CN105646750A - Method for preparation of organic porous monolithic material based on photoinduced thiol-ene polymerization - Google Patents
Method for preparation of organic porous monolithic material based on photoinduced thiol-ene polymerization Download PDFInfo
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Abstract
The invention relates to a method for rapid preparation of an organic monolithic material based on photoinduced thiol-ene polymerization reaction. Specifically, the method includes: mixing a trivinyl compound (functional monomer), a multi-mercapto compound (functional monomer), a pore-forming agent and a photoinitiator and conducting ultrasonic dissolving, then carrying out photoinduced thiol-ene polymerization reaction under the irradiation of an ultraviolet lamp with certain wavelength so as to obtain a porous organic monolithic material by one step. The preparation method has the advantages of mild conditions, high efficiency and controllability, etc., also can select different functional monomers according to different application requirements or adjust the pore-forming agent system to prepare a series of organic monolithic materials with different physical and chemical properties.
Description
Technical field
The present invention relates to a kind of method preparing organic porous integral material based on light-initiated sulfydryl-alkene base polyreaction fast, specifically by ultrasonic to trivinyl compound, many sulfhydryl compounds, porogenic solvents and light-initiated dose of mixing evenly after, utilize light-initiated sulfydryl-alkene base polyreaction (photoinducedthiol-enepolymerizationreaction) organic porous integral material of preparation fast.
Background technology
Porous integral material is a kind of novel separating medium, has that preparation is easy, permeability is good, a stable performance and be easy to the features such as modification, has been widely used in chromatographic separation analysis and sample pretreatment field at present. Capillary monolithic column adopts the mode of in-situ polymerization to be formed in kapillary to have integral material equal, vesicular structure. According to the difference of preparation method and raw material, integral material is divided into again organic whole material, inorganic integral material and organic-inorganic hybrid integral material. Wherein, inorganic integral material physical strength height, skeletal distribution is even, and post effect is high, but preparation process is complicated, and the cycle is longer, and rear modification is also very loaded down with trivial details; Organic whole material preparation process is simple, and permeability and aperture realize by adjusting the proportioning of pore-creating agent, good biocompatibility, pH scope of application width. In addition alternative monomer is very abundant, substantially unrestricted in kind, can select corresponding organic functions monomer according to different needs, also can modify further on the surface of matrix or derive and meets different compartment analysis demands; Hybrid integral material combines organic and inorganic integral material and prepares the advantages such as simple, good mechanical property and high efficiency separation, but there is the problem of pH stability difference. By contrast, organic whole material still occupies the leading position of integral material research, and its preparation method mainly contains radical polymerization, controlled living polymerization etc., but the integral material irregular structure that these methods prepare, and be prepare when thermal initiation mostly, reaction time is still longer. Thus the three-dimensional framework integral material that researcher trial utilizes light-initiated quick preparation orderly.
Click chemistry (clickchemistry) at complex functionality polymkeric substance, prepare and have a wide range of applications in topological framework polymer, finishing and bio-pharmaceutical etc., particularly without metal catalytic sulfydryl-alkene click-reaction (thiol-eneclickreaction) by means of photochemically reactive fast, simple, do not cause the concern of more and more researcher by the advantage such as impact of oxygen.At present, have big quantity research for aspects such as the mechanism of sulfydryl-alkene counterattack reaction, monomer reactivity, reaction kineticses, but it is still little to utilize sulfydryl-alkene polyreaction to prepare the report of porous integral material.
In order to realize preparing organic porous integral material fast, and its microtexture being improved, the present invention has developed a kind of method preparing organic porous integral material based on light-initiated sulfydryl-alkene polyreaction fast. Porous organic whole material prepared by the method has that permeability is good, bio-compatibility is good, and there is following feature: 1, its hole surface modifiability is strong, by methods such as chemical bondings, its surface can be carried out modification, to meet different application request; 2, highly versatile, can adopt other many vinyl compound and many sulfhydryl compounds to be raw material; 3, the method is consuming time short, can complete within general 20min; 4, reaction conditions is gentle, is easy to control, and circulation ratio is better.
Summary of the invention
It is an object of the invention to more quickness and high efficiency prepare a series of organic porous integral material, make prepared organic polymer integral material have high stability, modifiability and efficient compartment analysis ability simultaneously.
For achieving the above object, the technical solution used in the present invention is:
Organic porous integral material is prepared fast: specifically evenly and after removing dissolved oxygen wherein, utilize light-initiated sulfydryl-alkene base polyreaction (photoinducedthiol-enepolymerizationreaction) one step to prepare porous organo polysilica compound integral material by ultrasonic to trivinyl compound (function monomer), many sulfhydryl compounds (function monomer), porogenic solvents and light-initiated dose of mixing based on light-initiated sulfydryl-alkene base polyreaction.
Its detailed process is as follows:
1) in reaction vessel, 12-30mg trivinyl compound is added;
2) in reaction vessel, add many sulfhydryl compounds, make mercapto functional group (-SH) be 1:1.5-1.5:1 with mole (mol) ratio for vinyl-functional (-C=C);
3) in reaction vessel, the diethylene glycol diethyl ether (diethyleneglycoldiethylether, DEGDE) of 80-160 �� L is added, polyoxyethylene glycol (PEG200);
4) in reaction vessel, add light-initiated dose of 2,2-dimethoxy-phenyl methyl phenyl ketone (2,2-dimethoxy-2-phenylacetophenone, DMPA) of 0-1 (not comprising 0) mg.
5) by above-mentioned mixed system at room temperature ultrasonic 1-2min make it dissolve completely to form homogeneous transparent solution, and remove dissolved oxygen wherein;
6) by step 5) in the mixing solutions that obtains be incorporated in container and seal;
7) by step 6) in the container filling mixing solutions that obtains be placed under ultraviolet lamp (��=365nm) reaction, until forming solid;
8) with the above-mentioned integral material of washed with methanol, with the material removing pore-creating agent and unreacted or do not combine, porous organo polysilica compound integral material is obtained.
A kind of method preparing organic porous integral material based on light-initiated sulfydryl-alkene base polyreaction fast of the present invention, its process is as shown in Figure 1.
Described step 1), 2), 3) and 4) in reaction vessel used be UV transparent vial; Described step 1) in the trivinyl compound that adopts be pentaerythritol triallyl ether (pentaerythritoltriallylether, APE), 1,2,4-triethylene cyclohexane (1,2,4-trivinylcyclohexane, TVCH); Described step 2) in many sulfhydryl compounds of adopting be trimethylolpropane tris-3-mercaptopropionic acid ester (trimethylolpropanetris (3-mercaptopropionate), 3SH), tetramethylolmethane four-3-mercaptopropionic acid ester (pentaerythritoltetrakis (3-mercaptopropionate), 4SH);Described step 6) in container used be UV transparent kapillary or UV transparent vial; Described step 7) in reaction times be 6-15min.
What present method adopted is light-initiated sulfydryl-alkene base polyreaction (photoinducedthiol-enepolymerizationreaction), the free radical polymerization reaction that light-initiated dose produces when ultra violet lamp, so reaction needs supersound process mixed solution to carry out deoxygenation before starting.
Sulfydryl-alkene base polyreaction that present method adopts has height specificity, and its polyreaction carries out mainly through vinyl-functional and mercapto functional group and forms integral material. The aperture of prepared porous integral material and pore structure can be regulated and controled by the amount of the composition or content and initiator that change porogenic solvents, light application time etc.
Organic whole material prepared by the present invention has the vesicular structure of comparatively equal, is suitable for chromatographic separation analysis. Liquid chromatography is investigated result and is shown, organic porous integral material surface has hydrophobic property, and centering compound shows typical anti-phase retention mechanism. The many sulfhydryl compounds selected in this experiment are respectively trimethylolpropane tris-3-mercaptopropionic acid ester (3SH) and tetramethylolmethane four-3-mercaptopropionic acid ester (4SH). Experiment shows, shows the post effect of stronger hydrophobicity and Geng Gao containing the organic porous integral post prepared by tetramethylolmethane four-3-mercaptopropionic acid ester (4SH) mixed solution.
The present invention utilizes light-initiated sulfydryl-alkene base polyreaction (photoinducedthiol-enepolymerizationreaction), by selecting different organic functions monomers and regulate pore-creating agent system to prepare a series of porous organic whole material with different physics and chemistry character. Porous organic whole material prepared by this kind of method has that permeability is good, bio-compatibility is good, and its hole surface modifiability is strong, it is possible to by methods such as chemical bondings, its surface is carried out modification, to meet different application request. In addition the method is consuming time short, can complete within general 20min; Highly versatile, can adopt other many vinyl compound and many sulfhydryl compounds to be raw material; Reaction conditions is gentle, is easy to control, and circulation ratio is better.
Accompanying drawing explanation
Fig. 1 prepares organic porous integral material schematic diagram fast based on light-initiated sulfydryl-alkene base polyreaction.
Fig. 2 is the chromatographic separation result of benzene series thing on TVCH-4SH (embodiment 2) organic whole post.
Fig. 3 is the chromatographic separation result of EPA610 on TVCH-4SH (embodiment 2) organic whole post.
Embodiment
Embodiment 1
1, in UV transparent vial, add the TVCH reagent of 20.2mg.
2, in above-mentioned UV transparent vial, add the 3SH of 35.8mg.
3, in above-mentioned UV transparent vial, the diethylene glycol diethyl ether of 120 �� L and the polyoxyethylene glycol of 50 �� L is added.
4, in above-mentioned UV transparent vial, add 0.2mg light-initiated dose of DMPA, wherein each component is mixed the above-mentioned ultrasonic 1min of UV transparent vial, and remove the dissolved oxygen being dissolved in wherein.
5, the mixed solution syringe obtained in step 4 is incorporated in advance in the UV transparent kapillary of 75 ��m (internal diameters) of vinyltrimethoxy silane activation treatment, kapillary two ends silica gel seals subsequently, and then the UV transparent vial sealing of residual mixed liquor will be housed.
6, under the UV transparent kapillary in step 5 and UV transparent vial being placed in ultraviolet lamp (��=365nm), reaction 10min, the mixed solution in UV transparent vial becomes the solid of white.
7, with washed with methanol UV transparent kapillary, the material that pore-creating agent wherein and some do not participate in react is gone out and is namely prepared into kapillary organic whole post. To the solid of the white in UV transparent vial then with methyl alcohol repeatedly washing by soaking namely obtain organic whole material.
Embodiment 2
1, in UV transparent vial, add the TVCH reagent of 16.2mg.
2, in above-mentioned UV transparent vial, add the 4SH of 36.7mg.
3, in above-mentioned UV transparent vial, the diethylene glycol diethyl ether of 105 �� L and the polyoxyethylene glycol of 55 �� L is added.
4, in above-mentioned UV transparent vial, add 0.2mg light-initiated dose of DMPA, wherein each component is mixed the above-mentioned ultrasonic 1-2min of UV transparent vial, and remove the dissolved oxygen being dissolved in wherein.
5, the mixed solution syringe obtained in step 4 is incorporated in advance in the UV transparent kapillary of 75 ��m (internal diameters) of vinyltrimethoxy silane activation treatment, kapillary two ends silica gel seals subsequently, and then the UV transparent vial sealing of residual mixed liquor will be housed.
6, under the UV transparent kapillary in step 5 and UV transparent vial being placed in ultraviolet lamp (��=365nm), reaction 6min, the mixed solution in UV transparent vial becomes the solid of white.
7, with washed with methanol UV transparent kapillary, the material that pore-creating agent wherein and some do not participate in react is gone out and can be prepared into kapillary organic whole post. To the solid of the white in UV transparent vial then with methyl alcohol repeatedly washing by soaking namely obtain organic whole material.
Embodiment 3
1, in UV transparent vial, add the APE reagent of 25.6mg.
2, in above-mentioned UV transparent vial, add the 3SH of 31.2mg.
3, in above-mentioned UV transparent vial, the diethylene glycol diethyl ether of 90 �� L and the polyoxyethylene glycol of 80 �� L is added.
4, in above-mentioned UV transparent vial, add 0.2mg light-initiated dose of DMPA, wherein each component is mixed the above-mentioned ultrasonic 1min of UV transparent vial, and remove the dissolved oxygen being dissolved in wherein.
5, the mixed solution syringe obtained in step 4 is incorporated in advance in the UV transparent kapillary of 75 ��m (internal diameters) of vinyltrimethoxy silane activation treatment, kapillary two ends silica gel seals subsequently, and then the UV transparent vial sealing of residual mixed liquor will be housed.
6, under the UV transparent kapillary in step 5 and UV transparent vial being placed in ultraviolet lamp (��=365nm), reaction 10min, the mixed solution in UV transparent vial becomes the solid of white.
7, with washed with methanol UV transparent kapillary, the material that pore-creating agent wherein and some do not participate in react is gone out and is namely prepared into kapillary organic whole post. To the solid of the white in UV transparent vial then with methyl alcohol repeatedly washing by soaking namely obtain organic whole material.
Embodiment 4
1, in UV transparent vial, add the APE reagent of 21.6mg.
2, in above-mentioned UV transparent vial, add the 4SH of 34.2mg.
3, in above-mentioned UV transparent vial, the diethylene glycol diethyl ether of 110 �� L and the polyoxyethylene glycol of 40 �� L is added.
4, in above-mentioned UV transparent vial, add 0.2mg light-initiated dose of DMPA, wherein each component is mixed the above-mentioned ultrasonic 1min of UV transparent vial, and remove the dissolved oxygen being dissolved in wherein.
5, the mixed solution syringe obtained in step 4 is incorporated in advance in the UV transparent kapillary of 75 ��m (internal diameters) of vinyltrimethoxy silane activation treatment, kapillary two ends silica gel seals subsequently, and then the UV transparent vial sealing of residual mixed liquor will be housed.
6, under the UV transparent kapillary in step 5 and UV transparent vial being placed in ultraviolet lamp (��=365nm), reaction 10min, the mixed solution in UV transparent vial becomes the solid of white.
7, with washed with methanol UV transparent kapillary, the material that pore-creating agent wherein and some do not participate in react is gone out and can be prepared into kapillary organic whole post. To the solid of the white in UV transparent vial then with methyl alcohol repeatedly washing by soaking namely obtain organic whole material.
Fig. 2 is the capillary liquid chromatography separating resulting of benzene series thing on TVCH-4SH (embodiment 2) organic whole post. Experiment condition: post is long, 22cm; Moving phase, acetonitrile/water (v/v, 65/35); Flow velocity, 160 �� L/min (before shunting). Peak in color atlas is followed successively by 1: thiocarbamide, 2: benzene, 3: toluene, 4: ethylbenzene, 5: propyl benzene, 6: butylbenzene, peak sequence by hydrophobicity by weak to going out by force peak, be typical reverse-phase chromatography retention mechanism.
Fig. 3 is the capillary liquid chromatography separating resulting of EPA610 on TVSCH-4SH (embodiment 2) organic whole post. Experiment condition: chromatographic condition post is long, 20cm; Mobile phase A, acetonitrile, Mobile phase B, water; Gradient, mobile phase A from 60% to 100%, time, 20min; Flow velocity, 140 �� L/min (before shunting). Peak in color atlas is followed successively by 1: naphthalene, and 2: acenaphthylene, 3: acenaphthene, 4: fluorenes, 5: luxuriant and rich with fragrance, 6: anthracene, 7: fluoranthene, 8: pyrene, 9: benzo (a) anthracene, 10: bend, 11: benzo (b) fluoranthene, 12: benzo (k) fluoranthene, 13: benzo (a) pyrene, 14: dibenzo (a, h) anthracene, 15: benzo (ghi), 16: indenes is [1,2,3-cd] pyrene also. Illustrate that it has certain application potential in complicated environmental sample field.
Claims (7)
1. based on the method for light-initiated sulfydryl-alkene base polymerization organic porous integral material of preparation, it is characterised in that:
Its process is as follows,
1) in reaction vessel, 12-30mg trivinyl compound is added;
2) in reaction vessel, add many sulfhydryl compounds, make vinyl-functional (-C=C) be 1:1.5-1.5:1 with mole (mol) ratio for mercapto functional group (-SH);
3) in reaction vessel, the diethylene glycol diethyl ether (diethyleneglycoldiethylether, DEGDE) of 80-160 �� L is added, the polyoxyethylene glycol (PEG200) of 0-100 �� L;
4) in reaction vessel, add light-initiated dose of 2,2-dimethoxy-phenyl methyl phenyl ketone (2,2-dimethoxy-2-phenylacetophenone, DMPA) of 0-1mg (not comprising 0);
5) by above-mentioned mixed system at normal temperatures ultrasonic 1-2min make it dissolve completely to form homogeneous transparent solution, and remove dissolved oxygen wherein;
6) by step 5) in the mixing solutions that obtains be incorporated in container and seal;
7) by step 6) in the container filling mixing solutions that obtains be placed under ultraviolet lamp (��=365nm) reaction, until forming solid;
8) with the above-mentioned integral material of washed with methanol, with the material removing pore-creating agent and unreacted or do not combine, organic porous integral material is obtained.
2. method according to claim 1, it is characterised in that: described step 1), 2), 3) and 4) in reaction vessel used be UV transparent vial.
3. method according to claim 1, it is characterized in that: described step 1) in the trivinyl compound that adopts be pentaerythritol triallyl ether (pentaerythritoltriallylether, and/or 1 APE), 2,4-triethylene cyclohexane (1,2,4-trivinylcyclohexane, TVCH).
4. method according to claim 1, it is characterized in that: described step 2) in many sulfhydryl compounds of adopting be trimethylolpropane tris-3-mercaptopropionic acid ester (trimethylolpropanetris (3-mercaptopropionate), 3SH) and/or tetramethylolmethane four-3-mercaptopropionic acid ester (pentaerythritoltetrakis (3-mercaptopropionate), 4SH).
5. preparation method according to claim 1, it is characterised in that: described step 6) in container used be UV transparent kapillary or UV transparent vial.
6. preparation according to claim 1, it is characterised in that: described step 7) in reaction times be 6-15min.
7. preparation according to claim 1, it is characterised in that: described step 5) in and the method that removes dissolved oxygen wherein is ultrasonic deoxygenation, ultrasonic not only make dissolution of solid, also play the effect of deoxygenation in a small amount of solvent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106890479A (en) * | 2017-03-07 | 2017-06-27 | 福州大学 | A kind of preparation method of difunctional affine organic polymer matrix capillary monolithic column |
| CN109461965A (en) * | 2018-11-08 | 2019-03-12 | 海南大学 | A kind of photocuring cellulose gel polymer film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103279011A (en) * | 2013-06-14 | 2013-09-04 | 中国科学院光电技术研究所 | Sulfydryl-alkene ultraviolet curing nanoimprint lithography material |
| CN104084178A (en) * | 2014-06-23 | 2014-10-08 | 广西师范大学 | Stationary phase of POSS hybrid capillary monolithic column, and preparation method thereof |
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2014
- 2014-12-02 CN CN201410720655.6A patent/CN105646750A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103279011A (en) * | 2013-06-14 | 2013-09-04 | 中国科学院光电技术研究所 | Sulfydryl-alkene ultraviolet curing nanoimprint lithography material |
| CN104084178A (en) * | 2014-06-23 | 2014-10-08 | 广西师范大学 | Stationary phase of POSS hybrid capillary monolithic column, and preparation method thereof |
Non-Patent Citations (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106890479A (en) * | 2017-03-07 | 2017-06-27 | 福州大学 | A kind of preparation method of difunctional affine organic polymer matrix capillary monolithic column |
| CN106890479B (en) * | 2017-03-07 | 2019-04-02 | 福州大学 | A kind of preparation method of difunctional affine organic polymer matrix capillary monolithic column |
| CN109461965A (en) * | 2018-11-08 | 2019-03-12 | 海南大学 | A kind of photocuring cellulose gel polymer film and preparation method thereof |
| CN109461965B (en) * | 2018-11-08 | 2022-02-08 | 海南大学 | Photocuring cellulose gel polymer film and preparation method thereof |
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