CN110252266A - A kind of chromatographic column for the rosinyl polymer microsphere and its preparation that esterification is modified - Google Patents
A kind of chromatographic column for the rosinyl polymer microsphere and its preparation that esterification is modified Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/265—Adsorption chromatography
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
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- B01J20/285—Porous sorbents based on polymers
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Abstract
The present invention discloses a kind of chromatographic column of rosinyl polymer microsphere and its preparation that esterification is modified; preparation method are as follows: maleic rosin acrylic acid glycol ester-(methyl) acryl acid-methyl methacrylate copolymer, that is, rosinyl polymer microsphere is first subjected to acylation reaction with acylating reagent; esterification is carried out with esterifying reagent again, the rosinyl polymer microsphere of the esterification modification can be obtained.The rosinyl polymer microsphere of the esterification modification is spherical porous material, and partial size is 5~15 μm, 5~50mgKOH/g of acid value, and average pore size is 10~15nm, and specific surface area is 80~150m2/g.The rosinyl polymer microsphere of esterification modification prepares chromatographic column with packing column machine wet method dress post, HPLC separates Gastrodin and its derivative 4- methoxyphenyl β-D- glucopyranoside, and separating degree is higher, is better than C18 column, Environmental Safety, selectivity are high, with good application prospect.
Description
The present patent application is divisional application, parent application number are as follows: 201610998945.6；A kind of female case title are as follows: esterification
The method of the rosin based high molecular chromatographic column separation Gastrodin of modification；Parent application day are as follows: on November 14th, 2016.
Technical field
The invention belongs to high performance liquid chromatography field, the rosinyl polymer microsphere of especially a kind of esterification modification and its
The chromatographic column of preparation.
Background technique
The chemical structural formula of Gastrodin (Gastrodin):
Gastrodin (Gastrodin) is the effective component of rare traditional Chinese medicine Rhizoma Gastrodiae, has and increases center and peripheral arterial blood
Pipe compliance reduces peripheral vascular resistance, increases cardiovascular and cerebrovascular blood flow, generates mild antihypertensive effect, and to cardiac muscle cell, brain
Tissue has protective effect, while having the effects that calmness, hypnosis, analgesia, enhancing are immune, is clinically widely used in treatment head
The illnesss such as pain dizziness, extremity numbness, child convulsion, epilepsy, twitch, tetanus, it is significant in efficacy, and non-evident effect.Especially
In recent years, Gastrodin has in symptoms such as depression, Alzheimer disease, ascitic type liver cancer, osteoporosis, liver fibrosis, migraine
New progress widens its field of medical applications significantly；Therefore it is to measure Rhizoma Gastrodiae processing work that Gastrodin, which extracts the height of yield,
The mark of skill researchs and develops significant to the filler of the selective separating effect of Gastrodin.
High performance liquid chromatography (High performance liquid chromatography, abbreviation HPLC) has following spy
Point: speed is fast, and usually analyze a sample can be completed in 15~30min；High resolution, can be to the substance pair of otherness very little
As chiral material carries out separation analysis；High sensitivity, for UV detector up to 0.01ng, fluorescence and electrochemical detector are reachable
0.1pg；Pillar Reusability separates different compounds with a root chromatogram column；Since it has used non-destructive detector,
After sample analysis, mobile phase can be removed, recycles a small amount of precious drug, also can be used for the purifying preparation of sample.
Currently, the report about Gastrodin high performance liquid chromatography separation method, we find the following document:
Huang jiao, Jiang Deng-jun.Determination of Gastrodin Contents in Wild
and Cultivated Gastrodia elata from Different Regions of Chongqing by RP-
HPLC.Medicinal Plant.2012,3 (5): 42-44；Method is boiled using RP-HPLC color, uses C18Chromatographic column (150mm
× 4.6mm, 5 μm), with -0.05% phosphoric acid solution of acetonitrile (3:97) for mobile phase, flow velocity 1mL/min, column temperature is 30 DEG C, inspection
Survey wavelength 220nm.
Liu Yuhong, Yi Jinhai, RP-HPLC method measure dissociate in Rhizoma Gastrodiae Gastrodin, the gloomy glycosides of Bali and total Gastrodin simultaneously, in
Patent medicine, 2012,34 (1): 182-184；Method is boiled using RP-HPLC color, uses C18Chromatographic column (250mm × 4.6mm, 5 μm),
Using -1% glacial acetic acid solution of methanol as mobile phase, gradient elution, flow velocity 0.8mL/min, column temperature is 35 DEG C, Detection wavelength
270nm。
The method of rosin based high molecular chromatographic column separation Gastrodin about application esterification modification, does not up to the present appear in the newspapers
Road.
Summary of the invention
It is above-mentioned it is an object of the invention to solve the problems, such as, a kind of rosin based high molecular chromatography of esterification modification is provided
The method of post separation Gastrodin, it is this method high sensitivity, easy to operate, secondary dirt will not be caused to drug, health care product, food
Dye.
To achieve the above object, the present invention the following technical schemes are provided:
1. a kind of rosinyl polymer microsphere of esterification modification, it is characterised in that: the abietyl high score of the esterification modification
Sub- method for preparing microsphere are as follows: be by maleic rosin acrylic acid glycol ester-(methyl) acryl acid-methyl methacrylate copolymer
Rosinyl polymer microsphere first carries out acylation reaction with acylating reagent, then carries out esterification with esterifying reagent, and institute can be obtained
The rosinyl polymer microsphere for the esterification modification stated.
As the further improvement of technical solution, the rosinyl polymer microsphere of above-described esterification modification is spherical more
Porous materials, partial size be 5~15 μm, 5~50mgKOH/g of acid value, average pore size be 10~15nm, specific surface area be 80~
150m2/g。
As the further improvement of technical solution, a kind of above-described rosinyl polymer microsphere of esterification modification, institute
The acylating reagent stated is oxalyl chloride or thionyl chloride.
As the further improvement of technical solution, the rosinyl polymer microsphere of esterification modification, described described in above 3
One of esterifying reagent methanol, ethylene glycol or glycerol.
Above to be esterified the rosinyl polymer microsphere modified as the further improvement of technical solution, the acylation is anti-
It answers are as follows: by maleic rosin acrylic acid glycol ester-(methyl) acryl acid-methyl methacrylate copolymer, that is, rosin based high molecular
One of microballoon and solvent hexamethylene, n-hexane, heptane, acetone, octane, 1,4- dioxane are 1:10~16 in mass ratio
It is placed in reaction vessel, under ice-water bath, stirring condition, acylating reagent, rosin based high molecular and acylated examination is added dropwise into reaction
Agent mass ratio is 1:0.3~0.9, and after being added dropwise, the heating reflux reaction 4~8 hours under the conditions of 60~85 DEG C will be acylated anti-
The reaction system that should terminate uses vacuum distillation apparatus, steams extra solvent and acylating reagent, obtains acylated rosin
Based high molecular microballoon.
As the further improvement of technical solution, a kind of above-described rosinyl polymer microsphere of esterification modification, institute
The esterification stated are as follows: by acylated rosinyl polymer microsphere and solvent hexamethylene, n-hexane, heptane, acetone, octane, 1,4-
One of dioxane is that 1:7~13 is added in reactor according to mass ratio, and esterifying reagent is then added, and acylated abietyl is high
The mass ratio of molecule microballoon and esterifying reagent is 1:0.2~3, is stirred at reflux reaction 1~4 hour under the conditions of 60~80 DEG C, temperature
Water washing microballoon to PH=6~7,10~50h of ethanolic extraction, addition distilled water agitating and heating boiling removes the small molecules objects such as ethyl alcohol
The rosinyl polymer microsphere of the esterification modification can be obtained in matter.
A kind of chromatographic column for the rosinyl polymer microsphere preparation that a kind of esterification by any description above is modified, will be esterified
The rosinyl polymer microsphere of modification is mixed in one of methanol, acetonitrile or chloroform, and ultrasonic disperse is uniform, and equal slurries are filled
In empty chromatographic column, 120~200min is loaded under 3000~3500psi pressure with packing column machine constant pressure pump, after column flattens weighing apparatus,
Chromatographic column is removed from packing column machine, loads onto column cap, the rosin based high molecular chromatographic column of esterification modification is made.
Compared with prior art, the invention has the benefit that
1. the rosinyl polymer microsphere for the esterification modification that the present invention prepares, dilation is small, large specific surface area, can be used for
The effective component of separating natural product, and can use in organic solvent, the netted knot of molecule microballoon will not be destroyed because of expansion
Structure causes recognition capability to be lost.
2. the abietyl high score that the present invention is modified using being esterified the rosinyl polymer microsphere of modification as esterification prepared by filler
Sub- chromatographic column has many advantages, such as that permeability is good, back pressure is low, efficient and high-throughput, higher because being rich in pore structure not of uniform size
Flow velocity and pressure under, there is not the phenomenon that be collapsed, can be used under high flow rate.
3. chromatographic column used in the present invention has preferably Gastrodin and 4- methoxyphenyl β-D- glucopyranoside
Separating effect；In C18Separating degree on column is 0.37, and the separating degree in the invention patent chromatographic column is 1.97 or more.
4. the rosin based high molecular of esterification modification used in the present invention is obtained by Material synthesis of natural products, safe nothing
Poison, high mechanical strength.
5. chromatographic column used in the present invention, high sensitivity is easy to operate.
Detailed description of the invention
Fig. 1 C18High performance liquid chromatography of the column to Gastrodin and 4- methoxyphenyl β-D- glucopyranoside mixed solution
Spectrogram；
Fig. 2 is height of the embodiment of the present invention 4 to Gastrodin and 4- methoxyphenyl β-D- glucopyranoside mixed solution
Effect liquid phase chromatogram spectrogram；
Fig. 3 is height of the embodiment of the present invention 5 to Gastrodin and 4- methoxyphenyl β-D- glucopyranoside mixed solution
Effect liquid phase chromatogram spectrogram；
Fig. 4 is height of the embodiment of the present invention 6 to Gastrodin and 4- methoxyphenyl β-D- glucopyranoside mixed solution
Effect liquid phase chromatogram spectrogram
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to
The range that embodiment indicates.
It is esterified the preparation of the rosinyl polymer microsphere of modification:
Referred to as " abietyl is high for maleic rosin acrylic acid glycol ester-(methyl) acryl acid-methyl methacrylate copolymer
Molecule microballoon "
Embodiment 1
Rosinyl polymer microsphere 5g will be weighed and measure 78g hexamethylene and be placed in reaction vessel, the two mass ratio is 1:
15.6, under ice-water bath, stirring condition, acylating reagent 2.55g oxalyl chloride, rosin based high molecular and acylated examination are added dropwise into reaction
Agent mass ratio is 1:0.51, after being added dropwise, is heated to reflux 80 DEG C and reacts 4 hours, then terminate acylation reaction anti-
It answers system using vacuum distillation apparatus, steams extra hexamethylene and acylating reagent, obtain acylated rosinyl polymer microsphere.
It is obtained aforementioned in acylated rosinyl polymer microsphere and solvent hexamethylene 39g addition reactor, the two mass ratio
For 1:7.8, esterifying reagent 4.75g methanol is then added, the mass ratio for being acylated rosinyl polymer microsphere and esterifying reagent is 1:
0.95, it is stirred at reflux 60 DEG C and reacts 1 hour, warm water washs microballoon to PH=6.0, ethanolic extraction 10h, and distilled water stirring is added and adds
Heat boiling removes the small-molecule substances such as ethyl alcohol, and the rosinyl polymer microsphere of the esterification modification can be obtained.
Through testing and analyzing, what the present embodiment obtained is esterified the rosinyl polymer microsphere modified, and the macromolecule after modification is micro-
Ball is spherical porous material, and partial size is 5~15 μm, 5~50mgKOH/g of acid value, and average pore size is 10~15nm, specific surface area
For 80~150m2/g。
Embodiment 2:
Isosorbide-5-Nitrae-the dioxane for weighing rosinyl polymer microsphere 10g and measurement 104g is placed in reaction vessel, the two
Mass ratio is 1:10.4, and under ice-water bath, stirring condition, acylating reagent 5.1g oxalyl chloride, abietyl high score are added dropwise into reaction
Son is 1:0.51 with acylating reagent mass ratio, after being added dropwise, is heated to 70 DEG C and reacts 6 hours, then terminate acylation reaction
Obtained reaction system uses vacuum distillation apparatus, steams extra Isosorbide-5-Nitrae-dioxane and acylating reagent, obtains acylated pine
Perfume base polymer microsphere.
It is obtained aforementioned in acylated rosinyl polymer microsphere and solvent Isosorbide-5-Nitrae-dioxane 100g addition reactor, the two
Mass ratio is 1:10, and esterifying reagent 9.93g ethylene glycol, the quality of acylated rosinyl polymer microsphere and esterifying reagent is then added
It is reacted 3 hours than for 1:0.99, stirring 70 DEG C, warm water washs microballoon to PH=6.5, and for 24 hours, distilled water stirring is added in ethanolic extraction
Ebuillition of heated removes the small-molecule substances such as ethyl alcohol, and the rosinyl polymer microsphere of the esterification modification can be obtained.
Through testing and analyzing, what the present embodiment obtained is esterified the rosinyl polymer microsphere modified, and the macromolecule after modification is micro-
Ball is spherical porous material, and partial size is 5~15 μm, 5~50mgKOH/g of acid value, and average pore size is 10~15nm, specific surface area
For 80~150m2/g。
Embodiment 3:
Rosinyl polymer microsphere 5g will be weighed and measure 78.8g acetone and be placed in reaction vessel, the two mass ratio is 1:
15.76, under ice-water bath, stirring condition, acylating reagent 4.01g thionyl chloride, rosin based high molecular and acyl are added dropwise into reaction
Change reagent quality ratio is 1:0.8, after being added dropwise, is heated to reflux 60 DEG C and reacts 8 hours, then terminate acylation reaction
Reaction system uses vacuum distillation apparatus, steams extra acetone and acylating reagent, obtains acylated rosinyl polymer microsphere.
It is obtained aforementioned in acylated rosinyl polymer microsphere and solvent acetone 59.1g addition reactor, the two mass ratio
For 1:11.82, esterifying reagent 4.85g glycerol is then added, the mass ratio for being acylated rosinyl polymer microsphere and esterifying reagent is
1:0.97 is stirred at reflux 80 DEG C and reacts 4 hours, and warm water washs microballoon to PH=7.0, ethanolic extraction 36h, and distilled water stirring is added
Ebuillition of heated removes the small-molecule substances such as ethyl alcohol, and the rosinyl polymer microsphere of the esterification modification can be obtained.
Through testing and analyzing, what the present embodiment obtained is esterified the rosinyl polymer microsphere modified, and the macromolecule after modification is micro-
Ball is spherical porous material, and partial size is 5~15 μm, 5~50mgKOH/g of acid value, and average pore size is 10~15nm, specific surface area
For 80~150m2/g。
Embodiment 4
Rosinyl polymer microsphere 5g will be weighed and measure 60g n-hexane and be placed in reaction vessel, the two mass ratio is 1:
12, under ice-water bath, stirring condition, acylating reagent 1.5g oxalyl chloride, rosin based high molecular and acylating reagent are added dropwise into reaction
Mass ratio is 1:0.3, after being added dropwise, is heated to reflux 85 DEG C and reacts 5 hours, the reactant for then terminating acylation reaction
System uses vacuum distillation apparatus, steams extra n-hexane and acylating reagent, obtains acylated rosinyl polymer microsphere.
It is obtained aforementioned in acylated rosinyl polymer microsphere and solvent hexane 45g addition reactor, the two mass ratio
For 1:9, esterifying reagent 10g methanol is then added, the mass ratio for being acylated rosinyl polymer microsphere and esterifying reagent is 1:2, is stirred
It mixes 65 DEG C of reflux to react 2 hours, warm water washs microballoon to PH=6.0, ethanolic extraction 50h, and the boiling of distilled water agitating and heating is added
The small-molecule substances such as ethyl alcohol are removed, the rosinyl polymer microsphere of the esterification modification can be obtained.
Through testing and analyzing, what the present embodiment obtained is esterified the rosinyl polymer microsphere modified, and the macromolecule after modification is micro-
Ball is spherical porous material, and partial size is 5~15 μm, 5~50mgKOH/g of acid value, and average pore size is 10~15nm, specific surface area
For 80~150m2/g。
Embodiment 5:
The heptane for weighing rosinyl polymer microsphere 10g and measurement 140g is placed in reaction vessel, the two mass ratio is
Acylating reagent 7.0g oxalyl chloride, rosin based high molecular and acylated examination are added dropwise into reaction under ice-water bath, stirring condition by 1:14
Agent mass ratio is 1:0.7, after being added dropwise, is heated to 65 DEG C and reacts 7 hours, the reactant for then terminating acylation reaction
System uses vacuum distillation apparatus, steams extra heptane and acylating reagent, obtains acylated rosinyl polymer microsphere.
It is obtained aforementioned in acylated rosinyl polymer microsphere and solvent heptane 130g addition reactor, the two mass ratio is
Then esterifying reagent 30g ethylene glycol is added in 1:13, the mass ratio for being acylated rosinyl polymer microsphere and esterifying reagent is 1:3, stirs
It mixes 75 DEG C to react 3 hours, warm water washs microballoon to PH=6.5, ethanolic extraction 30h, and the boiling of distilled water agitating and heating is added and removes
The rosinyl polymer microsphere of the esterification modification can be obtained in the small-molecule substances such as ethyl alcohol.
Through testing and analyzing, what the present embodiment obtained is esterified the rosinyl polymer microsphere modified, and the macromolecule after modification is micro-
Ball is spherical porous material, and partial size is 5~15 μm, 5~50mgKOH/g of acid value, and average pore size is 10~15nm, specific surface area
For 80~150m2/g。
Embodiment 6:
Rosinyl polymer microsphere 5g will be weighed and measure 55g octane and be placed in reaction vessel, the two mass ratio is 1:11,
Under ice-water bath, stirring condition, acylating reagent 3.0g thionyl chloride, rosin based high molecular and acylating reagent matter are added dropwise into reaction
Amount is than being 1:0.6, after being added dropwise, is heated to reflux 75 DEG C and reacts 8 hours, the reaction system for then terminating acylation reaction
Using vacuum distillation apparatus, extra octane and acylating reagent are steamed, acylated rosinyl polymer microsphere is obtained.
It is obtained aforementioned in acylated rosinyl polymer microsphere and solvent octane 55.0g addition reactor, the two mass ratio
For 1:11, esterifying reagent 1g glycerol is then added, the mass ratio for being acylated rosinyl polymer microsphere and esterifying reagent is 1:0.2,
It is stirred at reflux 65 DEG C to react 4 hours, warm water washs microballoon to PH=7.0, ethanolic extraction 40h, and the boiling of distilled water agitating and heating is added
It rises and removes the small-molecule substances such as ethyl alcohol, the rosinyl polymer microsphere of the esterification modification can be obtained.
Through testing and analyzing, what the present embodiment obtained is esterified the rosinyl polymer microsphere modified, and the macromolecule after modification is micro-
Ball is spherical porous material, and partial size is 5~15 μm, 5~50mgKOH/g of acid value, and average pore size is 10~15nm, specific surface area
For 80~150m2/g。
Using the method for the rosin based high molecular chromatographic column separation Gastrodin of esterification modification
Embodiment 7:
A method of the rosin based high molecular chromatographic column of esterification modification separates Gastrodin, carries out in accordance with the following steps:
(1) the rosin based high molecular chromatographic column preparation of esterification modification: the rosin based high molecular that the esterification of embodiment 1 will be modified
Microballoon is mixed in methanol, and ultrasonic disperse is uniform, and equal slurries are filled in sky chromatographic column, with packing column machine constant pressure pump in 3000psi
120min is loaded under pressure, after column flattens weighing apparatus, chromatographic column is removed from packing column machine, loads onto column cap, esterification modification is made
Rosin based high molecular chromatographic column.The rosin based high molecular chromatographic column of resulting esterification modification is rinsed with methanol to baseline again and is balanced
It can sample introduction.
(2) it prepares sample solution: taking appropriate Gastrodin, 4- methoxyphenyl β-D- glucopyranoside, dissolved with methanol,
Every 1L is configured to containing Gastrodin 2.5 × 10-4The Gastrodin and 4- methoxyphenyl β-D- glucopyranoside mixed solution of mol,
Sample introduction；
(3) setup parameter: the rosin based high molecular chromatographic column of esterification modification is accessed into liquid chromatograph, liquid chromatogram is set
The flow rate of mobile phase of instrument be 0.3mL/min, Detection wavelength 220nm, 25 DEG C of column oven；
(4) separate: starting sampling valve brings methanol by sample in the rosin based high molecular chromatographic column of esterification modification into, realizes
The separation of Gastrodin, acquired results are as shown in Fig. 2, there is Gastrodin peak in retention time 11.06min, in retention time
Occur 4- methoxyphenyl β-D- glucopyranoside peak, separating degree 2.31 when 12.39min.
Embodiment 8:
A method of the rosin based high molecular chromatographic column of esterification modification separates Gastrodin, carries out in accordance with the following steps:
(1) the rosin based high molecular chromatographic column preparation of esterification modification: the rosin based high molecular that the esterification of embodiment 2 will be modified
Microballoon is mixed in acetonitrile, and ultrasonic disperse is uniform, and equal slurries are filled in sky chromatographic column, with packing column machine constant pressure pump in 3300psi
160min is loaded under pressure, after column flattens weighing apparatus, chromatographic column is removed from packing column machine, loads onto column cap, esterification modification is made
Rosin based high molecular chromatographic column.The rosin based high molecular chromatographic column of resulting esterification modification is rinsed with methanol to baseline again and is balanced
It can sample introduction.
(2) it prepares sample solution: taking appropriate Gastrodin, 4- methoxyphenyl β-D- glucopyranoside, dissolved with methanol,
Every 1L is configured to containing Gastrodin 2.5 × 10-4The Gastrodin and 4- methoxyphenyl β-D- glucopyranoside mixed solution of mol,
Sample introduction；
(2) setup parameter: the rosin based high molecular chromatographic column of esterification modification is accessed into liquid chromatograph, liquid chromatogram is set
The flow rate of mobile phase of instrument be 0.6mL/min, Detection wavelength 250nm, 35 DEG C of column oven；
(3) separate: starting sampling valve brings methanol by sample in the rosin based high molecular chromatographic column of esterification modification into, realizes
The separation of Gastrodin, acquired results are as shown in figure 3, there is Gastrodin peak in retention time 11.22min, in retention time
Occur 4- methoxyphenyl β-D- glucopyranoside peak, separating degree 1.97 when 12.57min.
Embodiment 9:
A method of the rosin based high molecular chromatographic column of esterification modification separates Gastrodin, carries out in accordance with the following steps:
(1) the rosin based high molecular chromatographic column preparation of esterification modification: the rosin based high molecular that the esterification of embodiment 3 will be modified
Microballoon is mixed in chloroform, and ultrasonic disperse is uniform, and equal slurries are filled in sky chromatographic column, with packing column machine constant pressure pump in 3500psi
200min is loaded under pressure, after column flattens weighing apparatus, chromatographic column is removed from packing column machine, loads onto column cap, esterification modification is made
Rosin based high molecular chromatographic column.The rosin based high molecular chromatographic column of resulting esterification modification is rinsed with methanol to baseline again and is balanced
It can sample introduction.
(2) it prepares sample solution: taking appropriate Gastrodin, 4- methoxyphenyl β-D- glucopyranoside, dissolved with methanol,
Every 1L is configured to containing Gastrodin 2.5 × 10-4The Gastrodin and 4- methoxyphenyl β-D- glucopyranoside mixed solution of mol,
Sample introduction；
(3) setup parameter: the rosin based high molecular chromatographic column of esterification modification is accessed into liquid chromatograph, liquid chromatogram is set
The flow rate of mobile phase of instrument be 1.0mL/min, Detection wavelength 270nm, 30 DEG C of column oven；
(4) separate: starting sampling valve brings methanol by sample in the rosin based high molecular chromatographic column of esterification modification into, realizes
The separation of Gastrodin, acquired results are as shown in figure 4, there is Gastrodin peak in retention time 11.18min, in retention time
Occur 4- methoxyphenyl β-D- glucopyranoside peak, separating degree 2.17 when 12.43min.
Likewise, applicant carries out Rhizoma Gastrodiae to the rosinyl polymer microsphere for implementing the preparation-obtained esterification modification of 4-6
The separation of element and 4- methoxyphenyl β-D- glucopyranoside, separating degree can achieve 1.97 or more.
Claims (7)
1. a kind of rosinyl polymer microsphere of esterification modification, it is characterised in that: the rosin based high molecular of the esterification modification is micro-
Ball is the preparation method comprises the following steps: by maleic rosin acrylic acid glycol ester-(methyl) acryl acid-methyl methacrylate copolymer, that is, rosin
Based high molecular microballoon first carries out acylation reaction with acylating reagent, then carries out esterification with esterifying reagent, can be obtained described
It is esterified the rosinyl polymer microsphere of modification.
2. the rosinyl polymer microsphere of esterification modification according to claim 1, it is characterised in that: the esterification is repaired
The rosinyl polymer microsphere of decorations is spherical porous material, and partial size is 5~15 μm, 5~50mgKOH/g of acid value, average pore size
For 10~15nm, specific surface area is 80~150m2/g。
3. a kind of rosinyl polymer microsphere of esterification modification according to claim 1 or 2, it is characterised in that: described
Acylating reagent is oxalyl chloride or thionyl chloride.
4. the rosinyl polymer microsphere of esterification modification according to claim 3, it is characterised in that: the esterifying reagent
One of methanol, ethylene glycol or glycerol.
5. the rosinyl polymer microsphere of esterification modification according to claim 3, it is characterised in that: the acylation reaction
Are as follows: maleic rosin acrylic acid glycol ester-(methyl) acryl acid-methyl methacrylate copolymer, that is, rosin based high molecular is micro-
One of ball and solvent hexamethylene, n-hexane, heptane, acetone, octane, 1,4- dioxane are set in mass ratio for 1:10~16
In reaction vessel, under ice-water bath, stirring condition, acylating reagent, rosin based high molecular and acylating reagent are added dropwise into reaction
Mass ratio is 1:0.3~0.9, after being added dropwise, the heating reflux reaction 4~8 hours under the conditions of 60~85 DEG C, by acylation reaction
Terminate obtained reaction system using vacuum distillation apparatus, steams extra solvent and acylating reagent, obtain acylated abietyl
Polymer microsphere.
6. a kind of rosinyl polymer microsphere of esterification modification according to claim 4 or 5, it is characterised in that: described
Esterification are as follows: by acylated rosinyl polymer microsphere and solvent hexamethylene, n-hexane, heptane, acetone, octane, 1,4- dioxy
One of six rings are that 1:7~13 is added in reactor according to mass ratio, and esterifying reagent, acylated rosin based high molecular is then added
The mass ratio of microballoon and esterifying reagent is 1:0.2~3, is stirred at reflux reaction 1~4 hour under the conditions of 60~80 DEG C, warm water is washed
Microballoon is washed to PH=6~7,10~50h of ethanolic extraction is added the boiling of distilled water agitating and heating and removes the small-molecule substances such as ethyl alcohol,
The rosinyl polymer microsphere of the esterification modification can be obtained.
7. a kind of chromatographic column of the rosinyl polymer microsphere preparation by a kind of any esterification modification of claim 1-6,
It is characterized by: the rosinyl polymer microsphere of esterification modification is mixed in one of methanol, acetonitrile or chloroform, ultrasonic disperse
Uniformly, equal slurries are filled in sky chromatographic column, load 120 under 3000~3500psi pressure with packing column machine constant pressure pump~
Chromatographic column is removed from packing column machine after column flattens weighing apparatus, loads onto column cap by 200min, and the abietyl high score of esterification modification is made
Sub- chromatographic column.
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