CN102432728A - Organic-inorganic hybrid polymer microballoon for ion chromatography and preparation method thereof - Google Patents
Organic-inorganic hybrid polymer microballoon for ion chromatography and preparation method thereof Download PDFInfo
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- CN102432728A CN102432728A CN2011102632623A CN201110263262A CN102432728A CN 102432728 A CN102432728 A CN 102432728A CN 2011102632623 A CN2011102632623 A CN 2011102632623A CN 201110263262 A CN201110263262 A CN 201110263262A CN 102432728 A CN102432728 A CN 102432728A
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Abstract
The invention relates to an organic-inorganic hybrid polymer microballoon for an ion chromatography and a preparation method thereof. The organic-inorganic hybrid polymer microballoon for an ion chromatography is a polystyrene-3-trimethoxysilyl propyl methacrylate ion exchange resin microballoon, and specifically, is a copolymer of styrene and 3-trimethoxysilyl propyl methacrylate, wherein a volume ratio of styrene to 3-trimethoxysilyl propyl methacrylate is in a range of (5: 1) to (20: 1); microballoon sizes are in a range of 2 to 10 micrometers; and the copolymer of styrene and 3-trimethoxysilyl propyl methacrylate is an imporous matrix. The preparation method adopts a two-step dispersion polymerization technology, is simple and is convenient for amplification. Through the preparation method, a matrix can be modified, wherein modification processes comprise carrying out direct bonding on a surface and carrying out latex agglomeration on the surface and thus ion separation is realized.
Description
[technical field]
The present invention relates to the ion chromatography field; Specifically; Be a kind of hybrid inorganic-organic polymer microballoon and preparation method who is used for chromatography of ions, be specially PS-methylacrylic acid-3-trimethoxy silicon propyl ester amberlite lipoid microsphere and preparation method and application.
[background technology]
Chromatography of ions is one of branch of performance liquid chromatography, and different with performance liquid chromatography is optionally changes in chromatography of ions mainly is the character that depends on stationary phase.The research of ion chromatographic column filler is exactly a hot subject in chromatography of ions field since coming out from chromatography of ions.
The chromatography of ions filler mainly is divided into inorganic silica gel matrix and organic polymer matrix, and silica matrix is through different ions cation exchange groups on the surface bond.Compare with organic polymer matrix; The good mechanical stability of silica matrix generally can swelling or contraction in organic solvent, can obtain high post and imitate (theoretical plate number can reach 15000～20000); Can use down at comparatively high temps (80 ℃); The distinct disadvantage of silica matrix is unstable in alkaline medium, can only use neutrality or slightly acidic (pH=2～8) moving phase, and its use receives certain restriction.
Organic polymer matrix mainly comprises: cross-linked polystyrene resin, cross-linked poly-methyl methacrylate esters resin and hydroxylated polyether resin etc.Organic polymer matrix is stable in very wide pH value scope (generally can in pH=0～14), and available strong acid or highly basic are done leacheate.But organic polymer matrix just has reasonable mechanical stability when high-crosslinking-degree.
Given this, need a kind of ion exchange resin that can combine inorganic and inorganic matrix advantage.PS-methylacrylic acid-3-trimethoxy silicon propyl ester ion exchange resin not only possesses good spherical morphology; Narrow size distribution; And siliconoxygen bond has improved the thermostability of polymkeric substance greatly; Strengthen the mechanical stability of matrix, and the microsphere surface phenyl ring modifies easily, be suitable for the chromatography of ions filler.
[summary of the invention]
The objective of the invention is to overcome the deficiency of prior art; A kind of hybrid inorganic-organic polymer microballoon and preparation method who is used for chromatography of ions is provided, is specially PS-methylacrylic acid-3-trimethoxy silicon propyl ester amberlite lipoid microsphere and preparation method and application.
The objective of the invention is to realize through following technical scheme:
A kind of hybrid inorganic-organic polymer microballoon that is used for chromatography of ions; It is characterized in that; Described polymer microballoon is PS-methylacrylic acid-3-trimethoxy silicon propyl ester amberlite lipoid microsphere; Be specially the multipolymer of vinylbenzene and methylacrylic acid-3-trimethoxy silicon propyl ester, wherein the volume ratio of vinylbenzene and methylacrylic acid-3-trimethoxy silicon propyl ester is 5: 1～20: 1, and microspherulite diameter is 2～10 μ m.
A kind of preparation method who is used for the hybrid inorganic-organic polymer microballoon of chromatography of ions is characterized in that, described preparation method is two step dispersion copolymerization methods, comprises the steps:
(1) the stablizer Vinylpyrrolidone polymer is joined in the absolute ethyl alcohol, at room temperature stirring and dissolving adds the vinylbenzene that is dissolved with the initiator Diisopropyl azodicarboxylate then, charges into nitrogen under the room temperature, gets rid of the oxygen in the reaction flask, 50 ℃ then～80 ℃ reacting by heating;
Wherein: the mass ratio of Vinylpyrrolidone polymer and Diisopropyl azodicarboxylate is 5: 1～10: 1;
(2) will be dissolved in the absolute ethyl alcohol with (1) equivalent with the vinylbenzene of (1) moderate and methylacrylic acid-3-trimethoxy silicon propyl ester, charge into nitrogen under the room temperature, get rid of the oxygen in the reaction flask, carry out 50 ℃～80 ℃ preheatings simultaneously with heating in (1) step;
Wherein: the volume ratio of vinylbenzene, methylacrylic acid-3-trimethyl silicane propyl ester and absolute ethyl alcohol is 5: 1: 25～5: 0.5: 25;
(3) after heating is carried out 40 minutes～60 minutes in step (1) and (2), will (2) in the reactant of preheating join in the reaction flask in (1), continue to heat 20 hours～24 hours, suction filtration obtains microballoon;
(4) microballoon that obtains in the step (3) was refluxed 20 hours～24 hours in the mixed solution of water, absolute ethyl alcohol and ammoniacal liquor with in 50 ℃～80 ℃, suction filtration, the microballoon at the beginning of obtaining behind the one-step hydrolysis:
Wherein: the volume ratio of water, absolute ethyl alcohol and ammoniacal liquor is 1: 1: 0.0000001～1: 3: 0.00000012;
(5) microballoon that obtains in the step (4) was refluxed 60 hours～72 hours in 60 ℃～65 ℃ in the mixed solution of water, absolute ethyl alcohol, THF and ammoniacal liquor, obtain final microballoon.
Wherein: the volume ratio of water, absolute ethyl alcohol, THF and ammoniacal liquor is 1: 1: 0.6: 0.3～1: 1.5: 0.8: 0.3;
A kind of sulfonating surface method that is used for the hybrid inorganic-organic polymer microballoon of chromatography of ions is characterized in that described method of sulfonating comprises the steps:
Microballoon is scattered in the anhydrous methylene chloride, under 0 ℃～100 ℃ conditions, stirs, and drips sulfonated reagent, reacts 10～30 minutes, uses the frozen water stopped reaction, suction filtration, and water and methyl alcohol difference washing leaching cake three times, drying obtains title product.
Wherein: the 1g microballoon is dispersed in the methylene dichloride of 25～35ml;
Sulfonated reagent is the vitriol oil or chlorsulfonic acid.
A kind of surperficial carboxylic acid method that is used for the hybrid inorganic-organic polymer microballoon of chromatography of ions is characterized in that described carboxylic acid method comprises the steps:
Microballoon is scattered in the anhydrous methylene chloride, under 0 ℃～25 ℃ conditions, stirs, and adds chloroacetyl chloride and aluminum trichloride (anhydrous), stirs 2 hours～5 hours, uses the frozen water stopped reaction, and suction filtration is once used THF, water and methanol wash filter cake, obtains title product.
Wherein: the 1g microballoon is dispersed in the methylene dichloride of 25～35ml;
The mol ratio of chloroacetyl chloride, aluminum trichloride (anhydrous) and methylene dichloride is 1: 3: 10～1: 3.5: 15;
Carboxylic acid reagent is along butyryl oxide, maleic anhydride and Tetra hydro Phthalic anhydride.
A kind of surperficial amination method that is used for the hybrid inorganic-organic polymer microballoon of chromatography of ions is characterized in that described amination method comprises the steps:
(1) be to mix in 1: 0.3: 8～1: 0.5: 12 the alcoholic solution of epoxy chloropropane, Trimethylamine 99 and ETHYLE ACETATE with volume ratio, stirred overnight under the room temperature, suction filtration obtains quaternary ammonium salt;
(2) chloroacetyl chloride and aluminum trichloride (anhydrous) are added in the anhydrous methylene chloride, stirred 10 minutes～30 minutes under the room temperature, add microballoon then; Be uniformly dispersed, under 0 ℃～30 ℃ conditions, reacted 15 minutes～150 minutes; Finish reaction with frozen water, suction filtration is used THF, water and methanol wash filter cake successively; Drying obtains the chlorination microballoon;
Wherein: the 1g microballoon is dispersed in the methylene dichloride of 25～35ml;
Chloroacetyl chloride, aluminum trichloride (anhydrous), with the mol ratio of methylene dichloride be 1: 3: 10～1: 3.5: 15;
(3) the chlorination microballoon that obtains in the step (2) is dispersed in the THF, adds aminated reagent, under 60 ℃～70 ℃ conditions, refluxed 2 hours～4 hours, suction filtration, water and methanol wash, drying obtains preliminary amination microballoon;
Wherein: the 1g microballoon is dispersed in the THF of 25～35ml;
The mol ratio of chloroacetyl chloride, aluminum trichloride (anhydrous), amination reagent and methylene dichloride is 1: 3: 10: 10～1: 3.5: 12: 15;
Amination reagent is diethylenetriamine, triethylene tetramine, polyethylene polyamine, quadrol and hexanediamine.
(4) say that the amination microballoon that obtains in the step (3) joins in the methyl alcohol and be uniformly dispersed, add the quaternary ammonium salt of preparation in the step (1), under 20 ℃～30 ℃ conditions, stirred 14 hours～16 hours, suction filtration, water and methanol wash, drying obtains title product.
Wherein: the 1g microballoon is dispersed in the methyl alcohol of 20～30ml;
Amination reagent is diethylenetriamine, triethylene tetramine, polyethylene polyamine, quadrol and hexanediamine.
A kind of surperficial quaternized method that is used for the hybrid inorganic-organic polymer microballoon of chromatography of ions is characterized in that described quaternized method comprises the steps:
(1) chloroacetyl chloride and aluminum trichloride (anhydrous) are added in the anhydrous methylene chloride, stirred 10 minutes～30 minutes under the room temperature, add microballoon then; Ultra-sonic dispersion is even, under 0 ℃～30 ℃ conditions, reacts 15 minutes～150 minutes; Finish reaction with frozen water, suction filtration is used THF, water and methanol wash filter cake successively; Drying obtains the chlorination microballoon;
Wherein: the 1g microballoon is dispersed in the methylene dichloride of 25～35ml;
The mol ratio of chloroacetyl chloride, aluminum trichloride (anhydrous), quaternary ammonium reagent and absolute ethyl alcohol is 1: 3: 10: 20～1: 3.5: 12: 25;
(2) the chlorination microballoon that obtains in the step (1) is dispersed in the absolute ethyl alcohol, adds quaternizing agent, under 60 ℃～70 ℃ conditions, refluxed 2 hours～4 hours, suction filtration, water and methanol wash, drying obtains quaternized microballoon;
Wherein: the 1g microballoon is dispersed in the absolute ethyl alcohol of 20～30ml;
Quaternizing agent is Trimethylamine 99, trolamine and N, the N-dimethylethanolamine.
A kind of preparation method of surperficial agglomeration type chromatography of ions of the hybrid inorganic-organic polymer microballoon that is used for chromatography of ions is characterized in that described preparation method comprises the steps:
(1) sodium lauryl sulphate and sodium hydroxide are added in the deionized water, under the room temperature dispersed with stirring evenly after, add p-chloromethyl styrene and methylacrylic acid-3-trimethoxy silicon propyl ester; Charge into nitrogen and remove oxygen, add Potassium Persulphate then, charge into nitrogen and remove oxygen; Then under 50 ℃～70 ℃ conditions; Heated 5 hours～8 hours, and left standstill, obtain emulsion particle solution;
Wherein: the mol ratio of sodium laurylsulfonate, sodium hydroxide, Potassium Persulphate, p-chloromethyl styrene, methylacrylic acid-3-trimethoxy silicon propyl ester and deionized water is 1: 0.5: 0.5: 15: 0.5: 150～1: 1: 1: 25: 0.8: 200;
(2) in the emulsion particle solution that (1) obtains, add quaternizing agent, under 50 ℃～70 ℃ conditions, heated 1 hour～3 hours, leave standstill, obtain quaternised emulsion particle solution;
Wherein: quaternizing agent is: Trimethylamine 99, triethylamine, trolamine and N, N-dimethylethanolamine.
(3) microballoon with sulfonating surface is dispersed in the quaternized emulsion particle solution that has diluted 5～10 times, stirs 1 hour～5 hours under the room temperature, and centrifugal, suction filtration obtains product;
Wherein: 1g sulfonation microballoon is dispersed in the quaternized emulsion particle solution of dilution of 5～10ml.
Compared with prior art, positively effect of the present invention is:
Characteristics of the present invention are through organic polymer, and inorganic sol-gel hydrolysis make filler under the low crosslinking degree condition, can reach the dress column condition, and the preparation method is simple, and particle diameter is controlled, scalable reaction.Wherein can reach Gao Zhuxiao through the agglomerant modifying method in surface, this is the existing unapproachable effect of polymer packing.And this filler can bear the alkaline condition of a bit, and this point has enlarged the pH use range of silica matrix again.
[description of drawings]
Fig. 1 is with the prepared polymer microballoon of embodiment 2;
Fig. 2 is for being the IC column material with embodiment 10 prepared targeted microspheres, to IO
3 -, BrO
3 -, Br
-, and NO
3 -The analysis of mixture:
Wherein: peak sequence is followed successively by: IO
3 -, BrO
3 -, Br
-, and NO
3 -
Fig. 3 is for being the IC column material with embodiment 10 prepared targeted microspheres, the relation curve of flow velocity and post pressure.
Fig. 4 is for being the IC column material with embodiment 12 prepared targeted microspheres, to IO
3 -, BrO
3 -, Br
-, and NO
3 -The analysis of mixture:
Wherein: peak sequence is followed successively by: IO
3 -, BrO
3 -, Br
-, and NO
3 -
Fig. 5 is for being the IC column material with embodiment 16 prepared latex agglomeration type microballoons, to IO
3 -, BrO
3 -, Br
-, NO
2 -And NO
3 -The analysis of mixture:
Wherein: peak sequence is followed successively by: IO
3 -, BrO
3 -, NO
2 -, Br
-, and NO
3 -
[embodiment]
The present invention below is provided a kind of hybrid inorganic-organic polymer microballoon of chromatography of ions and embodiment of preparation method of being used for.
Embodiment 1
Step (1) adds the 25ml absolute ethyl alcohol that is dissolved with stablizer Vinylpyrrolidone polymer 1.0g in the 250ml round-bottomed flask; Add the 5ml vinylbenzene that is dissolved with initiator Diisopropyl azodicarboxylate 0.2g then; Charge into nitrogen half hour under the room temperature; Get rid of the oxygen in the reaction flask, 68 ℃ then～71 ℃ reacting by heating;
Step (2) adds 5ml vinylbenzene, 1ml silane and 25ml absolute ethyl alcohol in the 50ml round-bottomed flask, pour nitrogen under the room temperature, gets rid of the oxygen in the reaction flask, carries out 70 ℃ of preheatings simultaneously with heating in (1) step;
After heating is carried out 40 minutes～60 minutes in step (3) step (1) and (2), will (2) in the reactant of preheating join in the reaction flask in (1), continue to heat 20 hours～24 hours, suction filtration obtains target compound.
Utilize ESEM analysis, recording the particle diameter mean size is 5 μ m.
Embodiment 2
In the step in embodiment 1 (1), the 1.0g Vinylpyrrolidone polymer is replaced with the 1.5g Vinylpyrrolidone polymer, other step is all by embodiment 1 operation, can obtain the little microballoon of particle diameter ratio embodiment one.Utilize ESEM analysis, the result sees Fig. 1, and recording the particle diameter mean size is 4 μ m.
Embodiment 3
The microballoon 3.0g of preparation among the embodiment 1 is joined in the 100ml round-bottomed flask, add the 30ml anhydrous methylene chloride, swelling is spent the night under the room temperature; Add 1.68 maleic anhydrides and 6.24g aluminum trichloride (anhydrous), react 4h under the room temperature, finish reaction with frozen water; Suction filtration is used THF successively, water and methanol wash filter cake; Drying, weighing obtains the 4.27g target compound, and calculating the chloroacetylation amount is 3.02mmol/g.
Embodiment 4
The microballoon 2.0g of preparation among the embodiment 1 is joined in the 250ml round-bottomed flask, add the 5.0g vitriol oil, reaction is 20 minutes in ice-water bath, and loading capacity is 8 μ mol/column.
Embodiment 5
In embodiment 4, ice-water bath is replaced with 20 ℃, all by embodiment 3 operations, loading capacity is 16 μ mol/column to other step.
Embodiment 6
In embodiment 4, ice-water bath is replaced with 60 ℃, all by embodiment 3 operations, filler can't be adorned post in other operation.
Embodiment 7
In the 250ml round-bottomed flask, add 3.2g chloroacetyl chloride and 3.8g aluminum trichloride (anhydrous), add the 45ml anhydrous methylene chloride, stir up to the solid dissolving, the 3.0g microballoon with preparation among the embodiment 1 adds in the reaction flask then; Ultra-sonic dispersion is even, and reaction is 15 minutes under ice-water bath, finishes reaction with frozen water; Suction filtration is used THF successively, water and methanol wash filter cake; Drying, weighing obtains the 4.06g target compound, and calculating the chloroacetylation amount is 3.37mmol/g.
Embodiment 8
In embodiment 7, the 3.2g chloroacetyl chloride is replaced with the 1.6g chloroacetyl chloride; The 3.8g aluminum trichloride (anhydrous) is replaced with the 1.9g aluminum trichloride (anhydrous); Other operation is all operated by embodiment 7, the left back 3.53g target compound that obtains, and calculating the chloroacetylation amount is 1.94mmol/g.
Embodiment 9
In embodiment 7, the 3.2g chloroacetyl chloride is replaced with the 0.8g chloroacetyl chloride; The 3.8g aluminum trichloride (anhydrous) is replaced with the 0.95g aluminum trichloride (anhydrous); Other operation all by embodiment 7 operations, obtains the 3.04g target compound at last, and calculating the chloroacetylation amount is 0.172mmol/g.
Embodiment 10
Step (1) replaces to room temperature with ice-water bath in embodiment 7, other operation is all operated by embodiment 7, the left back 4.5g target compound that obtains, and calculating the chloroacetylation amount is 4.36mmol/g.
Step (2) adds the chloroacetylation microballoon that step (1) obtains in the 250ml round-bottomed flask, add 50ml THF and 14g diethylenetriamine, and ultra-sonic dispersion is even, and 70 ℃ were heated 2.5 hours, suction filtration, and water and methanol wash filter cake, drying obtains the amination microballoon.
Step (3) adds the Trimethylamine 99 alcoholic solution of 20ml epoxy chloropropane and 18ml in the round-bottomed flask of 250ml, stirred overnight under the room temperature, and suction filtration, drying obtains target compound.
Step (4) adds the amination microballoon of 3.0g step (2) preparation and the target compound of 1.7g step (3) preparation in the 250ml round-bottomed flask, add the 50ml absolute ethyl alcohol then, reacts 4 hours down at 70 ℃; Suction filtration; Water and methanol wash filter cake, drying obtains quaternized microballoon.
The quaternized microballoon of preparation is loaded into 4.6 * 150i.d.mm stainless steel chromatogram post with the homogenate method, to IO
3-, BrO
3-, Br-and NO
3-ion chromatography, the result sees Fig. 2.The liquid-phase chromatographic analysis condition is following:
Configuration 8mmol/lNaHCO
3Be moving phase, flow velocity 1.0ml/min, wavelength are 210nm.
Embodiment 11
The anion-exchange column that obtains among the embodiment 10 is with 8mmol/lNaHCO
3Be moving phase, under different flow rate 1.0ml/min, 1.5ml/min, 2.0ml/min, 2.5ml/min, 3.0ml/min and 3.5ml/min, the record post is pressed, and obtains Fig. 3.Flow velocity and post are pressed and are straight line, and illustrative material has favorable mechanical stability.
Embodiment 12
Step (1) replaces to room temperature with ice-water bath in embodiment 7, other operation is all operated by embodiment 7, the left back 4.5g target compound that obtains, and calculating the chloroacetylation amount is 4.36mmol/g.
Step (2) adds the chloroacetylation microballoon that step (1) obtains in the 250ml round-bottomed flask, add 50ml absolute ethyl alcohol and 15gN, the N-dimethylethanolamine; Ultra-sonic dispersion is even, and 70 ℃ were heated suction filtration 2 hours; Water and methanol wash filter cake, drying obtains quaternary ammoniated microballoon.
The quaternized microballoon of preparation is loaded into 4.6 * 150i.d.mm stainless steel chromatogram post with the homogenate method, to IO
3-, BrO
3-, Br-and NO
3-ion chromatography, the result sees Fig. 4.The liquid-phase chromatographic analysis condition is following:
Configuration 10mmol/lNaClO
4Be moving phase, flow velocity 1.0ml/min, wavelength are 210nm.
Embodiment 13
With 15gN, the N-dimethylethanolamine replaces with 3.0gN in embodiment 12, the N-dimethylethanolamine, and other operation is 3.21mmol/g according to weightening finish calculation key resultant all by embodiment 12 operations at last.
Embodiment 14
With 15gN, the N-dimethylethanolamine replaces with 1.0gN in embodiment 12, the N-dimethylethanolamine, and other operation is 2.81mmol/g according to weightening finish calculation key resultant all by embodiment 12 operations at last.
Embodiment 15
With 15gN, the N-dimethylethanolamine replaces with 0.5gN in embodiment 12, the N-dimethylethanolamine, and other operation is 1.61mmol/g according to weightening finish calculation key resultant all by embodiment 12 operations at last.
Embodiment 16
Step (1) adds 0.025g sodium hydroxide, 0.03g sodium lauryl sulphate and 70ml deionized water in the 250ml round-bottomed flask; Dissolve under the room temperature, add methylacrylic acid-3-trimethoxy silicon propyl ester of 2.0g p-chloromethyl styrene and 0.05ml, stir into emulsion; Charged into nitrogen 20 minutes; Add the 0.018g Potassium Persulphate under the room temperature, be reflected in the nitrogen atmosphere 50 ℃ of heating 5 hours, obtain emulsion particle solution;
Step (2) is got the emulsion particle solution of preparation in the 7ml step (1), adds the 3ml trimethylamine aqueous solution, and 50 ℃ are reacted half a hour in the 25ml round-bottomed flask, obtain quaternised emulsion particle solution;
Step (3) is dispersed in sulfonation microballoon among the embodiment 5 in the quaternized emulsion particle solution of step (2) preparation, centrifugal several, and suction filtration obtains surperficial agglomeration type anion chromatographic filler.
The surperficial agglomeration type anion chromatographic filler of preparation is loaded into 4.6 * 150i.d.mm stainless steel chromatogram post with the homogenate method, to IO
3-, BrO
3-, Br-, NO
2-and NO
3-ion chromatography, the result sees Fig. 5.The liquid-phase chromatographic analysis condition is following:
Configuration 100mmol/lNa
2CO
3+ 50mmol/lNaHCO
3Be moving phase, flow velocity 1.0ml/min, wavelength are 210nm.
The present invention adopts two step dispersion copolymerization methods, and method is easy, is convenient to amplify.Can modify matrix through method of the present invention, wherein modifying method comprises direct surface bonding and surperficial agglomeration latex, thereby reach ionic is separated.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the present invention's design; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention
Claims (7)
1. hybrid inorganic-organic polymer microballoon that is used for chromatography of ions; It is characterized in that; Described polymer microballoon is PS-methylacrylic acid-3-trimethoxy silicon propyl ester amberlite lipoid microsphere; Be specially the multipolymer of vinylbenzene and methylacrylic acid-3-trimethoxy silicon propyl ester, wherein the volume ratio of vinylbenzene and methylacrylic acid-3-trimethoxy silicon propyl ester is 5: 1～20: 1, and microspherulite diameter is 2～10 μ m.
2. a preparation method who is used for the hybrid inorganic-organic polymer microballoon of chromatography of ions is characterized in that, described preparation method is two step dispersion copolymerization methods, comprises the steps:
(1) the stablizer Vinylpyrrolidone polymer is joined in the absolute ethyl alcohol, at room temperature stirring and dissolving adds the vinylbenzene that is dissolved with the initiator Diisopropyl azodicarboxylate then, charges into nitrogen under the room temperature, gets rid of the oxygen in the reaction flask, 50 ℃ then～80 ℃ reacting by heating;
Wherein: the mass ratio of Vinylpyrrolidone polymer and Diisopropyl azodicarboxylate is 5: 1～10: 1;
(2) will be dissolved in the absolute ethyl alcohol with (1) equivalent with the vinylbenzene of (1) moderate and methylacrylic acid-3-trimethoxy silicon propyl ester, charge into nitrogen under the room temperature, get rid of the oxygen in the reaction flask, carry out 50 ℃～80 ℃ preheatings simultaneously with heating in (1) step;
Wherein: the volume ratio of vinylbenzene, methylacrylic acid-3-trimethyl silicane propyl ester and absolute ethyl alcohol is 5: 1: 25～5: 0.5: 25;
(3) after heating is carried out 40 minutes～60 minutes in step (1) and (2), will (2) in the reactant of preheating join in the reaction flask in (1), continue to heat 20 hours～24 hours, suction filtration obtains microballoon;
(4) microballoon that obtains in the step (3) was refluxed 20 hours～24 hours in the mixed solution of water, absolute ethyl alcohol and ammoniacal liquor with in 50 ℃～80 ℃, suction filtration, the microballoon at the beginning of obtaining behind the one-step hydrolysis:
Wherein: the volume ratio of water, absolute ethyl alcohol and ammoniacal liquor is 1: 1: 0.0000001～1: 3: 0.00000012;
(5) microballoon that obtains in the step (4) was refluxed 60 hours～72 hours in 60 ℃～65 ℃ in the mixed solution of water, absolute ethyl alcohol, THF and ammoniacal liquor, obtain final microballoon;
Wherein: the volume ratio of described water, absolute ethyl alcohol, THF and ammoniacal liquor is 1: 1: 0.6: 0.3～1: 1.5: 0.8: 0.3.
3. a kind of sulfonating surface method that is used for the hybrid inorganic-organic polymer microballoon of chromatography of ions as claimed in claim 1 is characterized in that described method of sulfonating comprises the steps:
Microballoon is scattered in the anhydrous methylene chloride, under 0 ℃～100 ℃ conditions, stirs, and drips sulfonated reagent, reacts 10 minutes～30 minutes, uses the frozen water stopped reaction, suction filtration, and water and methyl alcohol difference washing leaching cake three times, drying obtains title product;
Wherein: the 1g microballoon is dispersed in the methylene dichloride of 25～35ml;
Described sulfonated reagent is the vitriol oil or chlorsulfonic acid.
4. a kind of surperficial carboxylic acid method that is used for the hybrid inorganic-organic polymer microballoon of chromatography of ions as claimed in claim 1 is characterized in that described carboxylic acid method comprises the steps:
Microballoon is scattered in the anhydrous methylene chloride, under 0 ℃～25 ℃ conditions, stirs, and adds chloroacetyl chloride and aluminum trichloride (anhydrous), stirs 2 hours～5 hours, uses the frozen water stopped reaction, and suction filtration is once used THF, water and methanol wash filter cake, obtains title product;
Wherein: the 1g microballoon is dispersed in the methylene dichloride of 25～35ml;
The mol ratio of described chloroacetyl chloride, aluminum trichloride (anhydrous) and methylene dichloride is 1: 3: 10～1: 3.5: 15;
Described carboxylic acid reagent is along butyryl oxide, maleic anhydride and Tetra hydro Phthalic anhydride.
5. a kind of surperficial amination method that is used for the hybrid inorganic-organic polymer microballoon of chromatography of ions as claimed in claim 1 is characterized in that described amination method comprises the steps:
(1) be to mix in 1: 0.3: 8～1: 0.5: 12 the alcoholic solution of epoxy chloropropane, Trimethylamine 99 and ETHYLE ACETATE with volume ratio, stirred overnight under the room temperature, suction filtration obtains quaternary ammonium salt;
(2) chloroacetyl chloride and aluminum trichloride (anhydrous) are added in the anhydrous methylene chloride, stirred 10 minutes～30 minutes under the room temperature, add microballoon then; Be uniformly dispersed, under 0 ℃～30 ℃ conditions, reacted 15 minutes～150 minutes; Finish reaction with frozen water, suction filtration is used THF, water and methanol wash filter cake successively; Drying obtains the chlorination microballoon;
Wherein: the 1g microballoon is dispersed in the methylene dichloride of 25～35ml;
Described chloroacetyl chloride, aluminum trichloride (anhydrous), with the mol ratio of methylene dichloride be 1: 3: 10～1: 3.5: 15;
(3) the chlorination microballoon that obtains in the step (2) is dispersed in the THF, adds aminated reagent, under 60 ℃～70 ℃ conditions, refluxed 2 hours～4 hours, suction filtration, water and methanol wash, drying obtains preliminary amination microballoon;
Wherein: the 1g microballoon is dispersed in the THF of 25～35ml;
The mol ratio of described chloroacetyl chloride, aluminum trichloride (anhydrous), amination reagent and methylene dichloride is 1: 3: 10: 10～1: 3.5: 12: 15;
Described amination reagent is diethylenetriamine, triethylene tetramine, polyethylene polyamine, quadrol and hexanediamine;
(4) say that the amination microballoon that obtains in the step (3) joins in the methyl alcohol and be uniformly dispersed, add the quaternary ammonium salt of preparation in the step (1), under 20 ℃～30 ℃ conditions, stirred 14 hours～16 hours, suction filtration, water and methanol wash, drying obtains title product;
Wherein: the 1g microballoon is dispersed in the methyl alcohol of 20～30ml;
Described amination reagent is diethylenetriamine, triethylene tetramine, polyethylene polyamine, quadrol and hexanediamine.
6. a kind of surperficial quaternized method that is used for the hybrid inorganic-organic polymer microballoon of chromatography of ions as claimed in claim 1 is characterized in that described quaternized method comprises the steps:
(1) chloroacetyl chloride and aluminum trichloride (anhydrous) are added in the anhydrous methylene chloride, stirred under the room temperature 10～30 minutes, add microballoon then; Ultra-sonic dispersion is even, under 0 ℃～30 ℃ conditions, reacts 15～150 minutes; Finish reaction with frozen water, suction filtration is used THF, water and methanol wash filter cake successively; Drying obtains the chlorination microballoon;
Wherein: the 1g microballoon is dispersed in the methylene dichloride of 25～35ml;
The mol ratio of described chloroacetyl chloride, aluminum trichloride (anhydrous), quaternary ammonium reagent and absolute ethyl alcohol is 1: 3: 10: 20～1: 3.5: 12: 25;
(2) the chlorination microballoon that obtains in the step (1) is dispersed in the absolute ethyl alcohol, adds quaternizing agent, under 60 ℃～70 ℃ conditions, refluxed 2 hours～4 hours, suction filtration, water and methanol wash, drying obtains quaternized microballoon;
Wherein: the 1g microballoon is dispersed in the absolute ethyl alcohol of 20～30ml;
Described quaternizing agent is Trimethylamine 99, trolamine and N, the N-dimethylethanolamine.
7. the preparation method of the surperficial agglomeration type chromatography of ions of a kind of hybrid inorganic-organic polymer microballoon that is used for chromatography of ions as claimed in claim 1 is characterized in that described preparation method comprises the steps:
(1) sodium lauryl sulphate and sodium hydroxide are added in the deionized water, under the room temperature dispersed with stirring evenly after, add p-chloromethyl styrene and methylacrylic acid-3-trimethoxy silicon propyl ester; Charge into nitrogen and remove oxygen, add Potassium Persulphate then, charge into nitrogen and remove oxygen; Then under 50 ℃～70 ℃ conditions; Heated 5 hours～8 hours, and left standstill, obtain emulsion particle solution;
Wherein: the mol ratio of sodium laurylsulfonate, sodium hydroxide, Potassium Persulphate, p-chloromethyl styrene, methylacrylic acid-3-trimethoxy silicon propyl ester and deionized water is 1: 0.5: 0.5: 15: 0.5: 150～1: 1: 1: 25: 0.8: 200;
(2) in the emulsion particle solution that (1) obtains, add quaternizing agent, under 50 ℃～70 ℃ conditions, heated 1～3 hour, leave standstill, obtain quaternised emulsion particle solution;
Wherein: quaternizing agent is: Trimethylamine 99, triethylamine, trolamine and N, N-dimethylethanolamine;
(3) microballoon with sulfonating surface is dispersed in the quaternized emulsion particle solution that has diluted 5～10 times, stirs 1 hour～5 hours under the room temperature, and centrifugal, suction filtration obtains product;
Wherein: 1g sulfonation microballoon is dispersed in the quaternized emulsion particle solution of dilution of 5～10ml.
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| CN109206555A (en) * | 2018-08-10 | 2019-01-15 | 郑州轻工业学院 | A kind of novel double cross connection silane polymer gellike and its application |
| CN113663742A (en) * | 2021-07-30 | 2021-11-19 | 无锡市凯奥善生物医药科技有限公司 | Preparation method of strong cation exchange chromatographic packing for glycosylated hemoglobin |
| CN114149594A (en) * | 2021-11-03 | 2022-03-08 | 赛分科技扬州有限公司 | Amine salt type polyacrylate emulsion and preparation method thereof |
| CN114324639A (en) * | 2021-12-22 | 2022-04-12 | 浙江工业大学 | Mixed-mode weak cation solid-phase extraction material and preparation method and application thereof |
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| 《Colloid and Polymer Science》 20061202 Xin Lu et al. "Synthesis of poly(styrene-co-3-trimethoxysilyl propyl methacrylate) microspheres coated with polysiloxane layer" 599-604 1-7 第285卷, 第5期 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206555A (en) * | 2018-08-10 | 2019-01-15 | 郑州轻工业学院 | A kind of novel double cross connection silane polymer gellike and its application |
| CN109206555B (en) * | 2018-08-10 | 2020-09-04 | 郑州轻工业学院 | Novel double-crosslinked silane polymer gel and application thereof |
| CN113663742A (en) * | 2021-07-30 | 2021-11-19 | 无锡市凯奥善生物医药科技有限公司 | Preparation method of strong cation exchange chromatographic packing for glycosylated hemoglobin |
| CN113663742B (en) * | 2021-07-30 | 2024-02-09 | 无锡市凯奥善生物医药科技有限公司 | Preparation method of strong cation exchange chromatographic packing for glycosylated hemoglobin |
| CN114149594A (en) * | 2021-11-03 | 2022-03-08 | 赛分科技扬州有限公司 | Amine salt type polyacrylate emulsion and preparation method thereof |
| CN114324639A (en) * | 2021-12-22 | 2022-04-12 | 浙江工业大学 | Mixed-mode weak cation solid-phase extraction material and preparation method and application thereof |
| CN114324639B (en) * | 2021-12-22 | 2023-09-29 | 浙江工业大学 | Mixed-mode weak cation solid phase extraction material and preparation method and application thereof |
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