CN102964541B - Preparation method of weak-acid cation chromatographic column filler exchange resin - Google Patents
Preparation method of weak-acid cation chromatographic column filler exchange resin Download PDFInfo
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- CN102964541B CN102964541B CN201210508029.1A CN201210508029A CN102964541B CN 102964541 B CN102964541 B CN 102964541B CN 201210508029 A CN201210508029 A CN 201210508029A CN 102964541 B CN102964541 B CN 102964541B
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- 239000011347 resin Substances 0.000 title claims abstract description 73
- 229920005989 resin Polymers 0.000 title claims abstract description 73
- 150000001768 cations Chemical class 0.000 title claims abstract description 64
- 239000000945 filler Substances 0.000 title claims abstract description 63
- 239000002253 acid Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000741 silica gel Substances 0.000 claims abstract description 52
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 52
- 238000005054 agglomeration Methods 0.000 claims abstract description 44
- 230000002776 aggregation Effects 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- UJKWLAZYSLJTKA-UHFFFAOYSA-N edma Chemical compound O1CCOC2=CC(CC(C)NC)=CC=C21 UJKWLAZYSLJTKA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920003053 polystyrene-divinylbenzene Chemical group 0.000 claims abstract description 15
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- 229920001296 polysiloxane Polymers 0.000 claims description 26
- 230000008961 swelling Effects 0.000 claims description 26
- 230000004913 activation Effects 0.000 claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010559 graft polymerization reaction Methods 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 abstract description 23
- 239000002585 base Substances 0.000 abstract description 22
- 150000002500 ions Chemical class 0.000 abstract description 21
- 238000000926 separation method Methods 0.000 abstract description 21
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract description 19
- 238000001514 detection method Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003729 cation exchange resin Substances 0.000 abstract description 6
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract 2
- 239000004005 microsphere Substances 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 abstract 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 235000002906 tartaric acid Nutrition 0.000 abstract 1
- 239000011975 tartaric acid Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000003513 alkali Substances 0.000 description 18
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 238000010992 reflux Methods 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 229940095064 tartrate Drugs 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The invention relates to a preparation method of weak-acid cation chromatographic column filler exchange resin of an ion chromatographic column. The exchange resin is used for preparing weak-acid cation chromatographic column filler. According to the invention, spherical silica gel base material, or PGMA/EDMA, PVA or PS-DVB exchange resin polymer microsphere base material firstly experiences a surface pre-agglomeration reaction with maleic anhydride and then is subjected to a regular grafting polymerization reaction to obtain exchange resin. The method provided by the invention solves the technical problems that ethylenediamine/tartaric acid leacheate is required for separating alkali metal and alkali metal ions at the same time and the system peak of the ethylenediamine influences the analysis result in the existing weak cation chromatographic column filler of exchange resin prepared by taking silica gel as a base body, the reaction process is relatively complicated and a Friedel-Crafts acylation reaction is needed before washing to remove chloride ions in the double-bond aliphatic weak-acid cation-exchange resin prepared by taking polymer microspheres as a base body, and the degree of separation and peak shape of the detection result of chromatographic column analysis of the filler prepared from the exchange resin are unsatisfactory.
Description
Technical field
The present invention relates to ion chromatographic column, is a kind of preparation method of weak-acid cation chromatographic column filler exchange resin concretely.
Background technology
Phase research notes in " analytical chemistry " February the 2nd in 1998 " polymaleic acid sandwiches silica matrix single-column weak cation chromatographic packing " discloses a kind of pretreated silica particles and methyl vinyl diethoxysilane reactions and obtains silylating reagent silica gel, again silylating reagent silica gel and maleic anhydride are obtained by reacting copolymerization product, prepare the technology of weak cation chromatographic packing, the chromatographic column of this filler overcomes existing polyhutadiene-toxilic acid coating silica matrix stationary phase to the alkali and alkaline earth metal ions ion unsatisfied technical problem of separating effect simultaneously, but need be separated with quadrol/tartrate leacheate, the system peak impact analysis result of quadrol subsequently." process engineering journal " the 7th volume the 5th phase " a kind of preparation of the aliphatics weakly acidic cation-exchange resin containing double bond " discloses a kind of MALEIC ANHYDRIDE that adopts as acylting agent, by the Friedel-Crafts acylation reaction of PS-DVB, obtain the technology containing double bond aliphatics weakly acidic cation-exchange resin preparing ion chromatographic column filler, it is low that this resin overcomes usual PS-DVB crosslinking copolymers degree, the technical problem that in multipolymer, suspended double bond content is not high, but there is reaction process more complicated, need after polymers swell to carry out Friedel-Crafts acylation reaction, and then wash dechlorination ion and just can obtain PS-MAH-COOH, this exchange resin makes the chromatographic column of filler and there is analytical results resolution and the undesirable drawback of peak shape.
Summary of the invention
It is that the weak cation chromatographic packing of exchange resin prepared by matrix exists alkali and alkaline earth metal ions ion and is separated simultaneously and need uses quadrol/tartrate leacheate, the system peak impact analysis result of quadrol with silica gel that the present invention will solve existing, take polymer microballoon as the reaction process more complicated that the aliphatics weakly acidic cation-exchange resin of double bond prepared by matrix exists, dechlorination ion is washed again after Friedel-Crafts acylation reaction need be carried out, this exchange resin makes the resolution of chromatogram column analysis result of filler and the undesirable technical problem of peak shape, there is provided a kind of Subacidity cation chromatographic column of making to be only separated with simple nitric acid leacheate alkali and alkaline earth metal ions ion simultaneously, not impact analysis result, analytical test cost is low, analyzing and testing result is reappeared, post effect is higher, resolution and ion peak shape good dynamically to activate, silicone hydroxyl spherical silica gel is base-material, empty consumption is low, the preparation method of the weak-acid cation chromatographic column filler exchange resin that percentage of grafting is high, or a kind of Subacidity cation chromatogram column analysis detected result of making is reappeared, post effect is higher, resolution and ion peak shape good with PGMA/EDMA, PVA or PS-DVB swelling exchange resin completely polymer microballoon is base-material, manufacture craft is simple, react completely, empty consumption is low, the preparation method of the weak-acid cation chromatographic column filler exchange resin that percentage of grafting is high.
In order to solve above-mentioned technical problem, the technical scheme that the present invention takes is: a kind of preparation method of weak-acid cation chromatographic column filler exchange resin, comprise dynamically activating, silicone hydroxyl spherical silica gel is base-material, or PGMA/EDMA, PVA or PS-DVB swelling exchange resin completely polymer microballoon is base-material, described invention, spherical silica gel base material, or described PGMA/EDMA, PVA or PS-DVB exchange resin polymer microballoon base-material first carries out the pre-agglomeration reaction in surface with maleic anhydride, regular graft polymerization reaction is carried out again with maleic anhydride, obtained weak-acid cation chromatographic column filler exchange resin.
The present invention adds the surface pre-agglomeration unsaturated carboxylic acid radical reaction process of dynamic activation, silicone hydroxyl spherical silica gel and PGMA/EDMA, PVA or PS-DVB swelling exchange resin completely polymer microballoon and maleic anhydride in the preparation method of existing weak-acid cation chromatographic column filler exchange resin, the preliminary grafting of working substance, be attached on base-material, next carry out degree of depth graft polymerization reaction with maleic anhydride again, achieve graft polymerization more completely.So, with silica gel be matrix prepare exchange resin void consumption low, percentage of grafting is high, the Subacidity cation chromatographic column making filler with this exchange resin to one of alkali and alkaline earth metal ions routine, the simple nitric acid leacheate of divalent cation is separated simultaneously, not impact analysis result, analytical test cost is low, analyzes to use that result is reappeared, post effect is higher, resolution and the good advantage of ion peak shape; The manufacture craft of the aliphatics weakly acidic cation-exchange resin containing double bond prepared for matrix with exchange resin polymkeric substance is simple, react completely, empty consumption is low, percentage of grafting is high, the Subacidity cation chromatographic column of this exchange resin filler has that analytical test result is reappeared, post effect is higher, resolution and the good advantage of ion peak shape.
Described invention, spherical silica gel base material, or described PGMA/EDMA, PVA or PS-DVB exchange resin polymer microballoon base-material first carries out surface agglomeration reaction in advance with maleic anhydride and vinylbenzene or divinyl.Vinylbenzene or divinyl unsaturates make maleic anhydride easily and the pre-agglomeration reaction of base-material surface grafting as polymerization toughener.
Diisopropyl azodicarboxylate initiator is adopted in the pre-agglomeration reaction in surface.Oil-soluble azo initiator stable reaction.
The temperature 35-65 DEG C of the pre-agglomeration in surface.Temperature is lower than 35 DEG C, and the pre-agglomeration speed in surface sharply slows down, and even can not carry out; Higher than 65 DEG C, the pre-agglomeration initiator in surface easily causes implode.
The temperature 45-55 DEG C of the pre-agglomeration in surface.This is preferred temperature.
The pre-agglomeration ultrasonic reaction 3.5-6.5 hour at ambient pressure in surface.The time of ultrasonic reaction affects by the temperature of the pre-agglomeration in surface.The temperature of the pre-agglomeration in surface is low, and ultrasonic reaction is long; The temperature of the pre-agglomeration in surface is high, and ultrasonic reaction is short.
The pre-agglomeration ultrasonic reaction 4.5-5.5 hour at ambient pressure in surface.This is the preferred ultrasonic reaction time.
Dynamic activation, silicone hydroxyl spherical silica gel, PGMA/EDMA, PVA or PS-DVB swelling exchange resin completely polymer microballoon is the spherical honeycombed grain of 5-10um.
Advantage of the present invention is: the present invention carries out surface agglomeration in advance to dynamically activation, silicone hydroxyl invention, spherical silica gel base material or PGMA/EDMA, PVA or PS-DVB swelling exchange resin completely polymer microballoon base-material elder generation and maleic anhydride, then the weak-acid cation chromatographic column filler exchange resin prepared with maleic anhydride graft polyreaction.Be that exchange resin void consumption prepared by matrix is low with silica gel, percentage of grafting is high, the Subacidity cation chromatographic column of this exchange resin filler have to alkali and alkaline earth metal ions routine one, the simple nitric acid leacheate of divalent cation is separated simultaneously, not impact analysis result, analytical test cost is low, analyze and use that result is reappeared, post effect is higher, resolution and the good advantage of ion peak shape; Simple with the aliphatics weakly acidic cation-exchange resin manufacture craft containing double bond that exchange resin polymkeric substance is prepared for matrix, react completely, empty consumption is low, percentage of grafting is high, the Subacidity cation chromatographic column of this exchange resin filler has to analyze and uses that result is reappeared, post effect is higher, resolution and the good advantage of ion peak shape.
Accompanying drawing explanation
Fig. 1 adopts the inventive method, dynamically to activate, the exchange resin prepared for base-material of silicone hydroxyl spherical silica gel as the Subacidity cation chromatographic column of filler to a kind of color atlas of sample separation detection;
Fig. 2 adopts the inventive method, the exchange resin prepared using PGMA/EDMA swelling exchange resin completely polymer microballoon base-material as the Subacidity cation chromatographic column of filler to a kind of color atlas of sample separation detection.
Embodiment
Embodiment 1
First makes the separator column of silica gel type Subacidity cation chromatographic column filler and the embodiment to separation detection while of alkali and alkaline earth metal ions.
1, the invention, spherical silica gel base material of dynamically activation, silicone hydroxyl is prepared
By 5.0g, spherical porous silica gel particle after 7um dynamically activates and 2.5g vinyltrimethoxy silane load with in the there-necked flask of cooling tube, then add 100ml toluene, are filtered by content after 100 DEG C of heated and stirred reflux 10 hours, with methyl alcohol and washing with acetone, vacuumize drying.Weigh and obtain the invention, spherical silica gel base material of dynamic activation that 5.5g is combined with vinyl silanes, silicone hydroxyl.
2, by dynamically activating, the pre-agglomeration in the spherical silica gel of silicone hydroxyl surface
1.26g maleic anhydride is dropped in the 20ml acetone in 100ml beaker and dissolve completely, add 0.135g(0.2% again) Diisopropyl azodicarboxylate and the dynamic activation of preparation, the invention, spherical silica gel base material of silicone hydroxyl, the 40 DEG C of supersound process that heat up 6 hours, then put into rotatory evaporator and find time (50mmHg) to invention, spherical silica gel base material surface drying, complete the pre-agglomeration in surface of invention, spherical silica gel base material.
3, by the spherical silica gel of the dynamic activation after pre-for surface agglomeration, silicone hydroxyl and vinylbenzene and maleic anhydride graft polyreaction, weak-type Zeo-karb is prepared
2.1g maleic anhydride is dropped in the toluene of 100ml, add the dynamic activation after the 0.35g benzoyl peroxide of 0.4%, the pre-agglomeration of 1.5g vinylbenzene and surface, silicone hydroxyl spherical silica gel, be uniformly mixed in 500ml Erlenmeyer flask, logical nitrogen removes oxygen, and after 30 minutes, the 100 DEG C of stirring and refluxing that heat up were cooled to 90 DEG C after 6 hours, add 2ml vinylbenzene again, isothermal reaction 15 hours, taking-up methyl alcohol → acetone → methanol wash → be filtered dry, vacuum-drying.Obtain 7.5g weak-type Zeo-karb polymkeric substance.
4, Subacidity cation chromatographic column filler is prepared
The weak-type Zeo-karb polymkeric substance of drying is dropped into and has in the single port flask of water cooler, add the 6mmol phosphoric acid solution of 150ml, heat up 85 DEG C, stirring and refluxing 6 hours, thus after hydrolysis, more fully wash with deionized water, obtain Subacidity cation chromatographic column filler.
5, the separator column of silica gel type Subacidity cation chromatographic column filler is made, to alkali and alkaline earth metal ions separation detection simultaneously
Dropped in homogenate tank by the Subacidity cation chromatographic column filler handled well, high pressure is loaded into internal diameter 4.6mm, in the stainless steel separator column of column length 150mm.Do leacheate with 6mmol nitric acid, carry out the separation of sample.
Survey compound sample sample to have concentration be Li:0.2mg/l, Na:1.5mg/l NH4:1.5mg/l, K:2.5mg/l, Mg:2.0mg/l, Ca:2.0mg/l.Analysis condition is flow velocity: 1. 0ml/min, column temperature: room temperature, sample size: 100ul, detector: Direct Conductivity.
The results are shown in Figure 1 color atlas.In figure, peak 1 is Li from left to right certainly, and peak 2 is Na, and peak 3 is NH4, and peak 4 is K, and peak 5 is Mg, and peak 6 is Ca.It is low that exchange resin of the present invention has empty consumption, percentage of grafting is high, the post effect of the separator column made of exchange resin of the present invention is higher, resolution and ion peak shape good, with simple nitric acid leacheate to one of the routine of alkali and alkaline earth metal ions, divalent cation is separated simultaneously, not impact analysis result, analytical test cost is low.
Embodiment 2
Be second and make the separator column of silica gel type Subacidity cation chromatographic column filler and the embodiment to separation detection while of alkali and alkaline earth metal ions.
1, the invention, spherical silica gel base material of dynamically activation, silicone hydroxyl is prepared
By 7.0g, spherical porous silica gel particle after 7um dynamically activates and 2.5g vinyltrimethoxy silane load with in the there-necked flask of cooling tube, then add 125ml toluene, are filtered by content after 112 DEG C of heated and stirred reflux 10 hours, with methyl alcohol and washing with acetone, vacuumize drying.Weigh and obtain the invention, spherical silica gel base material of dynamic activation that 8.0g is combined with vinyl silanes, silicone hydroxyl.
2, the pre-agglomeration in spherical silica gel surface that is rear, silicone hydroxyl will dynamically be activated
1.40g maleic anhydride is dropped in the 20ml acetone in 100ml beaker and dissolve completely, add the Diisopropyl azodicarboxylate of 0.376g (0.4%) and the dynamic activation of preparation, the invention, spherical silica gel base material of silicone hydroxyl again, heat up 50 DEG C, supersound process 5 hours, then put into rotatory evaporator and find time (50mmHg) to invention, spherical silica gel base material surface drying, complete the pre-agglomeration in surface of invention, spherical silica gel base material.
3, by the spherical silica gel of the dynamic activation after pre-for surface agglomeration, silicone hydroxyl and vinylbenzene and maleic anhydride graft polyreaction, weak-type Zeo-karb is prepared
2.8g maleic anhydride is dropped in the toluene of 100ml, add the dynamic activation after the 0.5g benzoyl peroxide of 0.5%, the pre-agglomeration of 2.0g vinylbenzene and surface, silicone hydroxyl spherical silica gel, be uniformly mixed in 500ml Erlenmeyer flask, logical nitrogen removes oxygen, and after 30 minutes, the 113 DEG C of stirring and refluxing that heat up were cooled to 90 DEG C after 5 hours, add 3.5ml vinylbenzene again, isothermal reaction 15 hours, taking-up methyl alcohol → acetone → methanol wash → be filtered dry, vacuum-drying.Obtain 11.0g weak-type Zeo-karb polymkeric substance.
4, Subacidity cation chromatographic column filler is prepared
The weak-type Zeo-karb polymkeric substance of drying is dropped into and has in the single port flask of water cooler, add the 6mmol phosphoric acid solution of 175ml, heat up 85 DEG C, stirring and refluxing 7 hours, thus after hydrolysis, more fully wash with deionized water, obtain Subacidity cation chromatographic column filler.
5, the separator column of silica gel type Subacidity cation chromatographic column filler is made, to alkali and alkaline earth metal ions separation detection simultaneously
Dropped in homogenate tank by the Subacidity cation chromatographic column filler handled well, high pressure is loaded into internal diameter 4.6mm, in the stainless steel separator column of column length 150mm.Do leacheate with 6mmol nitric acid, carry out the separation of sample.
Survey compound sample sample, analysis condition is identical with embodiment 1.Close with the separating resulting of embodiment 1, ion peak error is less than 3%.Embodiment 2 does not have color atlas.
Embodiment 3
3rd makes the separator column of silica gel type Subacidity cation chromatographic column filler and the embodiment to separation detection while of alkali and alkaline earth metal ions.
1, the invention, spherical silica gel base material of dynamically activation, silicone hydroxyl is prepared
By 10.0g, spherical porous silica gel particle after 7um dynamically activates and 2.5g vinyltrimethoxy silane load with in the there-necked flask of cooling tube, then add 150ml toluene, are filtered by content after 125 DEG C of heated and stirred reflux 10 hours, with methyl alcohol and washing with acetone, vacuumize drying.Weigh and obtain the invention, spherical silica gel base material of dynamic activation that 11.0g is combined with vinyl silanes, silicone hydroxyl.
2, the pre-agglomeration in spherical silica gel surface that is rear, silicone hydroxyl will dynamically be activated
1.52g maleic anhydride is dropped in the 20ml acetone in 100ml beaker and dissolve completely, add 0.512g(0.64% again) Diisopropyl azodicarboxylate and the dynamic activation of preparation, the invention, spherical silica gel base material of silicone hydroxyl, the 60 DEG C of supersound process that heat up 4 hours, then put into rotatory evaporator and find time (50mmHg) to invention, spherical silica gel base material surface drying, complete the pre-agglomeration in surface of invention, spherical silica gel base material.
3, by the spherical silica gel of the dynamic activation after pre-for surface agglomeration, silicone hydroxyl and vinylbenzene and maleic anhydride graft polyreaction, weak-type Zeo-karb is prepared
3.5g maleic anhydride is dropped in the toluene of 100ml, add the dynamic activation after the 0.55g benzoyl peroxide of 0.5%, the pre-agglomeration of 2.5g vinylbenzene and surface, silicone hydroxyl spherical silica gel, be uniformly mixed in 500ml Erlenmeyer flask, logical nitrogen removes oxygen, and after 30 minutes, the 125 DEG C of stirring and refluxing that heat up were cooled to 90 DEG C after 4 hours, add 5ml vinylbenzene again, isothermal reaction 15 hours, taking-up methyl alcohol → acetone → methanol wash → be filtered dry, vacuum-drying.Obtain 14.5g weak-type Zeo-karb polymkeric substance.
4, Subacidity cation chromatographic column filler is prepared
The weak-type Zeo-karb polymkeric substance of drying is dropped into and has in the single port flask of water cooler, add the 6mmol phosphoric acid solution of 200ml, heat up 85 DEG C, stirring and refluxing 8 hours, thus after hydrolysis, more fully wash with deionized water, obtain Subacidity cation chromatographic column filler.
5, the separator column of silica gel type Subacidity cation chromatographic column filler is made, to alkali and alkaline earth metal ions separation detection simultaneously
Dropped in homogenate tank by the Subacidity cation chromatographic column filler handled well, high pressure is loaded into internal diameter 4.6mm, in the stainless steel separator column of column length 150mm.Do leacheate with 6mmol nitric acid, carry out the separation of sample.
Survey compound sample sample, analysis condition is identical with embodiment 1.Close with the separating resulting of embodiment 1, ion peak error is less than 3%.Embodiment 3 does not have color atlas.
As can be seen from embodiment 2 and embodiment 3, the exchange resin utilizing the present invention to prepare uses detected result to reappear better as the analysis of the separator column of filler.
Embodiment 4
First makes the separator column of exchange resin micro polymer ball-type Subacidity cation chromatographic column filler and the embodiment to separation detection while of alkali and alkaline earth metal ions.
1, the swelling polymer microballoon of exchange resin completely base-material is prepared
The 5g polymer P GMA/EDMA spherical honeycombed grain of ∮ 5um, is placed in 250ml beaker with deionized water-washing with alcohol drying, adds 50ml ethylene dichloride ultrasonic swelling 3 hours.Cross and be filtered dry.
2, by the pre-agglomeration in the swelling polymer microballoon of exchange resin completely surface
1.26g maleic anhydride drops in 20ml acetone, dissolve in 100ml beaker completely and add the Diisopropyl azodicarboxylate of 0.125g (0.2%) and the swelling exchange resin of PGMA/EDMA completely polymer microballoon, the 40 DEG C of supersound process that heat up are put into rotatory evaporator (50mmHg) and are evacuated to polymer microballoon surface drying after 6 hours.
3, by the swelling polymer microballoon of exchange resin completely after pre-for surface agglomeration and vinylbenzene and maleic anhydride graft polyreaction, weak-type Zeo-karb is prepared
The swelling polymer microballoon of exchange resin completely after pre-for surface agglomeration is added in the reaction flask that 100ml toluene is housed, again by 1.5g vinylbenzene, 2.1g maleic anhydride and 0.4% about 0.35g benzoyl peroxide add in reaction flask, be positioned in water-bath, be warming up to 90 DEG C of stirring and refluxing 10 hours.After cooling, by methyl alcohol → acetone → methanol wash, then use deionized water wash 1 time, oven drying at low temperature after filtering, weigh 8.0g contains the aliphatics weak-type Zeo-karb of double bond.
4, Subacidity cation chromatographic column filler is prepared
By 6mmol phosphoric acid 85 DEG C of stirring and refluxing of the weak-type Zeo-karb 150ml of drying, be hydrolyzed 6 hours, with deionized water wash one time, obtain Subacidity cation chromatographic column filler.
5, the separator column of Subacidity cation chromatographic column filler is made, to alkali and alkaline earth metal ions separation detection simultaneously
Dropped in homogenate tank by the Subacidity cation chromatographic column filler handled well, high pressure is loaded into internal diameter 4.6mm, in the stainless steel separator column of column length 150mm.Do leacheate with quadrol/tartrate (0.25/5.0mmol), carry out the separation of sample.
Survey compound sample sample, analysis condition is identical with embodiment 1.
Result is as Fig. 2 color atlas.In figure, peak 1 is Li from left to right certainly, and peak 2 is Na, and peak 3 is NH4, and peak 4 is K, and peak 5 is Mg, and peak 6 is Ca.It is simple that exchange resin of the present invention has manufacture craft, and empty consumption is low, and percentage of grafting is high, and the post effect of the separator column made of exchange resin of the present invention is as can be seen from Figure 2 higher, resolution and ion peak shape good.The ion peak error of the present embodiment and embodiment 1,2 and 3 is less than 5%.
Embodiment 5
Second makes the separator column of exchange resin micro polymer ball-type Subacidity cation chromatographic column filler and the embodiment to separation detection while of alkali and alkaline earth metal ions.
1, the swelling polymer microballoon of exchange resin completely base-material is prepared
The 7.5g polymer P VA spherical honeycombed grain of ∮ 7.5um, is placed in 250ml beaker with deionized water-washing with alcohol drying, adds 50ml ethylene dichloride ultrasonic swelling 4 hours.Cross and be filtered dry.
2, by the pre-agglomeration in the swelling polymer microballoon of exchange resin completely surface
1.40g maleic anhydride drops in 20ml acetone, dissolve in 100ml beaker completely and add the Diisopropyl azodicarboxylate of 0.360g (0.4%) and the swelling exchange resin of PVA completely polymer microballoon, the 50 DEG C of supersound process that heat up are put into rotatory evaporator (50mmHg) and are evacuated to polymer microballoon surface drying after 5 hours.
3, by the swelling polymer microballoon of exchange resin completely after pre-for surface agglomeration and vinylbenzene and maleic anhydride graft polyreaction, weak-type Zeo-karb is prepared
The swelling polymer microballoon of exchange resin completely after pre-for surface agglomeration is added in the reaction flask that 100ml toluene is housed, again by 2.0g vinylbenzene, 2.6g maleic anhydride and 0.5% 0.55g benzoyl peroxide add in reaction flask, be positioned in water-bath, be warming up to 90 DEG C of stirring and refluxing 10 hours.After cooling, by methyl alcohol → acetone → methanol wash, then use deionized water wash 2 times, filter oven drying at low temperature, weigh 11.2g contains the aliphatics weak-type Zeo-karb of double bond.
4, Subacidity cation chromatographic column filler is prepared
By 6mmol phosphoric acid 85 DEG C of stirring and refluxing of the weak-type Zeo-karb 175ml of drying, be hydrolyzed 7 hours, with deionized water wash one time, obtain Subacidity cation chromatographic column filler.
5, the separator column of Subacidity cation chromatographic column filler is made, to alkali and alkaline earth metal ions separation detection simultaneously
Dropped in homogenate tank by the Subacidity cation chromatographic column filler handled well, high pressure is loaded into internal diameter 4.6mm, in the stainless steel separator column of column length 150mm.Do leacheate with quadrol/tartrate (0.25/5.0mmol), carry out the separation of sample.
Survey compound sample sample, analysis condition is identical with embodiment 1.Close with the separating resulting of embodiment 4, ion peak error is less than 3%.Embodiment 5 does not have color atlas.
Embodiment 6
3rd makes the separator column of exchange resin micro polymer ball-type Subacidity cation chromatographic column filler and the embodiment to separation detection while of alkali and alkaline earth metal ions.
1, the swelling polymer microballoon of exchange resin completely base-material is prepared
The 10g polymer P S-DVB spherical honeycombed grain of ∮ 10um, is placed in 250ml beaker with deionized water-washing with alcohol drying, adds 50ml ethylene dichloride ultrasonic swelling 5 hours.Cross and be filtered dry.
2, by the pre-agglomeration in the swelling polymer microballoon of exchange resin completely surface
1.52g maleic anhydride drops in 20ml acetone, dissolve in 100ml beaker completely and add the Diisopropyl azodicarboxylate of 0.691g (0.6%) and the swelling exchange resin of PS-DVB completely polymer microballoon, the 60 DEG C of supersound process that heat up are put into rotatory evaporator (50mmHg) and are evacuated to the drying of polymer spherical particle surface after 4 hours.
3, by the swelling polymer microballoon of exchange resin completely after pre-for surface agglomeration and vinylbenzene and maleic anhydride graft polyreaction, weak-type Zeo-karb is prepared
The swelling polymer microballoon of exchange resin completely after pre-for surface agglomeration is added in the reaction flask that 100ml toluene is housed, again by 2.5g vinylbenzene, 3.0g maleic anhydride and 0.6% 0.66g benzoyl peroxide add in reaction flask, be positioned in water-bath, be warming up to 90 DEG C of stirring and refluxing 10 hours.After cooling, by methyl alcohol → acetone → methanol wash, then use deionized water wash 3 times, filter oven drying at low temperature, weigh 14.5g contains the aliphatics weak-type Zeo-karb of double bond.
4, Subacidity cation chromatographic column filler is prepared
By 6mmol phosphoric acid 85 DEG C of stirring and refluxing of the weak-type Zeo-karb 200ml of drying, be hydrolyzed 8 hours, with deionized water wash one time, obtain Subacidity cation chromatographic column filler.
5, the separator column of Subacidity cation chromatographic column filler is made, to alkali and alkaline earth metal ions separation detection simultaneously
Dropped in homogenate tank by the Subacidity cation chromatographic column filler handled well, high pressure is loaded into internal diameter 4.6mm, in the stainless steel separator column of column length 150mm.Do leacheate with quadrol/tartrate (0.25/5.0mmol), carry out the separation of sample.
Survey compound sample sample, analysis condition is identical with embodiment 1.Close with the separating resulting of embodiment 4, ion peak error is less than 3%.Embodiment 6 does not have color atlas.
As can be seen from embodiment 5 and embodiment 6, the exchange resin utilizing the present invention to prepare uses detected result to reappear better as the analysis of the separator column of filler.
Claims (7)
1. the preparation method of a weak-acid cation chromatographic column filler exchange resin, comprise dynamically activating, silicone hydroxyl spherical silica gel is base-material, or PGMA/EDMA, PVA or PS-DVB swelling exchange resin completely polymer microballoon is base-material, it is characterized in that described invention, spherical silica gel base material, or described PGMA/EDMA, PVA or PS-DVB exchange resin polymer microballoon base-material first carries out the pre-agglomeration reaction in surface with maleic anhydride, regular graft polymerization reaction is carried out again, obtained weak-acid cation chromatographic column filler exchange resin with maleic anhydride; The temperature 35-65 DEG C of the pre-agglomeration in surface.
2. the preparation method of weak-acid cation chromatographic column filler exchange resin according to claim 1, it is characterized in that described invention, spherical silica gel base material, or described PGMA/EDMA, PVA or PS-DVB exchange resin polymer microballoon base-material first carries out surface agglomeration reaction in advance with maleic anhydride and vinylbenzene or divinyl.
3. the preparation method of weak-acid cation chromatographic column filler exchange resin according to claim 1 and 2, is characterized in that adopting Diisopropyl azodicarboxylate initiator in the pre-agglomeration reaction in surface.
4. the preparation method of weak-acid cation chromatographic column filler exchange resin according to claim 1, is characterized in that the temperature 45-55 DEG C of the pre-agglomeration in surface.
5. the preparation method of weak-acid cation chromatographic column filler exchange resin according to claim 1, is characterized in that the pre-agglomeration ultrasonic reaction 3.5-6.5 hour at ambient pressure in surface.
6. the preparation method of weak-acid cation chromatographic column filler exchange resin according to claim 1, is characterized in that the pre-agglomeration ultrasonic reaction 4.5-5.5 hour at ambient pressure in surface.
7. the preparation method of weak-acid cation chromatographic column filler exchange resin according to claim 1, it is characterized in that dynamic activation, silicone hydroxyl spherical silica gel, PGMA/EDMA, PVA or PS-DVB swelling exchange resin completely polymer microballoon is the spherical honeycombed grain of 5-10 μm.
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| CN108187765B (en) * | 2018-01-31 | 2020-07-28 | 河南省科学院化学研究所有限公司 | PP-ST-DVB-based cation exchange fiber and synthetic method thereof |
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| CN110292955A (en) * | 2019-06-28 | 2019-10-01 | 华东理工大学 | Weak acid ion exchange chromatography filler and preparation method thereof and ion chromatographic column |
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