CN107474254A - The preparation and application of organic-inorganic hydrophilic hybrid integral material - Google Patents
The preparation and application of organic-inorganic hydrophilic hybrid integral material Download PDFInfo
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- CN107474254A CN107474254A CN201610407720.9A CN201610407720A CN107474254A CN 107474254 A CN107474254 A CN 107474254A CN 201610407720 A CN201610407720 A CN 201610407720A CN 107474254 A CN107474254 A CN 107474254A
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000004088 foaming agent Substances 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 4
- -1 sulfhydryl compound Chemical class 0.000 claims abstract description 3
- 239000003999 initiator Substances 0.000 claims abstract 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000009396 hybridization Methods 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical class OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- VHJLVAABSRFDPM-QWWZWVQMSA-N dithiothreitol Chemical compound SC[C@@H](O)[C@H](O)CS VHJLVAABSRFDPM-QWWZWVQMSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 7
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000012650 click reaction Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 7
- 238000005286 illumination Methods 0.000 claims 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005201 scrubbing Methods 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 229910000077 silane Inorganic materials 0.000 abstract description 6
- 230000010148 water-pollination Effects 0.000 abstract description 4
- 238000007445 Chromatographic isolation Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 10
- 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
- 150000001875 compounds Chemical class 0.000 description 6
- 238000003981 capillary liquid chromatography Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 238000002013 hydrophilic interaction chromatography Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 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 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 241000555268 Dendroides Species 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000002398 materia medica Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000003415 nucleophilic catalysis Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000002470 solid-phase micro-extraction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/282—Porous sorbents
- B01J20/285—Porous sorbents based on polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J2220/86—Sorbents applied to inner surfaces of columns or capillaries
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a kind of method for preparing hydrophily hybrid integral material based on sulfydryl-alkene clicking chemistry reaction, the polyhedral oligomeric sesquialter silane reagent after modification, sulfhydryl compound, initiator and pore-foaming agent are specifically mixed into simultaneously ultrasonic dissolution, then generation sulfydryl in situ-alkene clicking chemistry reaction can prepare organic-inorganic hydrophilic hybrid integral material under ultraviolet light.Porous hybrid integral material microstructure is homogeneous regular, and duct is more orderly, there is good application in chromatographic isolation.Described preparation method have the advantages that it is easy to operate it is quick, reaction speed is fast, it can in addition contain select different function monomers and pore-foaming agent system according to different application requirements, a series of porous hybrid integral materials with different physics and chemical property are prepared.
Description
Technical field
Parent is prepared based on light-initiated sulfydryl-alkene clicking chemistry rapid reaction the present invention relates to a kind of
Water-based organic-inorganic hybridization porous monolithic material and its preparation method and application, specifically will be through
Eight vinyl sesquialter silane after the modification of 1- thioglycerols, sulfhydryl compound and light trigger are causing
Ultrasonic dissolution in the solvent of hole, reacted using light-initiated sulfydryl-alkene clicking chemistry
(photoinduced thiol-ene click polymerization reaction) is formed in situ hydrophilic
Organic-the inorganic hybridization porous monolithic material of property.By adjusting the concentration of monomer and the ratio of pore-foaming agent
Example, you can be prepared into the porous hybrid integral material with different surfaces property and function.
Background technology
Since 20th century, the nineties integral post occurred, integral material is as a kind of novel porous
Micro- separating medium is of great interest in Analyze ＆ separate field.With traditional packed column
Compare, capillary monolithic column be easily achieved it is quick prepare and quick separating, have concurrently stable performance,
The advantages that being easy to modification and good permeability, and when analyzing complex sample, the antipollution of integral post
Ability will be significantly stronger than packed column.Because it shows good performance in work is analyzed in separation,
The forth generation chromatography separation media being described as after polysaccharide, crosslinking and coated, single dispersing,
It is widely used in the fields such as materia medica, environmental science and life science.Based on integral material matrix
The difference of property, capillary monolithic column are broadly divided into three classes, i.e. Organic Polymer Monolithic Columns, nothing
Machine integral post and organic-inorganic hybridization integral post.First, organic whole post has preparation process
Simply, good biocompatibility, the advantages that pH scope of applications are wide and selectable monomeric species are relative
It is abundant, it can also be modified or derived in stromal surface.But, organic whole post there is also
Specific surface area is smaller, poor to the separating property of micromolecular compound, in organic phase flow easily
In swelling the problems such as.By comparison, the high mechanical strength of inorganic integral post, solvent tolerance is good,
But prepare cumbersome, also need the processing of further subsequent derivation just to can apply to chromatographic isolation.
The advantages of organic-inorganic hybridization integral post combines both to a certain extent, from 2000
After year Hayes and Malik prepares hydridization integral post using sol-gal process first, hydridization is whole
Scapus is paid close attention to by more and more chromatogram workers, has been widely used in minute yardstick point at present
Matrix from analysis, SPME and immobilized enzyme reactor etc..By years of researches and
Development, have developed a variety of preparation methods, wherein mainly include colloidal sol-gel method,
One kettle way and some other polymerization etc..But it is whole to prepare inorganic-organic hybrid containing silicon substrate
Body material still will pass through multiple steps, and easily influenceed by PH, on repeatability is prepared
Deficiency limits its development, thus develop more quickness and high efficiency hybrid integral material preparation method be
It is necessary.
Click chemistry (click chemistry) has been widely used big in Macroscopic single crystal, dendroid
The field such as molecule preparation and surface modification.Wherein, sulfydryl-alkene clicking chemistry reaction need not
It is transition metal-catalyzed, so that it may to be rapidly completed under the conditions of free radical or nucleophilic catalysis.At present, adopt
The report of integral material is prepared with click chemistry also increasingly to be increased, such as the integral post successfully prepared
Also it is widely used in from simple small molecule to the pretreatment of large biological molecule and complex sample and color
Spectrum separation.The it is proposed of sulfydryl-alkene clicking chemistry reaction opens for the preparation of hybrid integral material
New approaches.Because the light initiating polymerizing reaction containing alkenyl monomer and mercapto monomers is in air and inertia
React same rapid in gas, therefore the reaction there can be preferable physical property to quick preparation
Hybrid integral material.
In recent years, with the development of the subjects such as proteomics, environmental science, pharmaceutical chemistry,
Strong supplement of the hydrophilic Interaction Chromatography (HILIC) as reversed-phase liquid chromatography (RPLC), by
To extensive concern and pay attention to.Relative with RPLC, HILIC uses the flowing of high content organic solvent
Relatively strong polar compound and ionic compound, which include polypeptide, poisonous substance, natural products etc., to be had
Suitable reservation and separating property.Between different types of hydrophilic stationary phase separation selectivity and should
Also differed greatly with scope, therefore the research to novel hydrophilic interaction chromatography material is established to promoting
Rapidly and efficiently method for separating and analyzing important in inhibiting.
The content of the invention
It is whole based on sulfydryl-alkene clicking chemistry reaction preparation hydrophily hydridization the invention provides one kind
The method of body material.Specifically by the function monomer containing sulfydryl, eight containing unsaturated double-bond
After vinyl sesquialter silane, porogenic solvents and light trigger mix ultrasound uniformly, ultraviolet light is utilized
The sulfydryl of initiation-alkene clicking chemistry reaction prepares organic-inorganic hybrid integral material.
The technical solution adopted by the present invention is：
By through 1- thioglycerols modification after the eight vinyl sesquialter silane containing unsaturated double-bond,
Function monomer and light trigger containing sulfydryl are dissolved in porogenic solvents, and ultrasonic mixing is uniformly simultaneously
After removing dissolved oxygen, it is overall to prepare organic-inorganic porous hydridization using sulfydryl-alkene click-reaction
Material, and according to different demands, by adjusting monomer concentration and pore-foaming agent ratio, can make
It is standby go out organic-inorganic porous hybrid integral material of different nature.
Organic-inorganic porous hybrid integral material prepared by the present invention can be applied to chromatogram point
Analysis, be particularly suitable for use in capillary liquid chromatography and liquid chromatogram-mass spectrometry, separation object point
Wei not four kinds of polar compounds, phenyl amines micromolecular compound, antibiotic and complex sample.Knot
Fruit is shown in that the lower four kinds of compounds of hydrophilic pattern reach baseline separation and peak shape is symmetrical, while
In LC-MS, this material can realize the separation and identification of composition in complex sample.
Beneficial effects of the present invention and advantage are:
This method clicks on polymerisation (photoinduced using light-initiated sulfydryl-alkene
Thiol-ene click polymerization reaction), in order to avoid dissolved oxygen produces shadow to reaction
Ring, reaction needs to be ultrasonically treated mixed liquor progress deoxygenation before starting.In order to improve eight vinyl times
The dissolubility of half silane, it is modified by adding a certain proportion of 1- thioglycerols.Have
The formation of machine-inorganic hybridization porous monolithic material only needs to react under ultraviolet lighting, and
And its aperture and pore structure can add crosslinking agent and function monomer concentration and change by changing
The compositions of porogenic solvents or content are regulated and controled.
Hybrid integral material prepared by the present invention has more homogeneous regular loose structure, fits
Analyzed in chromatographic isolation.Liquid chromatogram is investigated result and shown, hybridization porous monolithic material surface tool
There is hydrophilic nmature, centering compound shows typical positive retention mechanism.
Porous organic-inorganic hybrid integral material prepared by the present invention has that permeability is good, color
It is good to compose separating capacity, functionalized modification method is easy, while versatility is stronger, can use other
Sulfydryl function monomer is raw material.
Brief description of the drawings
Fig. 1 is the eight vinyl sesquialter silane after the modification of 1- thioglycerols
MADLI-TOF-MS phenograms.
Fig. 2 be capillary hydridization integral post scanning electron microscope (SEM) photograph (a be 1000 times, b 10000
Times).
Fig. 3 is the capillary liquid chromatography separation figure of capillary hydridization integral post.
Fig. 4 is that the van Deemter of capillary hydridization integral post scheme.
Fig. 5 is the mechanical strength of capillary hydridization integral post.
Fig. 6 is the reaction equation for preparing hybridization porous monolithic material.
Embodiment
One group of embodiment is provided, technical scheme is described, but is not restricted to
Within the scope of this Parameter Conditions, for those skilled in the art, it still can be to reality
Apply the technical scheme described in example to modify, or which part technical characteristic is equal
Replace, within the spirit and principles of the invention, any modification for being made, equivalent substitution,
Improve etc., it should be included in the scope of the protection.
Embodiment 1
Preparation process is as follows：
1) the vinyl silsesquioxanes of 300mg eight are added into UV transparent centrifuge tube；
2) 107.9mg 1- thioglycerols are added into the UV transparent centrifuge tube of step 1)；
3) 10mL tetrahydrofurans are added into the UV transparent centrifuge tube of step 1)；
4) 20 μ L light trigger 2,2- diformazans are added into the UV transparent centrifuge tube of step 1)
Epoxide-phenyl acetophenone (2,2-dimethoxy-2-phenylacetophenone, DMPA)；
5) mixed system that will be obtained after step 4) is ultrasonic at normal temperatures, makes it completely molten
Solution forms homogeneous transparent solution, to remove the dissolved oxygen in mixed system；
6) mixed solution for obtaining step 5) is sealed in UV transparent vial；
7) the UV transparent vial that mixed solution is encapsulate in step 6) is placed under uviol lamp
React 20min；
8) the product at reduced pressure evaporation of solvent for obtaining step 7) UV transparent vial；
9) product that step 8) obtains is added into UV transparent centrifuge tube；
10) 12mg dithiothreitol (DTT)s are added into the UV transparent centrifuge tube of step 9)；
11) 130 μ L tetrahydrofurans and 5 μ L are added into the UV transparent centrifuge tube of step 10)
Lauryl alcohol is as pore-foaming agent；
12) 1 μ L light triggers 2,2- bis- is added into the UV transparent centrifuge tube of step 11)
Methoxyl group-phenyl acetophenone (2,2-dimethoxy-2-phenylacetophenone, DMPA)；
13) mixed system that will be obtained after step 12) is ultrasonic at normal temperatures, makes its complete
Dissolving forms homogeneous transparent solution, to remove the dissolved oxygen in mixed system；
14) mixed solution for obtaining step 13) is sealed in UV transparent centrifuge tube；
15) reactor that mixed solution is encapsulate in step 14) is placed under uviol lamp and reacts 5
min；
16) product that at least 3 step 15) reactors obtain is washed with methanol, by pore-foaming agent
And unreacted or it is uncombined on material go out, it is hybridization porous whole to obtain organic-inorganic hydrophilic
Body material.
The preparation process of embodiment 2 is as follows：
1) the vinyl silsesquioxanes of 300mg eight are added into UV transparent centrifuge tube；
2) 161.8mg 1- thioglycerols are added into the UV transparent centrifuge tube of step 1)；
3) 10mL tetrahydrofurans are added into the UV transparent centrifuge tube of step 1)；
4) 20 μ L light trigger 2,2- diformazans are added into the UV transparent centrifuge tube of step 1)
Epoxide-phenyl acetophenone (2,2-dimethoxy-2-phenylacetophenone, DMPA)；
5) mixed system that will be obtained after step 4) is ultrasonic at normal temperatures, makes it completely molten
Solution forms homogeneous transparent solution, to remove the dissolved oxygen in mixed system；
6) mixed solution for obtaining step 5) is sealed in UV transparent vial；
7) the UV transparent vial that mixed solution is encapsulate in step 6) is placed under uviol lamp
React 20min；
8) the product at reduced pressure evaporation of solvent for obtaining step 7) UV transparent vial；
9) product that step 8) obtains is added into UV transparent centrifuge tube；
10) 12mg dithiothreitol (DTT)s are added into the UV transparent centrifuge tube of step 9)；
11) 130 μ L tetrahydrofurans and 5 μ L are added into the UV transparent centrifuge tube of step 10)
Lauryl alcohol is as pore-foaming agent；
12) 1 μ L light triggers 2,2- bis- is added into the UV transparent centrifuge tube of step 11)
Methoxyl group-phenyl acetophenone (2,2-dimethoxy-2-phenylacetophenone, DMPA)；
13) mixed system that will be obtained after step 12) is ultrasonic at normal temperatures, makes its complete
Dissolving forms homogeneous transparent solution, to remove the dissolved oxygen in mixed system；
14) the μ L of pre-polymerization liquid 1 obtained in step 13) are incorporated into syringe and passed through in advance
Cross 75 μm (internal diameters) of 3- (trimethoxy first silicon substrate) propyl methacrylate activation process
UV transparent capillary in, sealed with postcapillary both ends with silica gel, then will be equipped with residue
The UV transparent centrifugation seal of tube of mixed liquor；
15) the UV transparent capillary in step 14) and UV transparent centrifuge tube are placed in purple
Under outer lamp (λ=365nm), 10min is reacted, the mixing liquid in UV transparent centrifuge tube becomes
Into the solid of white.
16) mixed liquor rinsed with methanol in UV transparent capillary, by pore-foaming agent therein and
Some materials for having neither part nor lot in reaction, which are gone out, is prepared into capillary organic-inorganic hybridization monolithic column,
White solid in UV transparent centrifuge tube is then obtained for 3 times with methanol washing by soaking organic
Integral material.The scanning electron microscope (SEM) photograph of capillary organic-inorganic hybridization monolithic column is shown in Fig. 2, step 8)
The MALDI-TOF-MS mass spectrograms of eight vinyl silsesquioxanes after obtained modification are shown in Fig. 1,
Capillary liquid chromatography separation figure is shown in Fig. 3, the van Deemter figures of capillary organic whole post
See Fig. 4, the mechanical strength of capillary organic-inorganic hybridization monolithic column is shown in Fig. 5, prepare it is organic-
The anti-schematic diagram of inorganic hybridization porous monolithic material is shown in Fig. 6.
Fig. 1 is the MALDI-TOF-MS mass spectrograms of eight vinyl silsesquioxanes after modification,
Mass Spectrometry Conditions are：Molecular weight ranges are 700to 1600Da, wavelength 355nm, detect mould
Formula is linear positive ion mode.The of poor quality of 108Da exactly corresponds to 1- thioglycerols in figure
Molecular weight.
Fig. 3 is toluene, DMF, formamide, thiocarbamide in capillary hybrid inorganic-organic entirety
The capillary liquid chromatography separation figure of post.Chromatographic condition is capillary column (20cm × 75 μm
I.d.), mobile phase is acetonitrile/water (95/5, v/v), and flow velocity is 200 μ L/min (before shunting).Color
Peak in spectrogram is followed successively by (1) toluene, (2) DMF, (3) formamide, (4) thiocarbamide.Appearance is suitable
Sequence grows from weak to strong appearance by hydrophily, is typical normal-phase chromatography retention mechanism.
Fig. 4 is that benzene homologues are schemed in the van Deemter of capillary organic whole post.Chromatographic condition
For capillary column (20cm × 75 μm i.d.), mobile phase is acetonitrile/water (95/5, v/v), flow velocity
For 40-250 μ L/min (before shunting)
From embodiment and accompanying drawing, this method preparation process is simple, and the reaction time is short, made
Standby hydrophily hydridization integral post pattern is homogeneous, and mechanical strength is good, for Separation of Neutral and pole
Property small molecule, there is good separating effect, the advantages that high post effect.Meanwhile by adjusting sulfydryl work(
Energy monomer and eight vinyl silsesquioxane reaction ratios, can prepare a series of different physics
With the hybrid integral material of chemical property, applied to capillary liquid chromatography difference clastotype.
Claims (9)
1. the preparation method of organic-inorganic hydrophilic hybrid integral material, it is characterised in that：
In the presence of photoinitiators, by eight vinyl silsesquioxane (Polyhedral
Oligomeric vinylsilsesquioxane, vinylPOSS) and 1- thioglycerols
(1-Thioglycerol) is dissolved in tetrahydrofuran, through UV illumination after ultrasonic dissolution,
Generation sulfydryl-alkene clicking chemistry reaction, the rotated evaporimeter of product are used as preparation after removing solvent
The presoma of integral material；Presoma further with dithiothreitol (DTT)
(DL-Dithiothreitol, DTT), pore-foaming agent and light trigger mixing and ultrasonic dissolution,
Then sulfydryl-alkene clicking chemistry reaction (thiol-ene occurs under ultra violet lamp
Polymerization click reaction), porous organic-inorganic hybridization is prepared
Integral material.
2. preparation method according to claim 1, it is characterised in that：
The pore-foaming agent is tetrahydrofuran (Tetrahydrofuran, THF) and lauryl alcohol
The mixing of (Dodecyl alcohol)；
The light trigger is 2,2- dimethoxy-phenylfs acetophenone (DMPA).
3. preparation method according to claim 1, it is characterised in that：The ultrasound is molten
The time of solution is 5-10min；The wavelength of the uviol lamp is 360-370nm；Light application time
5-10min。
4. according to the preparation method described in claim 1,2 or 3, it is characterised in that：Its mistake
Journey is as follows,
1) eight vinyl silsesquioxanes are added into UV transparent centrifuge tube；
2) 1- thioglycerols are added into the UV transparent centrifuge tube of step 1)；
3) tetrahydrofuran is added into the UV transparent centrifuge tube of step 1)；
4) added into the UV transparent centrifuge tube of step 1) light trigger 2,2- dimethoxys-
Phenyl acetophenone (2,2-dimethoxy-2-phenylacetophenone, DMPA)；
5) mixed system that will be obtained after step 4) is ultrasonic at normal temperatures, makes it completely molten
Solution forms homogeneous transparent solution, to remove the dissolved oxygen in mixed system；
6) mixed solution for obtaining step 5) is sealed in UV transparent vial；
7) the UV transparent vial that mixed solution is encapsulate in step 6) is placed under uviol lamp
Reaction；
8) the product at reduced pressure evaporation of solvent for obtaining step 7)；
9) product that step 8) obtains is added into UV transparent centrifuge tube；
10) dithiothreitol (DTT) is added into the UV transparent centrifuge tube of step 9)；
11) tetrahydrofuran and lauryl alcohol conduct are added into the UV transparent centrifuge tube of step 10)
Pore-foaming agent；
12) light trigger 2,2- dimethoxies are added into the UV transparent centrifuge tube of step 11)
Base-phenyl acetophenone (2,2-dimethoxy-2-phenylacetophenone, DMPA)；
13) mixed system that will be obtained after step 12) is ultrasonic at normal temperatures, makes its complete
Dissolving forms homogeneous transparent solution, to remove the dissolved oxygen in mixed system；
14) mixed solution for obtaining step 13) is sealed in UV transparent centrifuge tube；
15) the UV transparent centrifuge tube that mixed solution is encapsulate in step 14) is placed in uviol lamp
Lower reaction, until forming solid；
16) product that at least 3 step 15) obtain is washed with methanol, it is by pore-foaming agent and not anti-
Material on should or being not associated with is gone out, and obtains Porous-Organic integral material.
5. the preparation method in step 1)-step 8) according to claim 4, its
It is characterised by：Eight vinyl silsesquioxanes：1- thioglycerols：Tetrahydrofuran：It is light-initiated
The raw material ratio of agent is 600-1000mg:200-700mg:15-30mL:2-5mg.
6. the preparation method in step 9)-step 16) according to claim 4, its
It is characterised by：Eight vinyl silsesquioxanes after the modification that step 8) obtains:Two sulphur threoses
Alcohol:Pore-foaming agent:The raw material ratio of initiator is 30mg:8-16mg:135μL:1-5μL；Institute
The volume range of tetrahydrofuran and lauryl alcohol is 8 in the porogenic solvents stated:1-26:1.
7. the preparation method according to claim 1 or 4, it is characterised in that：By step
14) mixed solution in UV transparent centrifuge tube after ultrasound is introduced into UV transparent capillary, then
Sealed, illumination reaction, methanol scrubbing step, that is, it is hydrophilic to obtain capillary organic and inorganic
Property hydridization integral post.
A kind of 8. organic-inorganic hybridization that any preparation methods of claim 1-8 obtain
Integral material.
9. porous organic-inorganic hybrid integral material is in chromatography described in claim 8
Application.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108187367A (en) * | 2018-01-05 | 2018-06-22 | 福州大学 | Sulfydryl derivatization L-PROLINE type organic-inorganic hybridization monolithic column and preparation method thereof |
| CN108452784A (en) * | 2018-04-04 | 2018-08-28 | 广西民族大学 | Catecholamine Solid Phase Extraction functional composite material and its preparation method and application |
| CN110872383A (en) * | 2018-08-29 | 2020-03-10 | 中国科学院大连化学物理研究所 | Preparation and application of penicillamine modified hierarchical pore hybrid material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172870A (en) * | 2011-12-26 | 2013-06-26 | 北京化工大学 | Polyhedral oligomeric silsesquioxane (POSS) modified double-bond containing elastomer and preparation method thereof |
| CN104109222A (en) * | 2013-04-22 | 2014-10-22 | 中国科学院大连化学物理研究所 | Preparation of hybrid integral materials containing polyhedral oligomeric silsesquioxane reagent |
| CN105504331A (en) * | 2014-09-23 | 2016-04-20 | 中国科学院大连化学物理研究所 | Preparation method of porous integral material |
| CN105566671A (en) * | 2014-10-13 | 2016-05-11 | 中国科学院大连化学物理研究所 | Preparation method of organic-inorganic hybrid porous integral material |
-
2016
- 2016-06-08 CN CN201610407720.9A patent/CN107474254B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172870A (en) * | 2011-12-26 | 2013-06-26 | 北京化工大学 | Polyhedral oligomeric silsesquioxane (POSS) modified double-bond containing elastomer and preparation method thereof |
| CN104109222A (en) * | 2013-04-22 | 2014-10-22 | 中国科学院大连化学物理研究所 | Preparation of hybrid integral materials containing polyhedral oligomeric silsesquioxane reagent |
| CN105504331A (en) * | 2014-09-23 | 2016-04-20 | 中国科学院大连化学物理研究所 | Preparation method of porous integral material |
| CN105566671A (en) * | 2014-10-13 | 2016-05-11 | 中国科学院大连化学物理研究所 | Preparation method of organic-inorganic hybrid porous integral material |
Non-Patent Citations (2)
| Title |
|---|
| FILIPA ALVES,IVO NISCHANG: "Tailor-Made Hybrid Organic-Inorganic Porous Materials Based on Polyhedral Oligomeric Silsesquioxanes (POSS) by the Step-Growth Mechanism of Thiol-Ene "Click" Chemistry", 《CHEMISTRY A EUROPEAN JOURNAL》 * |
| SHEN SHUFEN，YE FANGGUI ET.AL: "Preparation of polyhedral oligomeric silsesquioxane based hybrid monoliths by thiol-ene click chemistry for capillary liquid chromatography", 《ANALYST》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108187367A (en) * | 2018-01-05 | 2018-06-22 | 福州大学 | Sulfydryl derivatization L-PROLINE type organic-inorganic hybridization monolithic column and preparation method thereof |
| CN108452784A (en) * | 2018-04-04 | 2018-08-28 | 广西民族大学 | Catecholamine Solid Phase Extraction functional composite material and its preparation method and application |
| CN108452784B (en) * | 2018-04-04 | 2021-01-26 | 广西民族大学 | Catecholamine solid phase extraction functional composite material, preparation method and application thereof |
| CN110872383A (en) * | 2018-08-29 | 2020-03-10 | 中国科学院大连化学物理研究所 | Preparation and application of penicillamine modified hierarchical pore hybrid material |
| CN110872383B (en) * | 2018-08-29 | 2021-06-22 | 中国科学院大连化学物理研究所 | Preparation and application of penicillamine modified hierarchical pore hybrid material |
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