CN103736470A - Method and special device for synthesizing liquid chromatogram stationary phase by catalysis of gas-solid phase - Google Patents
Method and special device for synthesizing liquid chromatogram stationary phase by catalysis of gas-solid phase Download PDFInfo
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- CN103736470A CN103736470A CN201310710412.XA CN201310710412A CN103736470A CN 103736470 A CN103736470 A CN 103736470A CN 201310710412 A CN201310710412 A CN 201310710412A CN 103736470 A CN103736470 A CN 103736470A
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Abstract
The invention discloses a method for synthesizing a liquid chromatogram stationary phase. The method comprises the following steps: firstly, performing heating pretreatment on a carrier; then, bonding a gasified catalyst and gasified silane to the carrier; finally, reacting the bonded carrier with a gasified silane capping reagent to obtain the liquid chromatogram stationary phase. A gas-solid phase catalytic fluidized bed synthesis reaction device is established on the basis of a principle that gas molecules have high diffusion speed and facilitate participation in a reaction with solid in each part of particles. The method and the device are easy and convenient to operate and have high reproducibility; the carbon loading amount and the bonding intensity of the chromatographic stationary phase can be greatly improved. A chromatographic filler prepared by the method and the device can be effectively used for the separation and the analysis of acidic, neutral and basic compounds.
Description
Technical field
The present invention relates to a kind of new method of synthetic Stationary Phase for HPLC, belong to liquid chromatogram parting material preparing technical field.
Background technology
High performance liquid chromatography (HPLC) is a kind of widely used analysis chromatographic technique, and its basic principle is to utilize the difference of the distribution coefficient of sample molecule between mutually fixing and mobile phase to realize separated.High-efficient liquid phase chromatogram technology with its fast, efficient, easily be automated and the feature such as high flux sample treatment, become the core analysis technological means of the various fields such as environmental monitoring, medical and health, food security, life science, petrochemical industry, geological prospecting, national security.Can say that chromatographic isolation analytical technology is all-pervasive, be penetrated into the various aspects of national economy.The essence of liquid chromatogram is exactly to improve the ability of chromatographic isolation, along with the complexity of sample, the not raising of intellectual, the separating power of liquid chromatogram is had higher requirement, and impels liquid chromatography technology towards more high-end levels.Liquid-phase chromatographic column is liquid chromatogram " heart ", and the performance of chromatographic column filler is the key that determines chromatogram separating capacity.At present, chromatographic stationary phases host material comprises silica gel, aluminium oxide, titanium oxide, zirconia and cerium oxide etc.In these host materials, silica matrix chromatogram is fixing is be most widely used a kind of mutually, its building-up process mainly comprises: synthetic, the silane of silane and bonding, end-blocking and the dress post etc. of silica gel, wherein bonding techniques is one of important step, is the core technology of production high-quality chromatographic column.At present, the preparation of Stationary Phase for HPLC mainly adopts liquid phase synthesizing method, and bonding density is lower.
Silica matrix bonded stationary phase is to prepare by the chemical reaction between the silicon hydroxyl of organosilan and Silica Surface.Under anhydrous solvent condition, organosilan links by sloughing little molecule formation siloxanes with the surperficial silicon hydroxyl of silica gel, must be except desolventizing, excess reagent and catalyst etc. after having reacted.The major defect of liquid phase bonding reaction is that the reaction site of organosilan molecule can be stoped the silicon hydroxyl reaction of silane and Silica Surface by solvent molecule solvation, thereby suppresses bonding reaction, reduces the fixedly bonding density of phase; The uneven distribution of particle in solvent phase and bonding are agglomerating, have reduced the reappearance of bonding reaction, and the inhomogeneities of this Bonded Phase preparation process, has also caused the fixedly separating property of phase to decline simultaneously; The removal of unreacted silane, catalyst and salt and isolate pure product from reactant mixture, not only loses time but also fritter away energy.In addition, liquid phase bonding reaction requires silane to have higher purity, to reduce impurity in silane and the side reaction of silica matrix as far as possible.
Summary of the invention
The object of the invention is to propose a kind ofly can significantly improve liquid chromatography stuffing carbon carrying capacity and bonding density, synthetic method is easy and simple to handle, reliable and stable, favorable reproducibility, be suitable for the new method of the synthetic Stationary Phase for HPLC of vapor solid catalysis thermopnore of large-scale production, to overcome the main deficiency of existing liquid phase synthetic technology;
A further object of the invention is to provide the special purpose device that above-mentioned vapor solid catalyzes and synthesizes Stationary Phase for HPLC.
Implementation procedure of the present invention is as follows:
A method for synthetic Stationary Phase for HPLC, is characterized in that comprising the following steps:
(1) carrier heating pretreatment;
(2) catalyst of gasification and silane and the carrier bonding of gasification;
(3) further obtain Stationary Phase for HPLC with the Silante terminated reagent reacting of gasification.
Described catalyst be selected from ammonia, methylamine, dimethylamine,
n, N-dimethylethyl amine,
n, N-dimethyl propyl amine,
n, N-dimethylbutyl amine, trimethylamine; Ethamine, diethylamine, triethylamine; Hexahydropyridine, pyridine,
n-picoline, 2-picoline, 2-ethylpyridine, 4-picoline, 2,4-lutidines, 2,6-lutidines, 2,4,6-trimethylpyridine; Imidazoles, 1-methylimidazole, 1-ethyl imidazol(e), glyoxal ethyline, 4-methylimidazole, 1,2-methylimidazole.
Described silane is the C of single or two or trifunctional
1-C
30one or more in organosilan, its chemical structure of general formula is R
1-SiR
2 ax
3-a,
R wherein
1=C
1-C
30replacement or not substituted alkyl, cycloalkyl, Heterocyclylalkyl, replaces or unsubstituted phenyl;
R
2=C
1-C
8replacement or not substituted alkyl, cycloalkyl, Heterocyclylalkyl, replaces or unsubstituted phenyl;
a?=?0,?1,?2;
X=halogen, alkoxyl, acyloxy or amido.
Described Silante terminated reagent is single, one or more in two, three, four or five silane.
Described single silane be trim,ethylchlorosilane,
n,N-dimethyl trimethyl silicane amine, trimethyl silicon based imidazole, methyl trichlorosilane, dimethyldichlorosilane, dimethoxy dimethylsilane, trimethyl silanol or
n-trimethyl silicane yl acetamide; Described disilane is HMDS or 1,3-dimethoxy tetramethyl disiloxane; Three described silane are hexamethyl cyclotrisiloxanes; Described tetrasilane is octamethylcy-clotetrasiloxane; Five described silane are decamethylcyclopentaandoxane.
Described carrier is silica gel, aluminium oxide, titanium dioxide, zirconia or cerium oxide.Described silica matrix particle is spherical porous silica gel, and metals content impurity is less than 30 ppm, and the particle size range of silica matrix particle is 1-60 mm, and pore diameter range is 50-1000, and specific area scope is 50-500 m
2/ g.
The reaction temperature of above-mentioned steps (2) and (3) is 180～400
0c, take and guarantee that catalyst, silane and Silante terminated reagent are vaporized state.
Above-mentioned vapor solid catalyzes and synthesizes the special purpose device of Stationary Phase for HPLC method, its Structural Tectonics is: reactor (0) lower end is communicated with preheater (6), and preheater (6) lower end is respectively by valve A(7), valve B(9), valve C(11) be communicated with vaporize device (8), inert gas, silane vaporizer (12) of catalyst; Apparatus,Soxhlet's (14) bottom is communicated with reactor (0) upper end and silane vaporizer (12) by Y tube (16), and apparatus,Soxhlet's (14) top is connected with condenser (15).
Reactor (0) is provided with top sieve plate (1), extraction plate (5), heater (4) and thermocouple (2).
Heater (4) can be steam or oil bath heating, can be also electric jacket heating.
Siphon pipe (13) the upper end height of apparatus,Soxhlet's (14) can be uncertain, but in order to reduce accumulating of phegma, siphon pipe is lower is advisable; Lower end extends to below steam (vapor) outlet, to avoid withdrawing fluid Returning reactor (0).
When catalyst is gaseous state, they also can for example nitrogen, argon gas, helium mix enter reactor (0) with inert gas.
Beneficial effect of the present invention:
(1) due to the greatest differences of gas-solid raw material physical property, cause raw material in mixed process, easily to produce raw material and mix inhomogeneous problem, thus the carrying out of impact reaction.Gas-solid phase reaction device of the present invention utilizes gas to make solid particle complete gas-solid-phase catalytic reaction process in suspended motion state by granular solids layer.The present invention utilizes silane to react the gas discharging with carrier situ, and inert gas, makes carrier granular in suspended motion state, thereby effectively maintains fluidization process, has realized granule carrier and in thermopnore, has evenly carried out bonding reaction.The motion of fluid and particle makes bed have good heat transfer property, and bed internal temperature is even, and is easy to control, and can effectively solve because gas-solid reaction raw material mixes inhomogeneous problem;
(2) vapor solid catalysis thermopnore reaction unit of the present invention utilizes gas molecule diffusion velocity fast, is conducive to participate in the principle of reacting at each position of particle with solid, and reaction speed is better than liquid-solid reaction.Be easy to control silane vaporization reaction temperature simultaneously, reduce high-boiling-point impurity and participate in reaction, be suitable for organosilan to be bonded to the synthetic method on solid carrier;
(3) vapor solid catalysis thermopnore reaction unit of the present invention utilizes Soxhlet to extract solvent and recycles principle, and the iterative cycles that is conducive to raw material silane is used, and avoids unreacted reactant condensation Returning reactor, reduces reaction efficiency;
(4) gas-solid-phase catalytic reaction device of the present invention can be in reactor dry support easily, avoid loading the process moisture absorption; In reactor, carry out post processing simultaneously, convenient succinct;
(5) compare with conventional liquid phase bonding techniques, vapor solid catalysis bonding reaction activity is high, and synthetic method is reliable and stable, favorable reproducibility, and bonding density is high, is easy to large-scale production and automation.
Accompanying drawing explanation
Fig. 1 is vapor solid catalysis thermopnore reaction unit structural representation of the present invention;
Fig. 2 is the C that utilizes the gas-solid catalysis process of embodiment 1 to prepare in embodiment 4
18chromatographic column, C prepared by embodiment 3 liquid phase synthesizing methods
18chromatographic column and Agilent TC-C
18the chromatogram of chromatographic column to the separation of pyridine-phenol;
Fig. 3 is chromatographic column and the GL Science Inertsil C that utilizes embodiment 2 preparations in embodiment 5
8(3) chromatogram of post to the separation of metacortandracin-cortisone-prednisolone-Beta meter Song-cortisone-hydrocortisone acetate-cortisone acetate mixture;
Fig. 4 is chromatographic column and the Waters SunFire C that utilizes embodiment 2 preparations in embodiment 6
8the chromatogram of post to the separation of pyridoxamine-ascorbic acid-orotic acid-niacinamide mixture;
In Fig. 1: 0 is reactor, and 1 is top sieve plate; 2 is thermocouple; 3 is carrier; 4 is heater; 5 is extraction plate; 6 is preheater; 7 is valve A; 9 is valve B; 11 is valve C; 8 is catalyst vaporization device; 10 is flowmeter; 12 is silane vaporizer; 13 is siphon pipe;
14for apparatus,Soxhlet's; 15 is condenser.
The specific embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Structural Tectonics and the operation principle of vapor solid catalysis thermopnore reaction unit of the present invention are as follows: reactor (0) top and bottom are top sieve plate (1) and extraction plate (5), and carrier (3) is inserted in reactor (0).The voidage of sieve plate can be changed as required, and the main purpose of using sieve plate is to support the weight of silica matrix, makes whole sieve plate surface have the pressure of homogeneous, thereby makes the interior air-flow of post bed more even.Inert gas is through flowmeter (10), valve B(
9)and preheater (
6)enter reactor (0).Silane silane vaporizer (
12)after middle heating vaporization, through valve C(
11)enter preheater (
6), further, after heating, enter reactor (0).Simultaneously by catalyst catalyst vaporize device (
8)middle vaporization, through valve A(
7)enter preheater (6), further after heating, enter reactor (0), carry out gas-solid-phase catalytic reaction with carrier (3).Heater for reactor (0) (
4)maintain reaction temperature, in the upper and lower portion of reactor (0), be respectively equipped with a thermocouple (
2), measure temperature in tower.Unreacted silane gas process apparatus,Soxhlet's (
14)side pipe rise to condenser tube (
15), after condensation, get back in apparatus,Soxhlet's (14), then through siphon pipe (
13)get back in silane vaporizer (12).Due to siphon pipe (
13)lower end extends to steam (vapor) outlet lower end, can guarantee that the liquid of backflow is all got back in silane vaporizer (12).Repeat-heating vaporization recycles, and repeatedly reacts with carrier (3).After reaction completes, in tower, Bonded Phase washs with different solvents, and waste liquid is through valve A(7) discharge.Then in tower, pass into inert gas, Bonded Phase heater via (4) heating is dried.Dried Bonded Phase, with above-mentioned similar approach, adds Silante terminated reagent to carry out end capping reaction, obtains fixedly phase of target product.
Embodiment
1gas-solid catalysis method is prepared C18 chromatographic stationary phases
By 100 grams of silica gel (
3)(AGC Si-Tech Co. Ltd., 5 mm, 100,440 m
2/ g) insert in reactor (0), open valve B(9), drying nitrogen passes in reactor (0) through flowmeter (10) and preheater (6), silica gel (3) heater via (
4)be heated to 170
0dry 24 hours of C.By 600 gram of 18 carbon dimethylchlorosilane join silane vaporizer (
12)in, and being heated to boiling, the silane after vaporization is through valve C(
11)enter preheater (
6), further after heating, pass in reactor (0), simultaneously by ammonia through the catalyst device (8) of vaporizing
,valve A(
7)and preheater (
6)pass in reactor (0) and react with silica gel (3).With heater (4), maintain reaction temperature 340
oc left and right.Unreacted 18 carbon dimethylchlorosilanes, after condenser (15) condensation, are got back in apparatus,Soxhlet's (14), then get back in silane vaporizer (12) through siphon pipe (13).Because siphon pipe (13) lower end extends to steam (vapor) outlet lower end, can guarantee that the liquid of backflow is got back in silane vaporizer (12) completely.Repeat-heating vaporization recycles, and repeatedly reacts with silica gel, stops reaction after 12 hours.Valve-off A(
7)with valve C(
11), reactor (0) is cooled to room temperature under nitrogen.Valve-off B(
9), Bonded Phase is used toluene, carrene, oxolane, methanol-water (1:1, v/v) successively, methanol wash, and waste liquid is through valve A(
7)discharge.Valve-off A(
7), open valve B(
9), in reactor, pass into inert gas, Bonded Phase heater via (
4)heating is dried.Dried Bonded Phase, with above-mentioned similar approach, adds Silante terminated reagent to carry out end capping reaction, obtains fixedly phase.
The gas-solid catalysis method of embodiment 2 is prepared C8 chromatographic stationary phases
By 100 grams of silica gel (3) (AGC Si-Tech Co. Ltd., 5 mm, 100,440 m
2/ g) insert in reactor (0), silica gel (3) is heated to 170
0dry 24 hours of C, by 150-200 milliliter pyridine join catalyst vaporization device (
8)in, and being heated to boiling, the catalyst after vaporization is through valve A(
7)enter preheater (
6), further, after heating, enter in reactor (0).500 milliliters of carbon, eight dimethyl methyl TMOSs are joined simultaneously silane vaporizer (
12)in, and being heated to boiling, the silane after vaporization is through valve C(
11)enter preheater (
6), further, after heating, enter in reactor (0) and react with silica gel (3), use heating system (
4)maintain reaction temperature 200
0c left and right.Unreacted eight carbon dimethyl methyl TMOSs through condenser (
15)after condensation, get back to apparatus,Soxhlet's (
14)in, then through siphon pipe (
13)get back in silane vaporizer (12).Repeat-heating vaporization recycles, and repeatedly reacts with silica gel, stops reaction, valve-off A(after 8 hours
7)with valve C(
11), reactor (0) is cooled to room temperature under nitrogen.Valve-off B(
9), Bonded Phase is used toluene, carrene, oxolane, methanol-water (1:1, v/v) successively, methanol wash, and waste liquid is through valve A(
7)discharge.Valve-off A(
7), open valve B(
9), in reactor, pass into inert gas, Bonded Phase heater via (
4)heating is dried.Dried Bonded Phase, with above-mentioned similar approach, adds Silante terminated reagent to carry out end capping reaction, obtains fixedly phase.
In three-necked bottle, add 10 grams of spherical silica gels (AGC Si-Tech Co. Ltd., 5 mm, 100,440 m
2/ g), 170
0under C, be dried 24 hours.After silica gel is cooling under argon gas atmosphere, add dimethylbenzene (100 milliliters), 18 carbon dimethylchlorosilanes (18 grams) and pyridine (5 milliliters), mechanical agitation is also heated to reflux under argon gas, reacts 16 hours.Stop reaction, vacuum filtration, uses toluene successively, carrene, oxolane, acetone, methanol-water (1:1, v/v), methanol wash, 80
0dry 24 hours of C.Bonded silica gel is put into reactor, add dimethylbenzene (100 milliliters) and HMDS (10 milliliters), mechanical agitation is also heated to reflux under argon gas atmosphere, reacts 16 hours.Stop reaction, vacuum filtration, uses toluene successively, carrene, oxolane, acetone, methanol-water (1:1, v/v), methanol wash, 80
0dry 24 hours of C, obtains fixedly phase.
Table 1 has compared vapor solid catalysis thermopnore and has prepared the fixedly method of phase of C18 with liquid phase bonding, C prepared by vapor solid catalysis thermopnore synthetic method
18fixing phase, carbon carrying capacity, bonding density, post effect and the pH scope of application are all greatly improved, and chromatographic column slightly increases the reservation of hydrophobic compound.
Adopt above-mentioned experimental technique, C prepared by the present invention
18the result that chromatographic column is compared with commercial like product is as shown in table 2.
From the results shown in Table 2, compare with commercial like product, the chromatograph packing material that utilizes vapor solid catalysis thermopnore technology to produce, carbon carrying capacity and bonding density obviously improve.
By the silica filler of preparing in above-described embodiment, adopt homogenate method to be filled in 150 x 4.6 mm I.D. stainless steel tubes, fill pressure is 40-80 MPa, gained chromatographic column is for separating of blend sample.
The separation of 4 pairs of pyridine-phenol of embodiment
Use respectively the chromatographic column of (a) embodiment of the present invention 1 preparation, (b) chromatographic column of embodiment 3 preparations and (c) Agilent Zorbax TC-C
18post, separated 1 pyridine, 2 phenol mixture, Fig. 2 is its chromatogram.Chromatographic condition is as follows: mobile phase, acetonitrile: water=1:1 (v/v); Flow velocity, 1 mL/min; Column temperature, 30
0c; Detect wavelength, UV 254 nm.The resulting peak shape of chromatographic column of the present invention is obviously better than traditional C
18the accordingly result of chromatographic column gained.
The separation of 5 pairs of steroids of embodiment
The chromatographic column of use (a) embodiment 2 preparations and (b) GL Science Inertsil C respectively
8(3) post, separated 1 metacortandracin, 2 cortisones, 3 prednisolones, 4 Beta rice pines, 5 cortisones, 6 hydrocortisone acetates, 7 cortisone acetate mixtures, Fig. 3 is its chromatogram.Chromatographic condition is as follows: mobile phase, methyl alcohol: water=1:1 (v/v); Flow velocity, 1 mL/min; Column temperature, 30
0c; Detect wavelength, UV 254 nm.
The separation of 6 pairs of water soluble vitamins of embodiment
The chromatographic column of use (a) embodiment 2 preparations and (b) Waters SunFire C respectively
8post, separated 1 pyridoxamine, 2 ascorbic acid, 3 orotic acids, 4 niacinamide mixtures, Fig. 4 is its chromatogram.Chromatographic condition is as follows: mobile phase, methyl alcohol: 10 mM NH
4the COOH aqueous solution (pH 3.0)=5:95 (v/v); Flow velocity, 1 mL/min; Column temperature, 30
0c; Detect wavelength, UV 254 nm.
Claims (10)
1. a method for synthetic Stationary Phase for HPLC, is characterized in that comprising the following steps:
(1) carrier heating pretreatment;
(2) catalyst of gasification and silane and the carrier bonding of gasification;
(3) further obtain Stationary Phase for HPLC with the Silante terminated reagent reacting of gasification.
2. the method for synthetic Stationary Phase for HPLC according to claim 1, is characterized in that: described catalyst be selected from ammonia, methylamine, dimethylamine,
n, N-dimethylethyl amine,
n, N-dimethyl propyl amine,
n, N-dimethylbutyl amine, trimethylamine; Ethamine, diethylamine, triethylamine; Hexahydropyridine, pyridine,
n-picoline, 2-picoline, 2-ethylpyridine, 4-picoline, 2,4-lutidines, 2,6-lutidines, 2,4,6-trimethylpyridine; Imidazoles, 1-methylimidazole, 1-ethyl imidazol(e), glyoxal ethyline, 4-methylimidazole, 1,2-methylimidazole.
3. synthesize according to claim 1 the method for Stationary Phase for HPLC, it is characterized in that: described silane is the C of single or two or trifunctional
1-C
30one or more in organosilan, its chemical structure of general formula is R
1-SiR
2 ax
3-a,
R wherein
1=C
1-C
30replacement or not substituted alkyl, cycloalkyl, Heterocyclylalkyl, replaces or unsubstituted phenyl;
R
2=C
1-C
8replacement or not substituted alkyl, cycloalkyl, Heterocyclylalkyl, replaces or unsubstituted phenyl;
a?=?0,?1,?2;
X=halogen, alkoxyl, acyloxy or amido.
4. synthesize according to claim 1 the method for Stationary Phase for HPLC, it is characterized in that: described Silante terminated reagent is single, one or more in two, three, four or five silane.
5. the method for synthetic Stationary Phase for HPLC according to claim 4, is characterized in that: described single silane be trim,ethylchlorosilane,
n,N-dimethyl trimethyl silicane amine, trimethyl silicon based imidazole, methyl trichlorosilane, dimethyldichlorosilane, dimethoxy dimethylsilane, trimethyl silanol or
n-trimethyl silicane yl acetamide; Described disilane is HMDS or 1,3-dimethoxy tetramethyl disiloxane; Three described silane are hexamethyl cyclotrisiloxanes; Described tetrasilane is octamethylcy-clotetrasiloxane; Five described silane are decamethylcyclopentaandoxane.
6. synthesize according to claim 1 the method for Stationary Phase for HPLC, it is characterized in that: described carrier is silica gel, aluminium oxide, titanium dioxide, zirconia or cerium oxide.
7. synthesize according to claim 6 the method for Stationary Phase for HPLC, it is characterized in that: described silica matrix particle is spherical porous silica gel, metals content impurity is less than 30 ppm, the particle size range of silica matrix particle is 1-60 mm, pore diameter range is 50-1000, and specific area scope is 50-500 m
2/ g.
8. synthesize according to claim 1 the method for Stationary Phase for HPLC, it is characterized in that: the reaction temperature of step (2) and (3) is 180～400
0c.
9. one of any described vapor solid of claim 1 to 8 catalyzes and synthesizes the special purpose device of Stationary Phase for HPLC method, it is characterized in that: reactor (0) lower end is communicated with preheater (6), preheater (6) lower end is respectively by valve A(7), valve B(9), valve C(11) be communicated with vaporize device (8), inert gas, silane vaporizer (12) of catalyst; Apparatus,Soxhlet's (14) bottom is communicated with reactor (0) upper end and silane vaporizer (12) by Y tube (16), and apparatus,Soxhlet's (14) top is connected with condenser (15).
10. special purpose device according to claim 9, is characterized in that: reactor (0) is provided with top sieve plate (1), extraction plate (5), heater (4) and thermocouple (2).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109704985A (en) * | 2019-01-04 | 2019-05-03 | 江苏汉邦科技有限公司 | A kind of condensed-nuclei aromatics base amide embedded type Stationary Phase for HPLC synthetic method |
| CN113694907A (en) * | 2020-05-22 | 2021-11-26 | 中国科学院大连化学物理研究所 | Pure water-resistant chromatographic stationary phase and preparation method and application thereof |
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Cited By (3)
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| CN109704985A (en) * | 2019-01-04 | 2019-05-03 | 江苏汉邦科技有限公司 | A kind of condensed-nuclei aromatics base amide embedded type Stationary Phase for HPLC synthetic method |
| CN109704985B (en) * | 2019-01-04 | 2022-03-11 | 江苏汉邦科技有限公司 | Method for synthesizing condensed ring aromatic alkyl amide embedded liquid chromatography stationary phase |
| CN113694907A (en) * | 2020-05-22 | 2021-11-26 | 中国科学院大连化学物理研究所 | Pure water-resistant chromatographic stationary phase and preparation method and application thereof |
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