CN105985484B - A kind of preparation method of the high hydrophobic organic whole material of crosslinking - Google Patents
A kind of preparation method of the high hydrophobic organic whole material of crosslinking Download PDFInfo
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- 238000004132 cross linking Methods 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
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- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- INXWLSDYDXPENO-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CO)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C INXWLSDYDXPENO-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 3
- -1 amyl- Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
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- 239000000243 solution Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- MLNKXLRYCLKJSS-RMKNXTFCSA-N (2e)-2-hydroxyimino-1-phenylethanone Chemical compound O\N=C\C(=O)C1=CC=CC=C1 MLNKXLRYCLKJSS-RMKNXTFCSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
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- 238000005516 engineering process Methods 0.000 abstract description 3
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- 229920000642 polymer Polymers 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000003981 capillary liquid chromatography Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 230000035699 permeability Effects 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
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- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
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- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The present invention relates to field of polymer technology, and in particular to a kind of method for preparing high cross-linked porous organic whole material based on Light lnduced Free Radicals polymerization.The present invention is by the acrylate containing multiple unsaturated double-bonds, function monomer and initiator containing the unsaturated double-bond ultrasonic dissolution in porogenic solvents, raw radical polymerization (free radical polymerization) reaction is issued in ultraviolet light, it is formed in situ porous organic whole material, you can be prepared into the Porous-Organic integral material with different surfaces property and function.Described preparation method has easy to operate quick, the advantages that reaction speed is fast, it can in addition contain select different organic functions monomers and pore-foaming agent system according to different application requirements, a series of porous organic whole materials with different physics and chemical property are prepared.
Description
Technical field
The present invention relates to a kind of method that Porous-Organic integral material is prepared based on radical reaction, will specifically contain not
The dipentaerythritol of saturation double bond is amyl-/hex- acrylic acid, function monomer lauryl methacrylate and initiator are in porogenic solvents
Middle ultrasonic dissolution, raw Raolical polymerizable then is issued in ultraviolet light, be formed in situ porous organic whole material, led to
Overregulate the concentration of monomer and the ratio of pore-foaming agent, you can be prepared into overall with the Porous-Organic of different surfaces property and function
Material.
Background technology
Integral material is a kind of New Stationary Phase developed in recent years, and its structure has a high-permeability, porous and
Big specific surface area, it is reached efficiently quick in work is analyzed in separation, the effect of high flux and low back pressure, be described as
Forth generation chromatography separation media after polysaccharide, crosslinking and coated, single dispersing, be current chromatographic field study hotspot it
One, just received more and more attention in fields such as life science, Pharmaceutical Analysis and environmental monitorings.By the difference of chemical property,
Integral material can be broadly divided into three classes, i.e. organic whole material, inorganic integral material and organic-inorganic hybrid integral material.
Wherein inorganic integral material is a kind of new material that there is bicontinuous structure and diplopore to be distributed, because its unique structure is special
Point, good performance is shown in the fields such as separation, catalysis.Inorganic integral material has good mechanical performance, to organic
The advantages that solvent tolerant is strong, but its preparation process is complicated, and the cycle is longer, introduces relatively difficult, the follow-up derivative work of functional group
Make also comparatively laborious, it is necessary to consume more times and manpower, thus also influence to prepare repeatability.Hybrid inorganic-organic is overall
The advantages of material appearance is later, but it combines organic whole material and inorganic integral material, receives extensive concern in recent years.
In view of silicon skeleton has the characteristics that shaping and easily modification, so existing organic-inorganic hybrid integral material is mainly silicon substrate
Hybrid integral material.But the hybrid integral material of this silicon substrate needs to be made by multiple steps, and process is still more numerous
It is trivial and more sensitive to pH value, along with the speed ratio of used radical polymerization is relatively unmanageable, so causing preparing
Larger deficiency in repeatability also be present.By contrast, organic whole material is the widest a kind of integral material of current research,
Its preparation method is simple, typically that organic monomer, crosslinking agent, pore-foaming agent etc. is well mixed, through thermal initiation or light-initiated original position
Radical polymerization or click-reaction, you can obtain organic whole material.It can be selected not due to the diversity of function monomer, during preparation
With monomer and obtain different selectivity.Simultaneously because its extensive resistance to pH stability, good biocompatibility, permeability
And aperture can be realized by adjusting the proportioning of pore-foaming agent, based on these factors, organic whole material is developed rapidly.
At present, radical polymerization (free radical polymerization) is most normal in prepared by organic whole material
The polymerization methodses of use.Radical polymerization refers to the vinyl monomer containing carbon-carbon double bond, is gathered by radical chain addition
Close the reaction for forming polymer.Because many monomers can carry out radical polymerization, can also carry out in an aqueous medium suspend and
Emulsion polymerization, polymerization process is easy, its favorable reproducibility, thus turns into the important technology of industrial production macromolecule product.
The content of the invention
In order to simplify the preparation process of organic whole material, the invention provides a kind of Porous-Organic entirety material of high crosslinking
The preparation method of material.Specifically by the crosslinking agent containing multiple unsaturated double-bonds, the function monomer containing unsaturated double-bond, pore
After solvent and light trigger mixing ultrasound are uniform, ultraviolet light-initiated Raolical polymerizable (free-radical is utilized
Polymerization) quickly Porous-Organic integral material is prepared.
The technical solution adopted by the present invention is:
Acrylate containing unsaturated double-bond, the function monomer containing unsaturated double-bond and light trigger are dissolved in cause
In the solvent of hole, ultrasonic mixing prepares Porous-Organic entirety uniformly and after removing dissolved oxygen, using the step of Raolical polymerizable one
Material, and according to different demands, by adjusting monomer concentration and pore-foaming agent ratio, can prepare of different nature organic more
Hole integral material.
The described acrylate containing unsaturated double-bond be dipentaerythritol it is amyl-/hex- acrylic acid
(dipentaerythritol penta-/hexa-acrylate, DPEPA), the function monomer containing unsaturated double-bond
For lauryl methacrylate (lauryl methacrylate, LMA).
The porogenic solvents used in described pore system is n-hexyl alcohol (hexyl alcohol) and ethylene glycol
(ethylene glycol) mixes system, or normal propyl alcohol (n-propanol) and BDO (Isosorbide-5-Nitrae-butanediol) mix
And system, the wherein ratio of n-hexyl alcohol and ethylene glycol is 8:1-5:3 (volume ratios);The ratio of normal propyl alcohol and 1,4- butanediols is 8:
1-5:3 (volume ratios).
Preparation method detailed process of the present invention is as follows:
1) acrylate that 20-40mg contains unsaturated double-bond is added into UV transparent centrifuge tube;
2) function monomer that 10-40mg contains unsaturated double-bond is added into the UV transparent centrifuge tube of step 1);
3) 120~220 μ L porogenic solvents are added into the UV transparent centrifuge tube of step 1);
4) 0-1mg light trigger 2,2- dimethoxy-phenylf benzene second is added into the UV transparent centrifuge tube of step 1)
Ketone (2,2-dimethoxy-2-phenylacetophenone, DMPA);
5) by above-mentioned mixed system, ultrasonic 5-10min is completely dissolved it to form homogeneous transparent solution at normal temperatures, and removes
Remove dissolved oxygen therein;
6) mixed solution resulting in step 5) is incorporated into reaction vessel and sealed, be incorporated into reaction vessel and mix
The volume of liquid is closed to make reaction vessel hydraulically full, remainder, which continues to seal in above-mentioned UV transparent centrifuge tube, to be protected
Deposit;
7) reaction vessel for filling mixed solution and UV transparent centrifuge tube resulting in step 6) are placed in uviol lamp
Reacted under (λ=365nm), the reaction time of the mixed liquor in reaction vessel is 3-30min, is mixed in UV transparent centrifuge tube molten
Liquid is reacted to formation solid;
8) use methanol rinsing step 7) reaction vessel in mixed solution, by pore-foaming agent therein and some have neither part nor lot in instead
The material answered, which is gone out, is prepared into organic whole post, then must with methanol washing by soaking 3-5 time to the solid in UV transparent centrifuge tube
To organic whole material.
Wherein, the reaction vessel described in step 6) is UV transparent capillary (75 or 100 μm of internal diameters) or UV transparent
Vial.
The process that the present invention prepares Porous-Organic integral material based on Raolical polymerizable original position is shown below:
This method is using light-initiated Raolical polymerizable, in order to avoid dissolved oxygen has an impact to reaction, instead
Deoxygenation is preferably carried out before should starting.The formation of Porous-Organic integral material only needs to react under ultraviolet lighting, Er Qieqi
Aperture and pore structure can be by changing the composition or content that add crosslinking agent and function monomer concentration and change porogenic solvents
To be regulated and controled.
Organic whole material prepared by the present invention has more homogeneous loose structure, is analyzed suitable for chromatographic isolation.Liquid
Phase chromatogram investigates result and shows that Porous-Organic integral material surface has hydrophobic property, and centering compound is shown typically
Anti-phase retention mechanism.The organic monomer compound selected in this experiment is lauryl methacrylate, has stronger hydrophobicity,
Prepared Porous-Organic integral post shows stronger hydrophobicity and higher post effect.
Porous organic whole material prepared by the present invention has permeability good, and bio-compatibility is good, and hole surface can be modified
Property it is strong, the methods of can passing through chemical bonding, carries out modification to its surface, to meet different application requests;It is general
Property is strong, can use other methacrylates or acrylate functional monomer as raw material;
Preparation method provided by the invention takes short, can be completed within general 20min;Reaction condition is gentle, is easy to control
System, reappearance are preferable.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of capillary organic whole post, wherein (a, c) is that capillary made from embodiment 1 is organic
The scanning electron microscope (SEM) photograph of integral post;(b, d) is the scanning electron microscope (SEM) photograph of capillary organic whole post made from embodiment 2.
Fig. 2 is that benzene homologues separate figure in the high capillary liquid chromatography being crosslinked on organic integral post (embodiment 1).
Fig. 3 is capillary liquid chromatography separation figure of the benzene homologues on low cross-linking organic whole post (embodiment 2).
Embodiment
Embodiment 1
1) 30mg DPEPA reagents, are added into UV transparent centrifuge tube.
2) 17.4mg function monomer LMA, is added into above-mentioned UV transparent centrifuge tube.
3) 140 μ L n-hexyl alcohol and 20 μ L ethylene glycol, are added into above-mentioned UV transparent centrifuge tube.
4) 0.15mg light triggers, are added into above-mentioned UV transparent centrifuge tube.
5), be well mixed each component therein above-mentioned centrifuge tube ultrasound 5min, and remove be dissolved in it is therein molten
Solve oxygen.
6), the μ L of pre-polymerization liquid 1 obtained in step 5) are incorporated into syringe and first pass through 3- (trimethoxy first silicon in advance
Base) propyl methacrylate activation process 75 μm (internal diameters) UV transparent capillary in, with postcapillary both ends silica gel
Sealing, the UV transparent equipped with residual mixed liquor is then centrifuged into the seal of tube.
7) the UV transparent capillary in step 6) and UV transparent centrifuge tube, are placed under uviol lamp (λ=365nm),
Mixed liquor reacts 5min in UV transparent capillary, and the mixed liquor in UV transparent centrifuge tube is reacted to the solid for becoming white.
8), with methanol rinse UV transparent capillary in mixed liquor, by pore-foaming agent therein and some have neither part nor lot in reaction
Material go out and be prepared into capillary organic whole post, the scanning electron microscope (SEM) photograph of capillary organic whole post is shown in Fig. 1 (a, c);It is right
White solid in UV transparent centrifuge tube then obtains organic whole material 3 times with methanol washing by soaking.
Embodiment 2
1) 25mg DPEPA reagents, are added into UV transparent centrifuge tube.
2) 22.4mg function monomer LMA, is added into above-mentioned UV transparent centrifuge tube.
3) 140 μ L n-hexyl alcohol and 20 μ L ethylene glycol, are added into above-mentioned UV transparent centrifuge tube.
4) 0.15mg light triggers, are added into above-mentioned UV transparent centrifuge tube.
5), be well mixed each component therein above-mentioned centrifuge tube ultrasound 5min, and remove be dissolved in it is therein molten
Solve oxygen.
6), the μ L of pre-polymerization liquid 1 obtained in step 5) are incorporated into syringe and first pass through 3- (trimethoxy first silicon in advance
Base) propyl methacrylate activation process 75 μm (internal diameters) UV transparent capillary in, with postcapillary both ends silica gel
Sealing, the UV transparent equipped with residual mixed liquor is then centrifuged into the seal of tube.
7) the UV transparent capillary in step 6) and UV transparent centrifuge tube, are placed under uviol lamp (λ=365nm),
5min is reacted, the mixing liquid in UV transparent centrifuge tube becomes the solid of white.
8), with methanol rinse UV transparent capillary in mixed liquor, by pore-foaming agent therein and some have neither part nor lot in reaction
Material go out and be prepared into capillary organic whole post, the scanning electron microscope (SEM) photograph of capillary organic whole post is shown in Fig. 1 (b, d).It is right
White solid in UV transparent centrifuge tube then obtains organic whole material 3 times with methanol washing by soaking.
Fig. 2 is that benzene homologues separate figure in the high capillary liquid chromatography being crosslinked on organic integral post (embodiment 1).Chromatostrip
Part is capillary column (18cm × 75 μm i.d.), and mobile phase is acetonitrile/water (60/40, v/v), and flow velocity is 170 μ L/min (shuntings
Before).Peak in chromatogram is followed successively by (1) thiocarbamide, (2) benzene, (3) toluene, (4) ethylbenzene, (5) propyl benzene, (6) butylbenzene.Peak sequence
Grown from weak to strong appearance by hydrophobicity, be typical reverse-phase chromatography retention mechanism.
Fig. 3 is capillary liquid chromatography separation figure of the benzene homologues on low cross-linking organic whole post (embodiment 2).Chromatostrip
Part is capillary column (18cm × 75 μm i.d.), and mobile phase is acetonitrile/water (60/40, v/v), and flow velocity is 170 μ L/min (shuntings
Before).Peak in chromatogram is followed successively by (1) thiocarbamide, (2) benzene, (3) toluene, (4) ethylbenzene, (5) propyl benzene, (6) butylbenzene.Peak sequence
Grown from weak to strong appearance by hydrophobicity, be typical reverse-phase chromatography retention mechanism.
From embodiment and accompanying drawing, this method preparation process is simple, and the reaction time is short, and the crosslinking of prepared height is organic whole
Scapus is used to separate small molecule, has the advantages that good separating effect, high post effect.It is possible thereby to infer, contain multiple functional groups
Crosslinking agent is used to prepare integral post, can promote to improve the separation efficiency of capillary liquid chromatography.Meanwhile add difference in functionality list
Body reacts with this crosslinking agent, can prepare the integral post applied to capillary liquid chromatography difference clastotype.
Claims (5)
- A kind of 1. preparation method of hydrophobic organic whole material, it is characterised in that:By the acrylate containing unsaturated double-bond and the function monomer containing unsaturated double-bond, the ultraviolet lighting in pore system Raw Raolical polymerizable is issued, is formed in situ with porous organic whole material;The described acrylate containing unsaturated double-bond be dipentaerythritol it is amyl-/hex- acrylic acid (dipentaerythritol Penta-/hexa-acrylate, DPEPA), the function monomer containing unsaturated double-bond is lauryl methacrylate (lauryl methacrylate, LMA)。
- 2. preparation method according to claim 1, it is characterised in that:The porogenic solvents used in described pore system for N-hexyl alcohol and ethylene glycol mix system, or normal propyl alcohol and BDO mix system.
- 3. preparation method according to claim 1, it is characterised in that:Specific preparation process is as follows,1)The acrylate that 20-40 mg contain unsaturated double-bond is added into UV transparent centrifuge tube;2)To step 1)UV transparent centrifuge tube in add 10-40 mg and contain the function monomer of unsaturated double-bond;3)To step 1)UV transparent centrifuge tube in add 120 ~ 220 μ L porogenic solvents;4)To step 1)UV transparent centrifuge tube in add 0-1 mg, and be 0mg light trigger 2,2- dimethoxys-benzene Benzoylformaldoxime;5)By above-mentioned mixed system, ultrasonic 5-10 min are completely dissolved it to form homogeneous transparent solution at normal temperatures, and remove it In dissolved oxygen;6)By step 5)In obtained by mixed solution be incorporated into reaction vessel and seal, be incorporated into mixed liquor in reaction vessel Volume to make reaction vessel hydraulically full, remainder continues to be sealed in above-mentioned UV transparent centrifuge tube;7)By step 6)In obtained by the reaction vessel for filling mixed solution and UV transparent centrifuge tube to be placed in the nm of λ=365 purple Reacted under outer lamp, reaction time of the mixed liquor in reaction vessel is 3-30min, mixed solution reaction in UV transparent centrifuge tube To formation solid;8)With methanol rinsing step 7)Reaction vessel in mixed solution, by pore-foaming agent therein and some have neither part nor lot in reaction Material, which is gone out, is prepared into organic whole post, is then had for 3-5 times with methanol washing by soaking to the solid in UV transparent centrifuge tube Machine integral material.
- 4. preparation method according to claim 3, it is characterised in that:Step 6)Described in reaction vessel be that internal diameter is 75 Or 100 μm of UV transparent capillaries or UV transparent vial.
- 5. preparation method according to claim 2, it is characterised in that:N-hexyl alcohol and ethylene glycol in described porogenic solvents Volume ratio ratio is 8:1-5:3;Or, the volume ratio ratio of normal propyl alcohol and BDO is 8:1-5:3.
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US20110240541A1 (en) * | 2010-04-06 | 2011-10-06 | Binghe Gu | Monolithic column technology for liquid chromatography |
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2015
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Non-Patent Citations (4)
Title |
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Highly crosslinked polymeric monoliths with various C6 functional groups for reversed-phase capillary liquid chromatography of small molecules;Kun Liu等;《J.Chromatogr.A》;20131029;第1321卷;第80-87页 * |
Monoliths from poly(ethylene glycol) diacrylate and dimethacrylate for capillary hydrophobic interaction chromatography of proteins;Yuanyuan Li等;《J.Chromatogr.A》;20100531;第1217卷;第4934-4945页 * |
Poly[hydroxyethyl acrylate-co-poly(ethylene glycol) diacrylate] Monolithic Column for Efficient Hydrophobic Interaction Chromatography of Proteins;Yuanyuan Li等;《Anal. Chem.》;20091019;第81卷(第22期);第9417页右栏第4段-9418页第1段、第9419页左栏第2段 * |
Sensitive determination of parabens in human urine and serum using methacrylate monoliths and reversed-phase capillary liquid chromatography-mass spectrometry;Enrique Javier Carrasco-Correa等;《J.Chromatogr.A》;20141224;第1379卷;第65-73页 * |
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