of time at a pH of -8 or higher, the column gradually deteriorates and its retention capacity decreases.

The results are shown in Table 2. It has been demonstrated that the resin capsule-type photoresist packed column according to the present invention can withstand much longer continuous operation and has better alkali resistance than commercially available photoresist columns.

Margin below Table 2

[Brief explanation of drawings]

FIG. 1 is a chromatogram using a conventional chemically bonded photostimulant, and FIGS. 2 and 3 are chromatograms using a resin capsule photosensitive agent of the present invention. In Figures 1 to 3, ■ is uracil, ■ is methyl benzoate,
■ indicates the toluene peak and ■ indicates the naphthalene peak.

Claims (1)

[Claims] 1. (a) General formula (R^1HSiO)a(R^2R^3SiO)b(R^
4R^5R^6SiO_1_/_2)c(I) (wherein R^1, R^2 and R^3 are each independently a carbon atom 1 which may be substituted with at least one halogen atom) ~10 hydrocarbon groups, and R^4,
R^5 and R^6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with at least one halogen atom, and a
is an integer of 0 or 1 or more, b is an integer of 0 or 1 or more, c is 0 or 2, and a, b, and c
(The sum of 3 to 300) is brought into contact with the powder and the silicone compound is polymerized on substantially the entire surface of the powder; b) Packing for liquid chromatography consisting of a powder carrying a silicone polymer film on substantially the entire surface, produced by a method consisting of each step of crosslinking unreacted Si-H groups in the presence of a catalyst. agent. 2. (c) A small amount of Si generated during the step (b)
The packing material for liquid chromatography according to claim 1, which is produced by a method further comprising the step of trimethylsilylating the -OH group with a trimethylsilylating agent. 3. General formula [(R^1SiO_3_/_2) x (R^1HSiO)
y]t(II) (wherein R^1 is a hydrocarbon group having 1 to 10 carbon atoms that may be substituted with at least one halogen atom, and t is a weight average molecular weight of 150,00
is an integer greater than or equal to 0, and x and y are x+y=
1 and 0.6≦x≦1) A packing material for liquid chromatography comprising a powder having a silicone polymer film supported on substantially the entire surface thereof. 4, (a) General formula (R^1HSiO)a(R^2R^3SiO)b(R^
4R^5R^6SiO_1_/_2)c(I) (wherein R^1, R^2 and R^3 are each independently a carbon atom 1 which may be substituted with at least one halogen atom) ~10 hydrocarbon groups, and R^4,
R^5 and R^6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with at least one halogen atom, and a
is an integer of 0 or 1 or more, b is an integer of 0 or 1 or more, c is 0 or 2, and a, b, and c
(The sum of 3 to 300) is brought into contact with the powder and the silicone compound is polymerized on substantially the entire surface of the powder; b) A liquid consisting of a powder carrying a film of silicone polymer on substantially its entire surface, produced by a process comprising the steps of adding a vinyl compound of up to 40 carbon atoms to unreacted Si-H groups. Packing material for chromatography. 5. The liquid packing material for chromatography according to claim 4, which is produced by a method further comprising the step of (c) crosslinking remaining unreacted Si-H groups in the presence of a catalyst. 6. (d) A small amount of Si generated during the step (c)
The packing material for liquid chromatography according to claim 5, which is produced by a method further comprising the step of trimethylsilylating the -OH group with a trimethylsilylating agent. 7. General formula [(R^1SiO_3_/_2)x'(R^1HSiO
)y'(R^1R^7SiO)z]u(III) (in the formula,
R^1 is a hydrocarbon group having 1 to 10 carbon atoms that may be substituted with at least one halogen atom;
^7 is a hydrocarbon group of up to 42 carbon atoms, u is an integer that makes the weight average molecular weight 150,000 or more,
And x', y' and z are numbers that satisfy the following relationships: x'+y'+z=1, 0≦x'≦0.5, 0≦y'≦0.4 and 0.5≦z≦1.0 A packing material for liquid chromatography consisting of a powder having a silicone polymer film supported on substantially the entire surface thereof.