CN100579650C - Preparation method of bonding-affinity compound polysaccharide chiral stationary phase - Google Patents

Preparation method of bonding-affinity compound polysaccharide chiral stationary phase Download PDF

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CN100579650C
CN100579650C CN200710191730A CN200710191730A CN100579650C CN 100579650 C CN100579650 C CN 100579650C CN 200710191730 A CN200710191730 A CN 200710191730A CN 200710191730 A CN200710191730 A CN 200710191730A CN 100579650 C CN100579650 C CN 100579650C
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polysaccharide
stationary phase
bonding
chiral stationary
polysaccharide derivates
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CN101259406A (en
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刘晓宁
魏荣卿
张晓晓
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Nanjing Tech University
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Abstract

The invention relates to a preparation method of a bonding-affinity compound polysaccharide chiral stationary phase. The method is suitable for separation and preparation of chiral enantiomers by liquid chromatography, enlarges the application range of a mobile phase, and overcomes the defects of low chiral resolution capability of a bonded stationary phase and the like. The method is characterized by comprising the following main steps: 1) chemically bonding a polysaccharide derivative I on a chiral stationary phase substrate to obtain a bonded stationary phase; 2) and (3) coating the polysaccharide derivative II on the bonding stationary phase through affinity to obtain the bonding-affinity compound type polysaccharide chiral stationary phase.

Description

A kind of bonding-affinity composite type polysaccharides chiral is the preparation method of phase fixedly
Technical field
The present invention relates to a kind of preparation method of chiral stationary phase, is that a kind of bonding-affinity composite type polysaccharides chiral fixedly is combined to method specifically.
Background technology
Over nearly 20 years, the chiral structure compound is one of research focus of pharmacology and analytical chemistry always, the chiral resolution of enantiomter is the effective means that obtains the optical voidness material, and chiral chromatogram particularly chiral high performance liquid chromatography is the chiral separation method that develops rapidly in recent years.The core of chiral chromatogram is chiral stationary phase (CSPs), and it is strong therefore to design and develop recognition capability, and load capacity is big, and the CSPs of applied range is the research forward position of chiral chromatogram always.In at present a large amount of chiral stationary phases, the fixing purposes widely that has been proved to be mutually of polysaccharides chiral.Chiral stationary phase with the preparation of polysaccharide derivates such as cellulose, starch has the ability that splits preferably, is one of most popular chiral stationary phase in the high performance liquid chromatography chiral resolution.
Commercial polysaccharide derivates is fixing to be to adopt the physics coating process that polysaccharide derivates is fixed on the chromatography matrix mutually, but it is not firm that physics applies its adhesion, the phase range of choice that flows is little, causes shortcomings such as the solubility of chiral material in flowing mutually is low, has limited its application.Also have in addition polysaccharide derivates is fixed on the chromatography matrix through chemical bonding, though the method has improved the fixedly solvent resistance of phase, but because of having reduced the orderly arrangement of polysaccharide derivates, the fractionation ability all is lower than coating-type chiral stationary phase (Tomoyuki Ikai, Chiyo Yamamoto, Masami Kamigaito, Yoshio Okamoto., 2007,1157:151-158.Bezhan Chankvetadze, Tomoyuki Ikai, Chiyo Yamamoto, Yoshio Okamoto..Journal ofChromatography A, 2004,1042:55-60.Natsuki Kasuyal, Yuko Kusakal, Naoto Habu andAtsushi Ohnishi.Cellulose 9:263-269,2002.X M Chen, Y Q Liu, F Qinetal.J.Chromatogr.A, 2003,1010:185~19).
Therefore, be badly in need of a kind of flowing of developmental research and select wide adaptability and the high chiral stationary phase of fractionation ability mutually.
Summary of the invention
The objective of the invention is to prepare the wide and high chiral stationary phase of fractionation ability of a kind of mobile phase range of choice.In order to achieve the above object, the present invention adopts coating process behind the first bonding to prepare a kind of chiral stationary phase of bonding-affinity composite type.The technical scheme that adopts is characterized as: at first prepare polysaccharide derivates (I) and (II), then polysaccharide derivates (I) is chemically bonded on the chiral stationary phase matrix, obtain fixedly phase of bonding type, again polysaccharide derivates (II) affinity is coated to that bonding type is fixing to be gone up mutually, obtains bonding-affinity composite type polysaccharide chiral stationary phase.The chemical bonding of this method by the first step can overcome fixedly shortcoming such as immobilized insecure, the easy loss of phase polysaccharide derivates of coating-type, and second step overcame fixedly shortcoming such as phase polysaccharide derivates configuration malleable of bonding type again by the affinity coating; Concrete reactions steps is as follows:
(1) preparation polysaccharide derivates (I) and polysaccharide derivates (II)
Polysaccharide is scattered in the pyridine of no water treatment, adds the polysaccharide derivatization reagent, reaction finishes and adds precipitating reagent after the cooling and make the product precipitation, after filtration, the washing afterproduct to constant weight, promptly obtains polysaccharide derivates in vacuum drying.
Described polysaccharide is: cellulose or starch or cyclodextrin or shitosan or xylan or glucan or carboxymethyl cellulose; The polysaccharide derivatization reagent is: phenyl isocyanate or 3,5-dimethylphenyl isocyanate or 3,5-dichloride base phenyl isocyanic acid or to methyl-phenyl isocyanate or 3,5-dinitrobenzoyl chloride or chlorobenzoyl chloride or 3,5-dinitrobenzoyl chloride or anisoyl chloride; Making product precipitation agents useful for same is methyl alcohol or ethanol; Its hydroxyl substitution value of polysaccharide derivates (I) is: 5%-50%; Its hydroxyl substitution value of polysaccharide derivates (II) is 30-100%.
(2) polysaccharide derivates (I) is scattered among the solvent I, is bonded on the chiral stationary phase matrix of solvent II swelling, obtain fixedly phase (A) of bonding type
Described solvent I is: oxolane or acetone or pyridine; Chiral stationary phase matrix is: the hydrolysate of polyacrylic acid or polymethylacrylic acid or polyacrylate or the hydrolysate of polymethacrylates or polyacrylamide or carboxymethyl cellulose or carboxylic polystyrene; Chiral stationary phase matrix is used after reacting chloride with thionyl chloride; Solvent II is: carrene or oxolane or pyridine or N, dinethylformamide.
(3) polysaccharide derivates (II) is coated to bonding type fixedly on the phase (A), obtains bonding-affinity composite type polysaccharide chiral stationary phase (B).
Remarkable advantage of the present invention is: polysaccharide derivates (I) is bonded on the chiral stationary phase matrix, obtain fixedly phase of bonding type, again by affine coating process, polysaccharide derivates (II) is coated in bonded polysaccharide chiral stationary phase surface, obtains bonding-affinity composite type polysaccharide chiral stationary phase and the chirality enantiomer is separated and prepares to be applicable to liquid chromatography.Method by chemical bonding is fixed on polysaccharide derivatives on the chiral stationary phase matrix, can use oxolane, carrene, chloroform etc. as the phase additive that flows, and having enlarged flows uses scope, the problem of avoiding chiral selector to run off mutually.And the affinity coating process by behind the bonding has overcome the fixedly low shortcoming of phase chiral resolution ability of bonding type.
Specific embodiments
Embodiment 1
Get the adding of 1g cyclodextrin and fill in the reactor of 30mL pyridine, add then and be equivalent to 3 of 1.5 times of amounts of cyclodextrin, 5-dichloride base phenyl isocyanate, 80 ℃ were reacted 24 hours.Cooling back adds a large amount of methyl alcohol makes the product precipitation, after filtration, to constant weight, promptly obtain its hydroxyl substitution value of polysaccharide derivates (I) is 50% to the washing afterproduct in vacuum drying; Under the constant condition of other conditions, change 3, the consumption of 5-dichloride base phenyl isocyanate is 1.87 times of cyclodextrin, promptly obtaining its hydroxyl substitution value of polysaccharide derivates (II) is 60%.
Get the 1g polyacrylic acid in round-bottomed flask, add the 10mL pyridine, swelling 1 hour, add the 1.5mL thionyl chloride, 50 ℃ were reacted 8 hours down, after unreacted thionyl chloride is removed, add 1g polysaccharide derivates (I) and 10mL acetone more successively, stirring is uniformly dispersed it, and 80 ℃ were reacted 12 hours.After the cooling, product is through washing, drying, promptly obtains rate of body weight gain and be fixedly phase (A) of 12% bonding type.
Get bonding type fixedly phase (A) 3g with 15mL acetone swelling 12 hours, other gets polysaccharide derivates (II) 0.529g and is dissolved in 30mL acetone soln standing over night, get that this solution 10mL adds swelling fixing mutually in, rotary evaporation in vacuo removes and desolvates, repeat this operation 3 times, promptly obtain bonding-affinity composite type polysaccharide chiral stationary phase (B).
Embodiment 2
Get the adding of 1g starch and fill in the reactor of 20mL pyridine, add then and be equivalent to 3 of 1.3 times of amounts of starch, the 5-dimethylphenyl isocyanate, 100 ℃ were reacted 24 hours.Cooling back adds a large amount of ethanol makes the product precipitation, after filtration, to constant weight, promptly obtain its hydroxyl substitution value of polysaccharide derivates (I) is 45% to the washing afterproduct in vacuum drying; Under the constant condition of other conditions, change 3,5-dimethylphenyl isocyanate consumption is 3.0 times of starch, promptly obtaining its hydroxyl substitution value of polysaccharide derivates (II) is 80%.
Get the 1g carboxymethyl cellulose in round-bottomed flask, add the 10mL oxolane, swelling 8 hours, add the 4mL thionyl chloride, 50 ℃ were reacted 8 hours down, after unreacted thionyl chloride is removed, added 1g polysaccharide derivates (I) and 10mL oxolane more successively, stirring is uniformly dispersed it, and 50 ℃ were reacted 12 hours.After the cooling, product is through washing, drying, promptly obtains rate of body weight gain and be fixedly phase (A) of 8% bonding type.
Get bonding type fixedly phase (A) 3g with 15mL acetone swelling 12 hours, other takes by weighing polysaccharide derivates (II) 0.529g and is scattered in 30mL acetone soln standing over night, get that this solution 10mL adds swelling fixing mutually in, rotary evaporation in vacuo removes and desolvates, repeat this operation 3 times, promptly obtain bonding-affinity composite type polysaccharide chiral stationary phase (B).
Embodiment 3
Get the adding of 1g cellulose and fill in the reactor of 15mL pyridine, add the phenyl isocyanate that is equivalent to 0.9 times of amount of cellulose then, 80 ℃ were reacted 24 hours.Cooling back adds a large amount of methyl alcohol makes the product precipitation, after filtration, to constant weight, promptly obtain its hydroxyl substitution value of polysaccharide derivates (I) is 39% to the washing afterproduct in vacuum drying; Under the constant condition of other conditions, changing the phenyl isocyanate consumption is cellulosic 5 times, and promptly obtaining its hydroxyl substitution value of polysaccharide derivates (II) is 95%.
Get the 1g carboxylic polystyrene in round-bottomed flask, add the 10mL carrene, swelling 12 hours, add the 0.75mL thionyl chloride, 40 ℃ were reacted 8 hours down, after unreacted thionyl chloride is removed, added 1g polysaccharide derivates (I) and 10mL pyridine more successively, stirring is uniformly dispersed it, and 80 ℃ were reacted 12 hours.The cooling afterproduct is through washing, drying, promptly obtains rate of body weight gain and be fixedly phase (A) of 19% bonding type.
Get bonding type fixedly phase (A) 3g with 15mL oxolane swelling 12 hours, other takes by weighing polysaccharide derivates (II) 0.529g and is scattered in 30mL tetrahydrofuran solution standing over night, get that this solution 10mL adds swelling fixing mutually in, rotary evaporation in vacuo removes and desolvates, repeat this operation 3 times, promptly obtain bonding-affinity composite type polysaccharide chiral stationary phase (B).
Embodiment 4
Get the 1g shitosan and add and to fill in the reactor of 15mL pyridine, add then be equivalent to 1.4 times of amounts of shitosan to methyl-phenyl isocyanate, 60 ℃ of reactions 24 hours.Cooling back adds a large amount of ethanol makes the product precipitation, after filtration, to constant weight, promptly obtain its hydroxyl substitution value of polysaccharide derivates (I) is 48% to the washing afterproduct in vacuum drying; Under the constant condition of other conditions, changing methyl-phenyl isocyanate consumption is 1.6 times of shitosan, and promptly obtaining its hydroxyl substitution value of polysaccharide derivates (II) is 55%.
The hydrolysate of getting the 1g polyacrylate is in round-bottomed flask, add 10mL N, dinethylformamide, swelling 6 hours adds the 2.5mL thionyl chloride, and 50 ℃ were reacted 8 hours down, after unreacted thionyl chloride removal, add 1g polysaccharide derivates (I) and 10mL acetone more successively, stirring is uniformly dispersed it, and 30 ℃ were reacted 12 hours.After the cooling, product is through washing, drying, and the bonding type of promptly obtaining rate of body weight gain 16% is phase (A) fixedly.
Get above-mentioned bonding type cellulose chiral fixedly phase 3g with 15mL oxolane swelling 12 hours, other takes by weighing polysaccharide derivates (II) 0.529g and is dissolved in 30mL tetrahydrofuran solution standing over night, get that this solution 10mL adds swelling fixing mutually in, rotary evaporation in vacuo removes and desolvates, repeat this operation 3 times, promptly obtain bonding-affinity composite type polysaccharide chiral stationary phase (B).
Embodiment 5
Get the adding of 1g xylan and fill in the reactor of 40mL pyridine, add then and be equivalent to 3 of 0.8 times of amount of xylan, the 5-dinitrobenzoyl chloride, 80 ℃ were reacted 24 hours.Cooling back adds a large amount of methyl alcohol makes the product precipitation, after filtration, to constant weight, promptly obtain its hydroxyl substitution value of polysaccharide derivates (I) is 25% to the washing afterproduct in vacuum drying; Under the constant condition of other conditions, change 3, the consumption of 5-dinitrobenzoyl chloride is 2.8 times of xylan, promptly obtaining polysaccharide derivates (II) hydroxyl substitution value is 70%.
Get the 1g carboxylic polystyrene in round-bottomed flask, add in the 5mL oxolane swelling 16 hours.Adding 0.75mL thionyl chloride, 50 ℃ were reacted 8 hours down, after unreacted thionyl chloride is removed, added 1g polysaccharide derivates (I) and 10mL pyridine more successively, stirred it is uniformly dispersed, and 80 ℃ were reacted 12 hours.After the cooling, product is through washing, drying, and the bonding type of promptly obtaining rate of body weight gain 10% is phase (A) fixedly.
Get above-mentioned bonding type cellulose chiral fixedly phase 3g with 15mL acetone swelling 12 hours, other takes by weighing polysaccharide derivates (II) 0.529g and is dissolved in 30mL acetone soln standing over night, get that this solution 10mL adds swelling fixing mutually in, rotary evaporation in vacuo removes and desolvates, repeat this operation 3 times, promptly obtain bonding-affinity composite type polysaccharide chiral stationary phase (B).
Embodiment 6
Get the adding of 1g glucan and fill in the reactor of 15mL pyridine, add the chlorobenzoyl chloride that is equivalent to 0.8 times of amount of glucan then, 100 ℃ were reacted 24 hours.Cooling back adds a large amount of ethanol makes the product precipitation, after filtration, to constant weight, promptly obtain its hydroxyl substitution value of polysaccharide derivates (I) is 31% to the washing afterproduct in vacuum drying; Under the constant condition of other conditions, the consumption that changes chlorobenzoyl chloride is 4 times of glucan, and promptly obtaining polysaccharide derivates (II) hydroxyl substitution value is 90%.
Get the 1g carboxylic polystyrene in round-bottomed flask, add in the 10mL pyridine, swelling 4 hours, add the 0.75mL thionyl chloride, 50 ℃ were reacted 8 hours down, after unreacted thionyl chloride is removed, added 1g polysaccharide derivates (I) and 10mL oxolane more successively, stirring is uniformly dispersed it, and 50 ℃ were reacted 12 hours.After the cooling, product is through washing, drying, and the bonding type of promptly obtaining rate of body weight gain 14% is phase (A) fixedly.
Get above-mentioned bonding type cellulose chiral fixedly phase 3g with 15mL oxolane swelling 12 hours, other takes by weighing polysaccharide derivates (II) 0.529g and is dissolved in 30mL tetrahydrofuran solution standing over night, get that this solution 10mL adds swelling fixing mutually in, rotary evaporation in vacuo removes and desolvates, repeat this operation 3 times, promptly obtain bonding-affinity composite type polysaccharide chiral stationary phase (B).
Embodiment 7
Get the adding of 1g carboxymethyl cellulose and fill in the reactor of 20mL pyridine, add then and be equivalent to 3 of 0.9 times of amount of carboxymethyl cellulose, the 5-dinitrobenzoyl chloride, 50 ℃ were reacted 24 hours.Cooling back adds a large amount of methyl alcohol makes the product precipitation, after filtration, to constant weight, promptly obtain its hydroxyl substitution value of polysaccharide derivates (I) is 39% to the washing afterproduct in vacuum drying; Under the constant condition of other conditions, change 3,5-dinitrobenzoyl chloride consumption is 1.9 times of carboxymethyl cellulose, promptly obtaining polysaccharide derivates (II) hydroxyl substitution value is 65%.
The hydrolysate of getting the 1g polymethacrylates adds in the 10mL carrene swelling 12 hours in round-bottomed flask.Adding 3.2mL thionyl chloride, 50 ℃ were reacted 8 hours down, and after unreacted thionyl chloride was removed, more successively with 1g polysaccharide derivates (I) and 10mL carrene, stirring was uniformly dispersed it, and 40 ℃ were reacted 12 hours.After the cooling, product is through washing, drying, and the bonding type of promptly obtaining rate of body weight gain 6% is phase (A) fixedly.
Get above-mentioned bonding type cellulose chiral fixedly phase 3g with 15mL acetone swelling 12 hours, other takes by weighing polysaccharide derivates (II) 0.529g and is dissolved in 30mL acetone soln standing over night, get that this solution 10mL adds swelling fixing mutually in, rotary evaporation in vacuo removes and desolvates, repeat this operation 3 times, promptly obtain bonding-affinity composite type polysaccharide chiral stationary phase (B).
Embodiment 8
Get the adding of 1g cyclodextrin and fill in the reactor of 30mL pyridine, add the anisoyl chloride that is equivalent to 1.0 times of amounts of cyclodextrin then, 100 ℃ were reacted 24 hours.Cooling back adds a large amount of ethanol makes the product precipitation, after filtration, to constant weight, promptly obtain its hydroxyl substitution value of polysaccharide derivates (I) is 40% to the washing afterproduct in vacuum drying; Under the constant condition of other conditions, the consumption that changes anisoyl chloride is 3.6 times of cyclodextrin, and promptly obtaining polysaccharide derivates (II) hydroxyl substitution value is 85%.
Get the 1g polymethylacrylic acid in round-bottomed flask, add in the 10mL oxolane swelling 5 hours.Adding 1.6mL thionyl chloride, 50 ℃ were reacted 8 hours down, after unreacted thionyl chloride is removed, added 1g polysaccharide derivates (I) and 10mL pyridine more successively, stirred it is uniformly dispersed, and 60 ℃ were reacted 12 hours.After the cooling, product is through washing, drying, and the bonding type of promptly obtaining rate of body weight gain 13% is phase (A) fixedly.
Get above-mentioned bonding type cellulose chiral fixedly phase 3g with 15mL oxolane swelling 12 hours, other takes by weighing polysaccharide derivates (II) 0.529g and is dissolved in 30mL tetrahydrofuran solution standing over night, get that this solution 10mL adds swelling fixing mutually in, rotary evaporation in vacuo removes and desolvates, repeat this operation 3 times, promptly obtain bonding-affinity composite type polysaccharide chiral stationary phase (B).
Embodiment 9
Get the adding of 1g starch and fill in the reactor of 35mL pyridine, add then and be equivalent to 3 of 1.5 times of amounts of starch, the 5-dinitrobenzoyl chloride, 80 ℃ were reacted 24 hours.The cooling back adds a large amount of methyl alcohol makes the product precipitation, after filtration, the washing afterproduct in vacuum drying to constant weight, promptly obtaining its hydroxyl substitution value of polysaccharide derivates (I) is 50%, under the constant condition of other conditions, change 3, the consumption of 5-dinitrobenzoyl chloride is 2.5 times of starch, and promptly obtaining polysaccharide derivates (II) hydroxyl substitution value is 70%.
Get the 1g carboxylic polystyrene in round-bottomed flask, add 10mL N, in the dinethylformamide, swelling 12 hours.Adding 0.75mL thionyl chloride, 50 ℃ were reacted 8 hours down, after unreacted thionyl chloride is removed, added 1g polysaccharide derivates (I) and 10mL oxolane more successively, stirred it is uniformly dispersed, and 50 ℃ were reacted 12 hours.After the cooling, product is through washing, drying, and the bonding type of promptly obtaining rate of body weight gain 15% is phase (A) fixedly.
Get above-mentioned bonding type cellulose chiral fixedly phase 3g with 15mL acetone swelling 12 hours, other takes by weighing polysaccharide derivates (II) 0.529g and is dissolved in 30mL acetone soln standing over night, get that this solution 10mL adds swelling fixing mutually in, rotary evaporation in vacuo removes and desolvates, repeat this operation 3 times, promptly obtain bonding-affinity composite type polysaccharide chiral stationary phase (B).
Embodiment 10
Get the adding of 1g cellulose and fill in the reactor of 40mL pyridine, add the phenyl isocyanate that is equivalent to 0.6 times of amount of cellulose then, 100 ℃ were reacted 24 hours.The cooling back adds a large amount of ethanol makes the product precipitation, after filtration, the washing afterproduct in vacuum drying to constant weight, promptly obtaining its hydroxyl substitution value of polysaccharide derivates (I) is 30%, under the constant condition of other conditions, the consumption that changes phenyl isocyanate is cellulosic 5.1 times, and promptly obtaining polysaccharide derivates (II) hydroxyl substitution value is 96%.
The hydrolysate of getting the 1g polymethacrylates adds in the 10mL pyridine swelling 12 hours in round-bottomed flask.Adding 1.6mL thionyl chloride, 50 ℃ were reacted 8 hours down, after unreacted thionyl chloride is removed, added 1g polysaccharide derivates (I) and 10mL pyridine more successively, stirred it is uniformly dispersed, and 80 ℃ were reacted 12 hours.After the cooling, product is through washing, drying, promptly obtains rate of body weight gain and be fixedly phase (A) of 17% bonding type.
Get above-mentioned bonding type cellulose chiral fixedly phase 3g with 15mL oxolane swelling 12 hours, other takes by weighing polysaccharide derivates (II) 0.529g and is dissolved in 30mL tetrahydrofuran solution standing over night, get that this solution 10mL adds swelling fixing mutually in, rotary evaporation in vacuo removes and desolvates, repeat this operation 3 times, promptly obtain bonding-affinity composite type polysaccharide chiral stationary phase (B).

Claims (4)

1. the preparation method of a bonding-affinity composite type polysaccharide chiral stationary phase is characterized in that described method comprises following two steps simultaneously:
(1) polysaccharide derivates I is scattered among the solvent I,, obtains fixedly phase A of bonding type through being chemically bonded on the chiral stationary phase matrix of solvent II swelling;
(2) polysaccharide derivates II is coated to bonding type fixedly on the phase A through affinity, obtains bonding-affinity composite type polysaccharide chiral stationary phase B,
The hydroxyl substitution value of polysaccharide derivates I is: 5-50%, and the hydroxyl substitution value of polysaccharide derivates II is: 55-100%;
The preparation method of polysaccharide derivates I and polysaccharide derivates II is: polysaccharide is scattered in the pyridine of no water treatment, add the polysaccharide derivatization reagent, reaction finishes and adds precipitating reagent after the cooling and make product precipitation, after filtration, the washing afterproduct to constant weight, promptly obtains polysaccharide derivates I and polysaccharide derivates II in vacuum drying;
Described polysaccharide is cellulose or starch or cyclodextrin or shitosan or xylan or glucan or carboxymethyl cellulose;
Described chiral stationary phase matrix is the hydrolysate of polyacrylic acid or polymethylacrylic acid or polyacrylate or hydrolysate or polyacrylamide or the carboxylic polystyrene or the carboxymethyl cellulose of polymethacrylates.
2. the preparation method of chiral stationary phase according to claim 1, it is characterized in that the polysaccharide derivatization reagent is phenyl isocyanate or 3,5-dimethylphenyl isocyanate or 3,5-dichloride base phenyl isocyanate or to methyl-phenyl isocyanate or 3,5-dinitrobenzoyl chloride or chlorobenzoyl chloride or anisoyl chloride.
3. the preparation method of chiral stationary phase according to claim 1 is characterized in that precipitating reagent is methyl alcohol or ethanol.
4. the preparation method of chiral stationary phase according to claim 1 is characterized in that solvent I is: oxolane or acetone or pyridine; Solvent II is carrene or oxolane or pyridine or N, dinethylformamide.
CN200710191730A 2007-12-17 2007-12-17 Preparation method of bonding-affinity compound polysaccharide chiral stationary phase Expired - Fee Related CN100579650C (en)

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