CN85100884A - High-efficiency anion microspheres resin - Google Patents
High-efficiency anion microspheres resin Download PDFInfo
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- CN85100884A CN85100884A CN198585100884A CN85100884A CN85100884A CN 85100884 A CN85100884 A CN 85100884A CN 198585100884 A CN198585100884 A CN 198585100884A CN 85100884 A CN85100884 A CN 85100884A CN 85100884 A CN85100884 A CN 85100884A
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- latex
- base ball
- quaternized
- granularity
- agglomeration
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Abstract
The invention relates to the preparation of anionic agglomeration microsphere resin and as the characteristic and the using method of high-performance ion chromatography column filler.
With the single dispersion quaternary ammoniated crosslinked polystyrene latex of granularity, on the surface of granularity, can be made into the anionic agglomeration microsphere resin of low ion exchange capacity greater than the crosslinked polystyrene microsphere of 5 μ m with the Coulomb force agglomeration less than 0.5 μ m.Resin can make trace anion (F as the high-performance ion chromatography column filler
-, CL
-, Br
-, NO
- 2, NO
- 3, HPO= 4, SO= 4) recombined sample, on the pillar of 10 centimeter length, obtaining good separation, post is imitated (Cl
-) every meter more than 3000 column plates, reach as high as every meter 9000 column plate.
Description
The field is high-performance ion chromatography column filler-negative ion agglomeration microsphere resin under of the present invention.
The performance that the objective of the invention is to develop a kind of negative high-efficiency anion microspheres resin and improve existing ion-exchange chromatography filler.
Chromatography of ions is a branch with fastest developing speed in the modern liquid chromatography technology; because it is suitable for measuring simultaneously different kinds of ions; particularly solved and be considered to the negative ion that is difficult to overcome and the trace analysis problem of organic ion sample for a long time, thereby in commercial production and environmental protection, be widely used.As the separating column packing of chromatography of ions core, the product with U.S. Dionex company is the best at present.Its anionic has HPIC-AS1-4 series.According to interrelated data and patent (U.S.Pat.No.4,101,460; 4,119,580; 4,351,909) report, AS series is to be that the crosslinked polymer resin of the macroporous structure that is sulfonated of the surface about 25 μ m is component A with granularity, the cross-linked polymer latex that contains different quaternary ammonium groups that with the granularity is 0.1-5 μ m is B component, B with the outside surface of individual layer attached to A, is formed the anion exchange compound that can use of stable low ion exchange capacity in extensive pH value scope.Another type chromatography of ions filler is that the product with Japanese Toyosoda company is representative, and its anionic has quaternised cross linked porous macromolecule resin (TSK-Gel-Anion-PW and the quaternised Bio-sil resin (TSK-Gel-IC-Anion-SW) of low ion exchange capacity.The all existing higher post of the above filler is imitated and selectivity, and widespread use.
Purpose of the present invention is as follows:
The present invention is on the crosslinked polystyrene base ball of granularity greater than the sulfonating surface of 5 μ m, and granularity forms anion microspheres resin less than the quaternised mono-dispersed latex of 0.5 μ m in the agglomeration.The control exchange capacity makes resin as the high-efficient ion chromatogram column packing, can in the pH value scope the various negative ion of trace be separated with organic ion widely with the long column jecket of 10Cm.
Technology of the present invention constitutes:
(1) be monomer with styrene in aqueous media, divinylbenzene is a crosslinking chemical, adopts the method for agalactosis polymerization to come the monodisperse cross-linked polystyrene latex of prepared sizes less than 0.5 μ m.This polymerization is based on monomer certain solubleness in water, when in a single day water soluble starter produces free radical, chain reaction just takes place in aqueous solution.When chain growth is arrived to a certain degree, just tangle and the association nucleation each other, the latter is stablized by the ionic strength of system, and progressively increases balling-up as " seed ".The size of latex microsphere warp can be passed through polymerization temperature, and the isoparametric adjusting of the ionic strength of monomer and initiator concentration and system is controlled, and adopts stereoscan photograph to measure.The advantage that this legal system is equipped with latex is: the first, and product is pure, and conversion ratio height (100%) need not to carry out aftertreatment; The second, homogeneous grain diameter, single dispersion degree reaches more than 90%, need not to carry out classification.Carry out chloromethylation and quaterisation after latex dewatered, obtain the crosslinked polystyrene latex of quaternary ammonium type at last.The degree of chloromethylation is decided by the degree of crosslinking of former latex, and degree of crosslinking is high more, and the degree of chloromethylation is low more.The latex that contains dissimilar quaternary ammonium groups has different selectivity in application.
(2) with styrene be monomer, divinylbenzene is that crosslinking chemical, azoisobutyronitrile are initiating agent, adopts the method for suspension polymerization in aqueous media, prepares crosslinked polystyrene-based ball.The granularity of base ball is to control by the selection of dispersed system and the conciliation of polymerization speed of agitator, and chooses suitable size with classification of sedimentation, the particle that distribution range is narrower.Basic in general ball size ratio latex is wanted a big 2-3 order of magnitude.The sulfonating reaction of base ball is to use the concentrated sulphuric acid to carry out.The sulfonation degree of depth depends mainly on the degree of crosslinking of basic ball, the time of sulfonation temperature and sulfonation.Degree of crosslinking generally is advisable between 2-16%.Degree of crosslinking too high can influence the distribution of sulfonation degree and sulfonation group, degree of crosslinking is crossed and is hanged down the homogeneity that then influences macromolecule network, rigidity is died down and is easy to swelling, has influenced the penetrability of pillar.
(3) agglomeration of sulfonation base ball and quaternized latex is based on storehouse, the storehouse gravitation between two kinds of ions of negative and positive.This strong interaction force is enough to make reinforcing yin essence ion-type latex stably attached to the surface of strong cation base ball, forms the anion exchange resins of individual layer " shell " structure, and the topped dense degree of ammonium latex depends mainly on the sulfonation degree of depth of basic ball.Agglomeration microsphere resin is as the chromatography of ions filler, and its exchanging equivalent is an important parameter that characterizes packing property, because exchanging equivalent has directly influenced the retention of chromatogram.The sulfonating surface base ball that the present invention controlled and the exchanging equivalent of quaternized latex are all 10
-2On the level of milligramequivalent/gram.
Effect:
The prepared anionic agglomeration microsphere resin of the present invention as the high-efficient ion chromatogram filler for multiple negative ion (as F
-, Cl
-, Br
-, NO
- 2, NO
- 3, HPO
= 4, SO
= 4And HCOO
-Deng) good centrifugation is arranged, be suitable for trace detection, the separating column packing AS of its performance and U.S. Dionex company is close, and separating column length reduces by more than half than AS.
Specific embodiment:
Example 1, agglomeration reaction
20% NaCO
3Aqueous solution 2ml
4% quaternized latex 4ml
3.5 gram crosslinked polystyrene base ball be sulfonated with classification after, be made into pulpous state liquid
In the 50ml reaction bulb of stirrer is housed, add NaCO
3Aqueous solution and quaternized latex, the slow pulpous state liquid that drips sulfonation base ball under strong agitation adds and continues to stir 20 minutes.Reactant is poured in the triangular flask, and the adding deionized water carries out ultrasonic, staticly settles then, and the supernatant liquid that inclines cleans, so repeatedly thoroughly to eliminate unnecessary latex.For the agglomeration microsphere resin that is obtained, can pass through its degree of agglomeration of scanning electron microscopic observation.
Example 2, chromatographic performance test
Instrument: the high-efficient ion chromatogram instrument (Beckman liquid chromatography infusion pump, Perkin-Elmer electric conductivity detector) of this laboratory assembling.
Sample: contain F
-, Cl
-, Br
-, NO
- 2, NO
- 3, HPO
= 4, SO
= 4In inorganic salts and formic acid (it is pure to be analysis).
Leacheate: Na
2CO
3-NaHCO
3Aqueous solution.
Separating column: the stainless steel column of φ 4.6 * 100mm, fill prepared anionic agglomeration microsphere resin Sinopak-LOIA.
Suppressed column: the stainless steel column of φ 4.6 * 250mm, filling male ion-exchange resin
Post is pressed: 300psi.
Flow velocity: 2.0ml/ branch.
Temperature: 30 ± 2 ℃
Chromatographic resolution result as shown in the figure.
Claims (6)
1, the present invention is a kind of ion chromatographic separation column packing, it is characterized in that on the crosslinked polystyrene base ball of granularity greater than the sulfonating surface of 5 μ m, agglomeration one deck granularity forms high-efficiency anion microspheres resin less than the monodispersed quaternized latex of 0.5 μ m.
2, ion chromatographic separation column packing as claimed in claim 1 is characterized in that high-efficiency anion microspheres resin can be suitable for the multiple trace anion of separation detection in the pH value scope, its chromatogram column efficiency (Cl widely
-) more than every meter 3000 column plate, being up to every meter 9000 column plate, separating column length reduces by more than half than the AS post of Dionex.
3, the present invention is a kind of manufacture method of ion chromatographic separation column packing, it is characterized in that the synthetic method of mono-dispersed latex, the synthetic method of crosslinked polystyrene base ball and the agglomeration reaction method of sulfonation base ball and quaternized latex.
4, the method for making of ion chromatographic column filler as claimed in claim 3, the synthetic method that it is characterized in that mono-dispersed latex is to be that monomer, divinylbenzene are crosslinking chemical with styrene in aqueous media, adopt agalactosis polymerization, the parameters such as ionic strength of control polymerization temperature, monomer and initiator concentration and system make the monodisperse cross-linked polystyrene latex of granularity less than 0.5 μ m.Made product is pure, conversion ratio is high (100%), need not aftertreatment, homogeneous grain diameter, and single dispersion degree reaches more than 90%.Latex adopts commonsense method to carry out quaterisation, and the degree of crosslinking and the granularity of control latex are so that the quaternized latex that makes has suitable exchange capacity.
5, the manufacture method of ion chromatographic column filler as claimed in claim 3, the synthetic method that it is characterized in that crosslinked polystyrene base ball is to be that monomer, divinylbenzene are crosslinking chemical with styrene, adopt suspension polymerization at aqueous phase, making granularity is the basic ball of 2-16% greater than 5 μ m, degree of crosslinking.The base ball uses the concentrated sulphuric acid to carry out surface sulfonation fast, and the sulfonating surface degree of depth is controlled by the degree of crosslinking of polymerization, the temperature and time of sulfonating reaction.
6, as claim 3, the manufacture method of 4,5 described ion chromatographic column fillers, the agglomeration reaction method that it is characterized in that sulfonation base ball and quaternized latex are with after quaternized latex and the aqueous solution, splash into sulfonation base ball pulpous state liquid under strong agitation.By reaction make quaternized latex equably agglomeration on sulfonation base ball surface, form the anion exchange resins of individual layer " shell " structure.Exchange capacity is decided by employed sulfonation base ball and quaternized latex, generally is controlled at 0.02 milligramequivalent/below the gram.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198585100884A CN85100884A (en) | 1985-04-01 | 1985-04-01 | High-efficiency anion microspheres resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198585100884A CN85100884A (en) | 1985-04-01 | 1985-04-01 | High-efficiency anion microspheres resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85100884A true CN85100884A (en) | 1986-02-10 |
Family
ID=4791500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198585100884A Pending CN85100884A (en) | 1985-04-01 | 1985-04-01 | High-efficiency anion microspheres resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85100884A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101533002A (en) * | 2008-03-10 | 2009-09-16 | 黄永 | Flat ion-exchange module |
| CN101806781A (en) * | 2010-03-16 | 2010-08-18 | 哈尔滨飞机工业集团有限责任公司 | Method for measuring anionic sulfate radicals in salt bath solution by using ion chromatography |
| CN107413395A (en) * | 2017-08-30 | 2017-12-01 | 苏州明昊色谱技术有限公司 | A kind of agglomeration type high-hydrophilic strong anion exchanger, preparation method and its application in liquid chromatographic packing materials |
-
1985
- 1985-04-01 CN CN198585100884A patent/CN85100884A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101533002A (en) * | 2008-03-10 | 2009-09-16 | 黄永 | Flat ion-exchange module |
| CN101806781A (en) * | 2010-03-16 | 2010-08-18 | 哈尔滨飞机工业集团有限责任公司 | Method for measuring anionic sulfate radicals in salt bath solution by using ion chromatography |
| CN107413395A (en) * | 2017-08-30 | 2017-12-01 | 苏州明昊色谱技术有限公司 | A kind of agglomeration type high-hydrophilic strong anion exchanger, preparation method and its application in liquid chromatographic packing materials |
| CN107413395B (en) * | 2017-08-30 | 2020-05-19 | 苏州明昊色谱技术有限公司 | Agglomeration type high-hydrophilicity strong anion exchanger, preparation method and application thereof in liquid chromatography column packing |
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