JP2005536719A - Adsorbing material and method for preparing adsorbing material - Google Patents

Abstract

【the purpose】
The present invention relates to an adsorption material for chromatography containing a polymer fixed to a support, and the polymer main chain is attached to the support by one or more bonds containing one or more amide groups. . The present invention also relates to a method for preparing an adsorbent material for chromatography in which a support is reacted with a polymer.

Description

  The present invention relates to an adsorbent material. The present invention also relates to a method for preparing an adsorbent material and the use of the adsorbent material in a chromatographic separation method.

  When using chromatography to separate individual chemical compounds present in a mixture, the choice of stationary phase is important to obtain good decomposition of the compounds, ie, good separation. There are a variety of stationary phases that can be utilized, which have different affinities for different compounds. More specifically, it is usually the surface of the stationary phase that interacts with the components of the mobile phase in the desired manner, ie, the stationary phase acts as an adsorbent material.

  Silica or other inorganic oxides can be used as a base for the stationary phase in chromatography. In order to functionalize the support material, certain organic compounds may be attached to the surface, for example by reaction with silanol groups on the silica surface. By varying the compound bound to the surface, various chromatographic behaviors are obtained. However, silica and other inorganic oxides may begin to dissolve at high pH and can result in leakage of inorganic materials, commonly referred to as inorganic leakage. It is important to cover as much of the support surface as possible to avoid inorganic leakage. The support is preferably a porous material having pores of various sizes. The major part of the surface area of the support material is the area within the pores. It is therefore important that this part is coated with, for example, a polymer to avoid inorganic leakage and to obtain good degradation.

  The chromatographic stability of the adsorbent material is also an important factor. Chromatographic stability means herein the ability of an adsorbent material to retain its selectivity and retention over the period of use.

Alternatively, the polymer may be attached to the support surface by first attaching the monomer to the support surface followed by further polymerization. H. Engelhardt et al., Chemically Modified Surfaces, Proc. Symp 4 ^th , Elsevier, 1992, 225-241, discloses a method of coating a solid support in which vinylsilane is bound to a silica surface and subsequently shared Copolymerization of acrylamide to the vinyl group of the bound vinyl silane is carried out. However, this results in a predominantly tentacle-type coating in which most polymer chains are attached in a single position, with each polymer chain extending as a “tentacle” from the support and unstable both chemically and mechanically. Causes adhesion. In general, the chemical bond between the coating and eg silica is often unstable, especially at low pH, which can lead to leakage of organic materials, commonly referred to as organic leakage. Also, when vinyl monomers are polymerized on a solid support, the remaining monomers can be present on the support surface, resulting in chemical instability. Alternatively, the pre-generated polymer may be attached to the support surface at a number of locations. WO 98/27418 A1 discloses a method for coating a silica support by first coupling a coupling agent to the support surface and then bonding a pre-formed polymer to the coupling agent. The preformed polymer contains fully saturated carbon chains with leaving groups. It is a fairly complex method that requires several process steps. Kurganov et al., Journal of Chromatography 261 (1983) 223-233 discloses a method for bonding a copolymer of styrene and methylvinyldimethoxysilane to the surface of silica. However, the reactivity of methylvinyldimethoxysilane is very low with respect to styrene, which favors the homopolymerization of styrene and results in only a few silane monomer moieties in the copolymer, thereby disadvantageously reducing the number of bonds to silica. Will affect. Alternatively, chloromethylated polystyrene is reacted with aminopropyltriethoxysilane and then bonded to the surface of the silica. However, the basic nitrogen in the amino group in the spacer between the polymer backbone and silica is not an inert group and may participate in undesirable reactions. U.S. Pat. No. 4,914,159 discloses a method for immobilizing copolymers of acrylamide and methacrylamide on silica gel. Acrylamide (or methacrylamide) monomers are copolymerized with a silylating agent such as methacryloyloxypropyltrimethoxysilane.

  There is a further need for improved adsorbent materials and improved methods of coating solid supports to produce adsorbent materials. The object of the present invention is therefore to provide a chromatographic adsorbing material with high chromatographic stability, which results in an excellent decomposition of the chemical compounds to be separated from the mixture and of the solid support. Has a high degree of surface coverage. It is a further object of the present invention to provide a method for the preparation of an adsorbent material for chromatography, the method comprising several steps, resulting in an adsorbent material having a high surface coverage of a solid support, and different. Allows flexibility in providing adsorbent materials with chromatographic behavior.

  In accordance with the present invention, an adsorbent material for chromatography can be provided that has chromatographic stability, has a high degree of coating of the support, provides excellent degradation, and can be customized to the desired separation characteristics. It was surprisingly found. The chromatographic adsorbent material comprises a polymer immobilized on a support, the polymer backbone of which is attached to the support by one or more bonds comprising one or more amide groups.

  Furthermore, the present invention includes a method for preparing an adsorptive material for chromatography comprising immobilizing a polymer to a support, wherein the support is reacted with the polymer, whereby one or more between the polymer backbone and the support. Wherein each bond contains one or more amide groups. Furthermore, the present invention provides for a chromatography comprising obtaining a polymer from a monomer mixture comprising an amide group-containing silane and reacting the polymer with a support to form one or more bonds between the polymer backbone and the support. A method for preparing the adsorbent material. In both methods of the invention it is preferred that the polymer is added as a solution to the suspension of the support. Suitably the support is filtered off, washed and dried. It is preferred that a further acid treatment step is also performed, followed by an end-capping step, in which an end-capping agent such as chloro-trimethylsilane, hexamethyldisilazane or (N , N-dimethylamino) -trimethylsilane is added to the support.

  Furthermore, the present invention includes the use of chromatographic adsorbent materials in chromatographic separation methods. The present invention also includes the use of a chromatographic adsorbent material prepared according to any of the methods of the present invention in a chromatographic separation method. Such chromatographic separation methods may be, for example, HPLC, supercritical fluid chromatography (SFC), and simulated moving bed (SMB).

  The present invention further includes a method for separating a chemical compound from a mixture comprising contacting the mixture with the chromatographic adsorbent material of the present invention.

The support material of the present invention is preferably a material whose surface contains groups that are susceptible to reaction with polymer groups. The support material may be an organic material or an inorganic material. Organic support materials include polymer support materials such as poly (styrene-divinylbenzene), polyacrylate resins and polyacrylamide resins. Organic support materials, eg, polymer support materials, are functionalized to contain groups that are susceptible to reaction with the polymer to be immobilized on the support, eg, hydroxyl groups, halogen groups, amino groups, or vinyl groups. Is preferred. An inorganic oxide is mentioned as an inorganic support material. The surface of the inorganic support material preferably contains hydroxyl groups or groups that can be converted to hydroxyl groups. The support is preferably an inorganic support and is preferably an inorganic oxide such as alumina, titania, zirconia, chromia, silica, boria, tria, beryllia, silica-alumina and combinations thereof. Most preferably, the support is silica. The support material may be a particulate material or, in the form of a piece, a sheet, rod or capillary coating. The support is preferably a particulate material having a volume average particle size suitably from about 0.5 μm to about 500 μm, preferably from about 0.7 μm to about 200 μm, and most preferably from about 1 μm to about 40 μm. The particles are preferably substantially spherical. The particulate material preferably includes pores. The pore size, pore volume and specific surface area of the particulate support material will vary depending on the type of support material used, the properties of the polymer to be bound to the support and the desired separation characteristics when in use. May be. The pore size range may be different for diffusion pores and for perfusion pores (flow pores). For diffusion pores, the pore size is suitably from about 20 to about 4000, and preferably from about 50 to about 500. For perfusion pores, the pore size is suitably from about 1000 to about 80,000, preferably from about 5000 to about 50,000. The pore volume is suitably from about 0.1 ml / g to about 4 ml / g, preferably from about 0.3 ml / g to about 2 ml / g, most preferably from about 0.5 ml / g to about 1.5 ml / g. . The specific surface area is suitably from about 1 m ² / g to about 1000 m ² / g, preferably from about 25 m ² / g to about 700 m ² / g, most preferably from about 100 m ² / g to about 500 m ² / g. is there.

  The polymer of the present invention preferably contains groups that are susceptible to reaction with the support. Such groups include, for example, vinyl groups, alkoxy groups such as methoxy, ethoxy, propoxy, butoxy and isobutoxy, halogens such as chlorine, bromine, iodine and fluorine, secondary amino groups such as dialkylamine, imidazole It may be a group, a morpholine group, or an azide group. Suitably the polymer is a preformed polymer, preferably a copolymer. The polymer has the general formula (I):

（式中、Ａはハロゲン、ビニル基、又はシラン基であり、ｘは1-30であり、R₁は水素又はC₁-C₄アルキルであり、かつR₂は水素又はメチルである）
の少なくとも一種のビニルモノマーm₁を含むモノマー混合物を重合することにより調製されることが好適である。モノマー混合物は一般式(II)：

(Wherein A is a halogen, vinyl group, or silane group, x is 1-30, R ₁ is hydrogen or C ₁ -C ₄ alkyl, and R ₂ is hydrogen or methyl)
It is preferable to be prepared by polymerizing a monomer mixture comprising at least one vinyl monomer m ₁ of. The monomer mixture has the general formula (II):

（式中、R₅は水素又はメチルであり、かつＥは基：

Wherein R ₅ is hydrogen or methyl and E is a group:

又は
R₇-O-のいずれかであり、
ｍは０から20までであり、R₆は水素又はC₁-C₄アルキルであり、かつR₇は完成吸着材料の所望の分離特性を生じるように選ばれた官能性部分である）
の少なくとも一種のビニルモノマーm₂を更に含むことが好適である。所望の分離特性は、関係する特定の化学化合物とその他の化合物の間の或る分解が得られることを本明細書では意味する。R₇を変えることにより、或る化学化合物に対する吸着材料のアフィニティーが異なるであろう。例えば、疎水性相互作用、双極子-双極子相互作用、π-π相互作用、静電相互作用、及び立体的相互作用の如き性質、又はキラル識別が変化し得る。官能性部分R₇は広い制限内で変化され、例えば、水素、C₁-C₃₀アルキル、C₁-C₃₀ヒドロキシアルキル、フェニル、ベンジル、カルボキシル、C₁-C₃₀アルキルカルボキシル、フェニルカルボキシル、ニトロフェニル、クロロフェニル、C₁-C₃₀アミノアルキル、アミノフェニル、-N(Me)₃ ⁺Cl^-、及び-N(Me)₂(CH₂)_pSO₃（式中、p=0-5）であってもよい。R₇がC₁-C₃₀アルキル、C₁-C₃₀ヒドロキシアルキル、C₁-C₃₀アルキルカルボキシル、及びC₁-C₃₀アミノアルキルのいずれかである場合、C₁-C₁₀アルキル、C₁-C₁₀ヒドロキシアルキル、C₁-C₁₀アルキルカルボキシル、及びC₁-C₁₀アミノアルキルが使用されることが好ましく、C₁-C₅アルキル、C₁-C₅ヒドロキシアルキル、C₁-C₅アルキルカルボキシル、及びC₁-C₅アミノアルキルが最も好ましい。モノマー混合物は一般式(III)：

Or
R ₇ -O-
m is from 0 to 20, R ₆ is hydrogen or C ₁ -C ₄ alkyl, and R ₇ is a functional moiety selected to produce the desired separation properties of the finished adsorbent material)
It is preferable that at least one vinyl monomer m ₂ is further contained. The desired separation characteristic means herein that some degradation between the particular chemical compound concerned and other compounds is obtained. By varying the R _7, affinity of the adsorbent material will be different for certain chemical compounds. For example, properties such as hydrophobic interactions, dipole-dipole interactions, π-π interactions, electrostatic interactions, and steric interactions, or chiral discrimination can be altered. The functional moiety R ₇ is varied within wide limits, for example hydrogen, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ hydroxyalkyl, phenyl, benzyl, carboxyl, C ₁ -C ₃₀ alkyl carboxyl, phenyl carboxyl, nitro Phenyl, chlorophenyl, C ₁ -C ₃₀ aminoalkyl, aminophenyl, —N (Me) ₃ ⁺ Cl ⁻ , and —N (Me) ₂ (CH ₂ ) _p SO ₃ (where p = 0-5) There may be. When R ₇ is any of C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ hydroxyalkyl, C ₁ -C ₃₀ alkyl carboxyl, and C ₁ -C ₃₀ aminoalkyl, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ hydroxyalkyl, C ₁ -C ₁₀ alkyl carboxyl, and C ₁ -C ₁₀ is preferably aminoalkyl is used, C ₁ -C ₅ alkyl, C ₁ -C ₅ hydroxyalkyl, C ₁ -C ₅ Alkyl carboxyl and C ₁ -C ₅ aminoalkyl are most preferred. The monomer mixture has the general formula (III):

（式中、ｎは１から20までであり、R₈は水素又はメチルであり、R₉はC₁-C₄アルキルであり、R₁₀はC₁-C₄アルキルであり、かつR₁₁は水素又はメチルである）
の少なくとも一種のビニルモノマーm₃を更に含むことが好適である。

Wherein n is from 1 to 20, R ₈ is hydrogen or methyl, R ₉ is C ₁ -C ₄ alkyl, R ₁₀ is C ₁ -C ₄ alkyl, and R ₁₁ is Hydrogen or methyl)
It is preferable to further contain at least one vinyl monomer m ₃ of.

In order for the polymer to be fixed to the inorganic support material, m ₁ is preferably a monomer containing a silane group. The silane group has the general formula (IV):
(B) _y (D) _3-y Si- (IV)
Wherein B is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, hydroxyl, hydrogen, -N (R ₃ ) _z (R ₄ ) _2-z , an imidazole group, a morpholine group, or an azide group D is C ₁ -C ₄ alkyl, y is 1-3, z is 1-2, and R ₃ and R ₄ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, or aryl. Is)
Is preferable. Preferred monomers m ₁ acrylamide alkylalkoxysilane, methacrylamide alkylalkoxysilanes, for example, acrylamide propyl trimethoxy silane, methacrylamide propyl trimethoxy silane, acrylamide propyl dimethoxy methyl silane, methacrylamide propyl dimethoxy methyl silane, acrylamide pyro pills dimethoxy triethylsilane , Methacrylamidopropyldimethoxyethylsilane, acrylamidopropyl-monomethoxydimethylsilane, methacrylamidopropyl-monomethoxydimethylsilane, acrylamidepropylmonomethoxydiethylsilane, methacrylamidopropylmonomethoxydiethylsilane, acrylamidopropyltriethoxysilane, methacrylamidepropyltrie Toki Silane, acrylamidopropyldiethoxymethylsilane, methacrylamidopropyldiethoxymethylsilane, acrylamidopropyldiethoxyethylsilane, methacrylamidopropyldiethoxyethylsilane, acrylamidopropylmonoethoxydimethylsilane, methacrylamidopropylmonoethoxydimethylsilane, acrylamidopropylmono Ethoxydiethylsilane, methacrylamidopropylmonoethoxydiethylsilane, acrylamidobutyl-trimethoxy-silane, methacrylamidobutyl-trimethoxy-silane, acrylamidobutyldimethoxymethylsilane, methacrylamidobutyldimethoxymethylsilane, acrylamidobutyldimethoxyethylsilane, methacrylamidobutyldimethoxy Ethylsilane, Kurylamidobutyl monomethoxydimethylsilane, methacrylamide butylmonomethoxydimethylsilane, acrylamide butylmonomethoxydiethylsilane, methacrylamide butylmonomethoxydiethylsilane, acrylamide butyltriethoxysilane, methacrylamide butyltriethoxysilane, acrylamide butyldiethoxymethylsilane , Methacrylamidobutyldiethoxymethylsilane, acrylamidobutyl-diethoxyethylsilane, methacrylamidobutyl-diethoxyethylsilane, acrylamidebutylmonoethoxydimethylsilane, methacrylamidobutylmonoethoxydimethylsilane, acrylamidobutylmonoethoxydiethylsilane, methacrylamide Butyl monoethoxydiethylsilane, acrylic amine Alkylaminosilanes, methacrylamide alkylaminosilanes such as acrylamide dimethylaminosilane, methacrylamide dimethylaminosilane, and acrylamide diethylaminosilane, methacrylamide diethylaminosilane, acrylamide alkylhalogen silanes, methacrylamide alkylhalogen silanes such as acrylamide dimethylchlorosilane, methacrylamide dimethylchlorosilane , Acrylamide diethyl chlorosilane, methacrylamide dimethyl silane, acrylamide dipropyl chloro silane, methacrylamide dipropyl chloro silane, acrylamide methyl dichloro silane, methacrylamide methyl dichloro silane, acrylamide ethyl dichloro silane, methacrylamide ethyl Chlorosilanes, and acrylamide - propyl dichlorosilane, methacrylamide - propyl dichlorosilane.

Examples of preferred acrylamide and methacrylamide monomers m ₂ are functionalized or unfunctionalized C ₁ -C ₃₀ alkyl butyl acrylamide, C ₁ -C ₃₀ alkyl butyl methacrylamide, eg propyl acrylamide, propyl Methacrylamide, isopropylacrylamide, isopropylmethacrylamide, butylacrylamide, butylmethacrylamide, tert-butylacrylamide, tert-butylmethacrylamide, pentylacrylamide, pentylmethacrylamide, hexylacrylamide, hexylmethacrylamide, heptylacrylamide, heptylmethacrylamide, octyl Acrylamide, octyl methacrylamide, nonyl acrylamide, nonyl methacrylamide, decyl acrylamide, decyl meta Kurylamide, octadecylacrylamide, and octadecylmethacrylamide.

Examples of preferred monomers m ₃ are bis-acrylamides, such as N, N′-ethylene bis-acrylamide, N, N′-propylene bis-acrylamide, and N, N′-butylene bis-acrylamide.

The monomers, m ₁ , m ₂ and m ₃ are preferably chosen so that a random distribution of the monomers in the polymer is obtained.

The polymer suitably comprises from about 1 mol% to about 100 mol%, preferably from about 10 mol% to about 90 mol%, most preferably from about 30 mol% to about 70 mol% units of monomer m _3. . Further, from 0 mole% to about 99 mol% it is suitably a polymer, preferably from about 10 mole% to about 90 mole%, and most preferably in unit of monomer m ₂ from about 30 mole% to about 70 mole% Including. Further, the polymer suitably comprises from 0 mol% to about 99 mol%, preferably from 0 mol% to about 50 mol% of monomer m ₃ units.

  The weight average molecular weight of the polymer is suitably from about 1000 g / mole to about 500,000 g / mole, preferably from about 1500 g / mole to about 100,000 g / mole, most preferably from about 2000 g / mole to about 25000 g / mole.

  The number of monomer units per polymer chain is suitably from about 5 to about 2000, preferably from about 8 to about 500, and most preferably from about 10 to about 100.

  The polymer is preferably prepared by polymerizing the monomer in an organic solvent in the presence of an initiator and optionally a chain transfer agent such as a mercapto compound. The solvent may be any organic solvent suitable as a polymerization medium and includes xylene, toluene, dioxane, tetrahydrofuran, chlorinated hydrocarbons, benzene, dimethylformamide, and N-methylpyrrolidone. Examples of suitable initiators include peroxides and azo compounds.

  Suitably the polymers of the present invention are covalently bonded to a support material.

  In a preferred embodiment of the invention, a preformed polymer (which is a copolymer of an acrylamide monomer containing silane and alkoxy groups and a further acrylamide monomer) is covalently bonded to the surface of the silica particles.

Suitably the polymer is reacted with the support material by preparing a mixture of the polymer with a solution of the support material from a suspension of the support material in a solvent. The solvent used to suspend the support material is preferably an organic solvent. Suitably, the amount of support material added to the solvent is from about 0.01 g to about 1 g per ml of solvent, preferably from about 0.05 g to about 0.5 g per ml of solvent. The amount of polymer added to the support material is a measure of the degree of surface coverage of the support material. The amount of polymer added to the support, calculated as the monomer in the polymer, is suitably from about 0.5 μmol to about 20 μmol of monomer per 1 m ² of support material surface, preferably 1 m ^{2 of} support material surface. monomers from about 1μ mole to about 15μ moles per, more preferably monomers from about 4μ mol to about 12μ moles per support material surface 1 m ^2, and most preferably about 10μ moles to about 6μ moles per support material surface 1 m ² Up to monomer. If the support material contains pores, the amount of polymer added to the support material may also depend on the pore size of the support material. Diffusion pores having a pore size of from 20Å to 150 Å, calculated as a monomer in the polymer, the amount of polymer added to the support material is about 10μ moles to about 3μ moles per support material surface 1 m ² It is preferable that it is a monomer up to. For diffusion pores having pore sizes from above 150 to 250 cm, the amount of polymer added to the support material, calculated as a monomer in the polymer, is about 5 μmol to about about 5 μmol / m ^{2 of} support material surface. Monomers up to 12 μmol are preferred. For diffusion pores having a pore size from above 250 cm to 500 mm, the amount of polymer added to the support material, calculated as a monomer in the polymer, is about 7 μmol / m ^{2 to} about 1 m ^{2 of the} support material surface. Preference is given to monomers up to 15 μmol.

  The temperature during the reaction is suitably from about 10 ° C to about 200 ° C, preferably from about 50 ° C to about 160 ° C. The mixture is preferably kept under an inert atmosphere.

  The invention will now be further described with reference to the following examples, which should not be construed as limiting the scope of the invention.

Example
[Example 1]
N- (tri-methoxypropylsilyl) acrylamide 8.5 g and n-octylacrylamide 13.4 g were dissolved in xylene 65 ml. This solution was added to the reaction vessel along with a peroxide initiator dissolved in 45 ml of xylene. The polymerization was carried out at 140 ° C. for 7 hours under an inert atmosphere. The resulting polymer had a weight average molecular weight of 7000 daltons. The monomer conversion was 98% or more.

[Example 2]
4.0 g of Chromasil® type silica particles having a volume average particle size of 5 μm, a pore size of 100 mm, and a specific surface area of 330 m ² / g were suspended in 30 ml of xylene. 12 ml of the polymer solution of Example 1 was added and the mixture was left at 140 ° C. for 18 hours under an inert atmosphere. The particles were then filtered off, washed and dried. The particles were analyzed by elemental analysis and contained 13.7% carbon and 1.53% nitrogen, which corresponds to a coating of 4.5 μmol / m ² calculated as μmol / m ² monomer contained in the polymer. . The formula for calculating the surface coverage (for nitrogen-containing polymers) is 10 ⁶ / [(14x100xn _c − (N _c xM −N _c )) xS], where N _c is the measured nitrogen weight%, n _c is the number of nitrogen atoms in the monomer of the polymer which is bonded to the silica, M is the average molecular weight of one or more monomers contained in the polymer, and S is a specific surface area of the silica).

[Example 3]
The same procedure as in Example 2 was employed, but Chromasil® type silica particles having a volume average particle size of 5 μm, a pore size of 200 mm, and a specific surface area of 213 m ² / g were used. These particles were analyzed to contain 11.3% carbon and 1.285% nitrogen, which corresponds to a surface coverage of 5.2 μmol / m ² .

[Example 4]
The same procedure as in Example 2 was employed, but Chromasil® type silica particles having a volume average particle size of 5 μm, a pore size of 300 mm, and a specific surface area of 77 m ² / g were used. These particles were analyzed to contain 5.75% carbon and 0.735% nitrogen, which corresponds to a surface coating of 7.6 μmol / m ² .

[Example 5]
N- (monomethoxy-dimethyl-propylsilyl) acrylamide 5.5 g and isopropylacrylamide 6.2 g were dissolved in 100 ml of xylene. This solution was added to the reaction vessel along with a peroxide initiator dissolved in 45 ml of xylene. The polymerization was carried out at 140 ° C. for 7 hours under an inert atmosphere. The resulting polymer had a weight average molecular weight of 3400 daltons. The monomer conversion was 98% or more.

[Example 6]
N- (monomethoxy-dimethyl-propylsilyl) acrylamide 5.5 g and n-butylacrylamide 7.0 g were dissolved in 100 ml of xylene. This solution was added to the reaction vessel along with a peroxide initiator dissolved in 45 ml of xylene. The polymerization was carried out at 140 ° C. for 6 hours under an inert atmosphere. The resulting polymer had a weight average molecular weight of 2500 daltons. The monomer conversion was 98% or more.

[Example 7]
15 g of Chromasil® type silica particles having a volume average particle size of 5 μm, a pore size of 100 mm and a specific surface area of 330 m ² / g were suspended in 150 ml of a polymer solution prepared according to Example 5. . The mixture was left at 140 ° C. for 18 hours under an inert atmosphere. The particles were then filtered off, washed and dried. The particles are analyzed by elemental analysis and contain 17.6% carbon and 2.7% nitrogen, which corresponds to a coating of 7.6 μmol / m ² calculated as the monomer μmol / m ² contained in the polymer. .

[Example 8]
The same procedure as in Example 7 was adopted except that the polymer solution prepared according to Example 6 was used. The particles were analyzed by elemental analysis and contained 16.7% carbon and 2.5% nitrogen, which corresponds to a surface coating of 7.0 μmol / m ² calculated as μmol / m ² monomer contained in the polymer. To do.

Claims (15)

  An adsorption material for chromatography containing a polymer fixed to a support, wherein the polymer main chain is attached to the support by one or more bonds containing one or more amide groups. Adsorption material.   A method of preparing an adsorbent material for chromatography comprising immobilizing a polymer to a support, wherein the support is reacted with the polymer, thereby providing one or more bonds between the polymer backbone and the support. A method for preparing an adsorbent material for chromatography, characterized in that each bond comprises one or more amide groups.   A chromatographic method characterized by obtaining a polymer prepared from a monomer mixture containing silane-containing amide groups and reacting the polymer with a support to form one or more bonds between the polymer backbone and the support. A method for preparing an adsorbent material for lithography.   The adsorbent material according to claim 1, or the method according to claim 2, wherein the support is an inorganic oxide.   The adsorbent material according to claim 1, or the method according to claim 2, wherein the support is silica. The polymer is prepared by polymerizing a monomer mixture comprising at least one vinyl monomer m ₁ having easy groups and one or more amide groups undergo reaction with the support, one of claims 1 or 4 of 5 The adsorbent material according to claim 1 or the method according to any one of claims 2 to 5. The vinyl monomer m ₁ is represented by the general formula (I):

(Wherein A is a halogen, vinyl group, or silane group, x is 1-30, R ₁ is hydrogen or C ₁ -C ₄ alkyl, and R ₂ is hydrogen or methyl)
The adsorbent material according to claim 6, or the method according to claim 6. The silane group has the general formula (IV):
(B) _y (D) _3-y Si- (IV)
Wherein B is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, hydroxyl, hydrogen, -N (R ₃ ) _z (R ₄ ) _2-z , an imidazole group, a morpholine group, or an azide group D is C ₁ -C ₄ alkyl, y is 1-3, z is 1-2, and R ₃ and R ₄ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, or aryl. Is)
The adsorbent material according to claim 7, or the method according to claim 7. The monomer mixture has the general formula:

Wherein R ₅ is hydrogen or methyl and E is a group:

Or
R ₇ -O-
m is from 0 to 20, R ₆ is hydrogen or C ₁ -C ₄ alkyl, and R ₇ is a functional moiety selected to produce the desired separation properties of the finished adsorbent material)
Further comprising adsorption material according to any of claims 6 8, or method according to any of claims 6 8 at least one vinyl monomer m ₂ of. The monomer mixture is represented by the general formula (III):

Wherein n is from 1 to 20, R ₈ is hydrogen or methyl, R ₉ is hydrogen or C ₁ -C ₄ alkyl, R ₁₀ is hydrogen or C ₁ -C ₄ alkyl, And R ₁₁ is hydrogen or methyl)
Further comprising adsorption material according to any of claims 8 9, or method according to any of claims 8 9 of at least one vinyl monomer m ₃ of.   11. The adsorbent material according to any of claims 1 or 4 to 10, or the method according to any of claims 2 to 10, wherein the weight average molecular weight of the polymer is from about 2000 g / mole to about 25000 g / mole.   12. An adsorbent material according to any of claims 1 or 4 to 11, or a method according to any of claims 2 to 11, wherein the support has a volume average particle size of from about 1 [mu] m to about 40 [mu] m.   13. A method according to any of claims 2 to 12, wherein the polymer is added as a solution to a suspension of the support.   An adsorption material for chromatography obtained by the method according to claim 2.   Use of the adsorptive material for chromatography according to any of claims 1, 4 to 12 or 14 in a chromatographic separation method, or for chromatography prepared by a method according to any of claims 2 to 13. Adsorption material.