CN101041438A - Preparation method of alkylated silica gel - Google Patents
Preparation method of alkylated silica gel Download PDFInfo
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- CN101041438A CN101041438A CN 200710054067 CN200710054067A CN101041438A CN 101041438 A CN101041438 A CN 101041438A CN 200710054067 CN200710054067 CN 200710054067 CN 200710054067 A CN200710054067 A CN 200710054067A CN 101041438 A CN101041438 A CN 101041438A
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Abstract
The invention discloses a silica gel and inorganic material power surface modify and preparing method, especially involves a preparing method of alkylated silica gel. The preparing method of alkylated silica gel includes the preparation of activated silica gel, hydrated silica gel and alkylated silica gel. The alkylated silica gel possess good stability and hydrolytic stability, which can be used as water treatment agent, gas adsorbent, absorptive parting material, bulk additive and activator.
Description
Technical field
The present invention relates to a kind of silica gel and inorganic material powder surface modification and preparation method thereof, relate in particular to a kind of preparation method of unimolecular layer organic polymer bonding alkylated silica gel.
Background technology
Alkylated silica gel is to be framework material with silica gel,, can be used as materials such as water conditioner, adsorbent, adsorption and separation material, catalyzer and chromatogram carrier and uses at a kind of functional materials of the various organic groups of its surface grafting by the processing of surface silicon alkanisation.At chromatographic field, alkylation bonded silica gel stationary phase is the main stuffing that the reverse phase liquid chromatography analytical procedure is used, and owing to factors such as steric restrictions, closed-end technology can not be eliminated the influence of silanol groups fully when it was synthetic, cause when analyzing the polar compound thing, tail is taken off in the distortion of the chromatographic peak of chromatographic column.In water treatment and adsorbing domain, silica gel passes through surface modification, but functional groups such as grafted amine groups, carboxyl, polymeric amine, cyanogen and become the absorption exchange material of adsorbable each metal ion species of separation, and can further carry out modification to alkylated silica gel by finishing.In addition, alkylated silica gel can form various complex compound solid catalysts by surface grafting and complexing.As seen, because the matrix of alkylated silica gel has Stability Analysis of Structures, the easily nearly property (substrate molecule accessibility) of functional group, good withstand voltage and resistance toheat, make alkylated silica gel obtain using widely in various occasions.
The preparation method that alkylated silica gel is commonly used is the dilute solution that coupling agent is configured to water, alcohol or organic solvent, pass through the method (ZL02114041.3 of dipping, coupling and radical polymerization then, ZL03119093.6, Liu Shujuan etc., polymer material science and engineering, 2003,19 (6): 65) various powders are handled.May exist silica gel surface silicon alcohol groups remaining quantity big but with these methods silica gel is carried out modification, there is multilayered structure in silica gel surface aggregate thing layer, the structure irregularity, and easily cause the duct of silica gel to stop up and defective such as complicated process of preparation in the modifying process.During research such as Ed.Rosenberg in 1997 silica gel polyamine matrix material, on the basis of traditional alkylated silica gel synthetic method, a kind of new synthetic route has been proposed.This synthetic method (patent No. is 5695882) relates to the silica gel alkylation, comprising: at first clean the silica gel surface with acid; Use the wet air wet silica-gel subsequently, make silica gel surface coverage unit molecule moisture film; Then in the presence of suitable quantity of water, with short chain anchoring agent (Cl
3Si (CH
2)
3Br) with the silica gel surface action.The synthetic alkylated silica gel can make organosilicon radical be close to and fully cover the silica gel surface in this way, and fraction of coverage is up to 94%.Because silanol groups exposes seldom on the silica gel surface, can improve the stability on silica gel surface significantly, greatly improve the acid and alkali-resistance stability and the anti-hydrolysis ability of matrix material.2005, people such as Shen Jian (patent publication No.: CN1687082A) based on the above method, silica gel is carried out hydration, make this method in the industrial operability that has more with climatic chamber.But this synthetic method makes silane coupling agent partial hydrolysis in organic solvent earlier, grafting is carried out on the silica gel surface in the back, certainly will cause silane coupling agent part silanol groups generation condensation reaction to be arranged entering when graft reaction is carried out on the silica gel surface, cause the surface aggregate layer inhomogeneous regular, occur multilayered structure easily, the easier polycondensate of silane coupling agent that causes stops up problems such as silica gel duct.
Summary of the invention
The objective of the invention is to defective, adopt the synthesizing alkylated silica gel of a kind of new preparation method at the prior art existence.This method comprises steps such as activated silica gel preparation, hydrated silica gel preparation and alkylated silica gel preparation, and wherein hydrated silica gel is controlled the silica gel hydration level by temperature by homemade airtight water saturation device; Alkylated silica gel preparation hydrolysis, condensation and the graft reaction by making silane coupling agent be at the phase interface generation reaction in of hydrated silica gel, makes the surface of alkylated silica gel generate neat, self-composed monomolecular polymeric layer uniformly.
In order to realize above-mentioned goal of the invention, the present invention adopts following technical proposals:
The structural formula of alkylated silica gel of the present invention is:
Wherein R is an alkyl, and X is hydrogen, halogen, amido, epoxy group(ing), sulfydryl or cyano functional group.
The method of the synthesizing alkylated silica gel of the present invention comprises the following steps:
1, activated silica gel preparation:
(1) silochrom being put into concentration is that the acid solution of 1mol/L heats, and Heating temperature is 90 ℃ ~ 110 ℃, and the pickling time is 4 ~ 8 hours;
(2) after the silica gel pickling is finished, under comparatively high temps, carry out overanxiously, wash silica gel successively, make its pH reach 6 ~ 7, in baking oven, be dried to constant weight under 90 ℃ ~ 120 ℃ conditions then with pure water and methyl alcohol.
2, hydrated silica gel preparation:
The dry silica gel of step 1 preparation is put into homemade water saturation device, and according to the hydration level of silica gel, the working temperature of regulating the water saturation device is in 45 ℃ ~ 70 ℃, makes silica gel adsorption moisture until reaching adsorption equilibrium.The silica gel hydration level can be estimated with following formula: the density of silica gel water content=silica gel surface-area * unit molecule water layer thickness * water;
Described water saturation device is homemade encloses container, contains automatic watering apparatus, and water is not contacted with silica gel, has temperature automatically controlled function, can make the interior steam partial pressure of container be in state of saturation.
3, alkylated silica gel preparation:
(1) a certain amount of organic solvent through processed is added in the hydrated silica gel of step 2 preparation, stir, under vacuum condition, outgased 5 ~ 10 minutes.
(2) accurate weighing silane coupling agent joins a certain amount ofly in the organic solvent of processed, and short mix is even in mixing tank under the dry gas protection.
(3) solution with step (2) gained joins in the silica gel of step (1), reacting 12 ~ 24 hours under stirring and the certain temperature at a slow speed, carry out reactant overanxious then, be neutral with organic solvent, pure water and methanol wash to pH successively, obtain the fixedly alkylated silica gel of siloxane groups of surface.
(4) alkylated silica gel of step (3) preparation is put into vacuum drying oven or baking oven inner drying, under 60 ℃ ~ 110 ℃, be dried to constant weight, obtain alkylated silica gel.
In the abovementioned alkyl reaction, used organic solvent and water do not dissolve each other, and can dissolve each other fully with selected silane coupling agent.Part solvent enters the silica gel duct during reaction under degassing condition, form the interface with silica gel surface unit molecule water layer, another part solvent to silane coupled dilution agent after, coupling agent is the interface that Medium Diffusion arrives solvent and water with the solvent, because the individual layer water on organic solvent and silica gel surface does not dissolve each other, make silane coupling agent hydrolysis, condensation and graft reaction take place successively at two-phase interface, be grafted on the silica gel surface with self-assembly form and even regular structure, form the unit molecule polymeric layer on the silica gel surface.
The present invention has following beneficial effect: various organic groups are contained on alkylated silica gel of the present invention surface, can be used as materials such as water conditioner, adsorbent, adsorption and separation material, weighting agent, catalyzer and chromatogram carrier, have wide range of applications.Compared with prior art, synthetic method of the present invention comprises steps such as activated silica gel preparation, hydrated silica gel preparation and alkylated silica gel preparation, wherein hydrated silica gel carries out hydration by homemade water saturation device, only the silica gel hydration level is controlled by temperature, technic index is easy to control, simple to operate, labour intensity is low; Alkylated silica gel preparation hydrolysis, condensation and the graft reaction by making silane coupling agent is at the phase interface generation reaction in of hydrated silica gel, make the surface of alkylated silica gel generate neat, uniform self-composed monomolecular polymeric layer, alkylated silica gel has better stable and resistance to hydrolysis energy.Method of the present invention can be used for other surface treatment with inorganic powder material of surface functional group.
Below in conjunction with embodiment, alkylated silica gel preparation method of the present invention is described, embodiment only is explanation the present invention but not content of the present invention is limited.
Embodiment
Embodiment 1:
Raw silicon micelle degree 40-60 order, mean pore size 11-12nm, surface-area 430m
2/ g, bulk density 0.43g/mL; Chloropropyl trichloro-silane is a coupling agent, and molecular formula is Cl (CH
2)
3SiCl
3, under 20 ℃ of conditions, proportion r=1.359-1.360; The synthetic method and the preparation technology of alkylated silica gel are as follows:
1, the preparation of activated silica gel: with 200 grams, granularity is that 40-60 purpose silica gel adds the pickling still, and adding 800mL concentration is the HNO of 1mol/L
3Solution boiled 6 hours under boiling temperature (103 ℃ of bubble point temperatures).After acid pickling step finished, reaction solution used sand core funnel overanxious immediately, washs silica gel successively with pure water and methyl alcohol, makes its pH reach 6, in baking oven, is dried to constant weight under 100 ℃ then.
2, the preparation of hydrated silica gel: activated silica gel is put into homemade encloses container, the working temperature of regulating container according to required silica gel water content is in about 55 ℃ ~ 60 ℃, make silica gel adsorption moisture reach adsorption equilibrium, obtain the hydrated silica gel of planar water about 8%.
3, the preparation of alkylated silica gel:
(1) 350mL is added in the hydrated silica gel of step 2 preparation through the normal hexane of processed, stir, under vacuum condition, outgased 5 ~ 10 minutes.
(2) accurately measure silane coupling agent 95mL, join 350mL in the normal hexane of processed, short mix is even in mixing tank and under the dry gas protection.
(3) solution with step (2) gained joins in the silica gel of step (1) preparation, reacting 16 hours under stirring and the normal temperature condition at a slow speed, reactant is overanxious with sand core funnel then, uses normal hexane, pure water and methanol wash successively, obtains the alkylated silica gel of surface bond siloxane groups.
(4) abovementioned alkyl silica gel is put into vacuum drying oven or baking oven inner drying, under 80 ℃, be dried to constant weight, obtain alkylated silica gel.
Show that through infrared spectra, wettability and pore structure mensuration the alkylated silica gel of preparation is successful.As reference, measure the infrared spectra of silica gel and alkylated silica gel with the KBr compressing tablet.The FTIR spectrogram shows that raw material silica gel is typical amorphous silica gel; The collection of illustrative plates of alkylated silica gel is obviously different with the silica gel collection of illustrative plates, at 2962.4cm
-1, 914.2cm
-1, and 698.2cm
-1The stretching vibration absorption peak that has occurred C-H and C-Cl key respectively illustrates that the silica gel surface introduced carbochain and chlorine atom.The measurement and determination of humidifying angle result of silica gel and alkylated silica gel shows, behind the Silanization reaction, since the surface coverage of silica gel the organism that do not soak of one deck, make silica gel become hydrophobic (90 °) by hydrophilic (0 °), greatly improved the acid and alkali-resistance stability and the anti-hydrolysis ability of alkylated silica gel material.The pore structure measurement result shows that behind the alkylated reaction, the surface-area of silica gel and aperture all slightly reduce.
Embodiment 2
Raw silicon micelle degree 16-80 order, mean pore size 15nm, bulk density 0.463g/mL; Chloropropyl trichloro-silane is a coupling agent, and molecular formula is Cl (CH
2)
3SiCl
3, under 20 ℃ of conditions, proportion r=1.359-1.360; The preparation technology of alkylated silica gel is as follows:
1, the preparation of activated silica gel: the micro-spherical silica gel 10Kg that will dry in advance directly adds the enamel stirring and pickling still that volume is 50L, metering and adding concentration are the hydrochloric acid soln 40L of 1mol/L, reflux under boiling temperature and 54rpm mixing speed then and boil 6 hours.The acid vapour that contains that steams in the pickling still in time returns the pickling still after the glass condenser condensation.Filter, wash the back and under 100 ~ 120 ℃ of temperature, be dried to constant weight.
2, the preparation of hydrated silica gel: place the bottom of φ 120 * 2000mm that the synthetic glass tower of filter screen is housed in the silica gel of 10Kg after pickling and oven dry, airtight, at a certain temperature by water saturation.Hydration time 16 hours, the water regain of hydrated silica gel are 7.4%.
3, the preparation of alkylated silica gel: add the 50L enamel stirring tank from charging opening with the silica gel after the 7.89Kg hydration with through the normal hexane 10L of processed, stir, under vacuum condition, outgased 5 ~ 10 minutes.Take by weighing the 4.74Kg silane coupling agent and measure the normal hexane that 16L handles through molecular sieve dehydration, in mixing tank, mix, add in the silica gel of 50L enamel stirring tank, stir reaction down 16 hours at a slow speed.Separate alkylated silica gel and reaction mother liquor, use normal hexane, pure water and methanol wash alkylated silica gel then respectively.Gained material air dried overnight is then 100-110 ℃ of drying 2 hours.Get the alkylated silica gel product at last.
Show that through infrared spectra, thermogravimetric analysis, wettability and pore structure mensuration the alkylated silica gel of preparation is successful.Wherein through infrared spectra, wettability and pore structure measurement result similar embodiment 1.It is 39.4% that silica gel obtains weight through theory behind the alkylated reaction, and the theoretical weight loss of calcination is 16.9%, and hot analysis revealed weight loss is 15.3%.
Claims (5)
1, a kind of alkylated silica gel is characterized in that the structural formula of alkylated silica gel is:
Wherein R is an alkyl, and X is hydrogen, halogen, amido, epoxy group(ing) or cyano functional group.
2, the synthetic method of the described alkylated silica gel of claim 1 is characterized in that: this method comprises the following steps:
(1) activated silica gel preparation: silochrom is put into acid solution, washed 4 ~ 8 hours down at 90 ℃ ~ 110 ℃; After the silica gel pickling is finished, overanxious, wash pH successively with pure water and methyl alcohol and reach 6 ~ 7; Under 90 ℃ ~ 120 ℃ conditions, be dried to constant weight then.
(2) hydrated silica gel preparation: the activated silica gel of step (1) preparation is put into homemade water saturation device, and according to the hydration level of silica gel, the working temperature of regulating the water saturation device is in 45 ℃ ~ 70 ℃, makes silica gel adsorption moisture reach adsorption equilibrium.
(3) alkylated silica gel preparation: will add in the hydrated silica gel of step (2) through the organic solvent of processed, and stir, under vacuum condition, outgas 5 ~ 10 minutes; Accurate weighing silane coupling agent joins a certain amount ofly in the organic solvent of processed, and short mix is even; Gained solution joins in the silica gel, is reacting 12 ~ 24 hours under stirring and the certain temperature at a slow speed; Overanxious reactant then, use organic solvent, pure water and methanol wash successively, and under 60 ℃ ~ 110 ℃, be dried to constant weight, obtain alkylated silica gel.
3, the described hydrated silica gel preparation of claim 2 is characterized in that the hydration level of hydrated silica gel is regulated the silica gel hydration level by the temperature of controlling homemade water saturation device.
4, the described alkylated silica gel of claim 2 preparation is characterized in that used organic solvent and water do not dissolve each other, and can dissolve each other fully with selected silane coupling agent.
5, the described alkylated silica gel preparation of claim 2 is characterized in that used organic solvent is divided into two portions.Part solvent enters the silica gel duct under degassing condition, form the interface with silica gel surface unit molecule water layer; Another part solvent is used for the diluted silane coupling agent, and and the solvent that soaks into silica gel in advance use as reaction medium.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011012019A1 (en) * | 2009-07-31 | 2011-02-03 | 中国科学院大连化学物理研究所 | Separation material based on silica gel having copolymerization reaction on surface and preparation method thereof |
| CN101716499B (en) * | 2009-11-27 | 2011-12-14 | 中国科学院广州地球化学研究所 | Mesoporous silica gel loading titanium pillared clay photocatalyst, preparation method and application thereof |
| CN102814058A (en) * | 2012-09-17 | 2012-12-12 | 工信华鑫科技有限公司 | Method for implementing nickel-magnesium separation, enrichment and purification by using heavy metal adsorbing material |
| CN103007905A (en) * | 2012-11-15 | 2013-04-03 | 郑州大学 | Tetraazacalix [2] arene [2] triazine bonded silica gel solid phase extraction material, preparation method and application thereof |
| CN103028383A (en) * | 2012-12-31 | 2013-04-10 | 浙江月旭材料科技有限公司 | Silica gel chromatography packing and preparation method thereof |
| CN101829551B (en) * | 2010-05-12 | 2013-04-24 | 武汉大学 | Silica gel fixed phase of mixed model as well as preparation method and application thereof |
| CN111954468A (en) * | 2018-03-29 | 2020-11-17 | 日挥触媒化成株式会社 | Pest repellent composition |
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2007
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011012019A1 (en) * | 2009-07-31 | 2011-02-03 | 中国科学院大连化学物理研究所 | Separation material based on silica gel having copolymerization reaction on surface and preparation method thereof |
| CN101987293B (en) * | 2009-07-31 | 2013-01-02 | 中国科学院大连化学物理研究所 | Chromatographic separation material based on copolymerization on silica gel surface and preparation thereof |
| CN101716499B (en) * | 2009-11-27 | 2011-12-14 | 中国科学院广州地球化学研究所 | Mesoporous silica gel loading titanium pillared clay photocatalyst, preparation method and application thereof |
| CN101829551B (en) * | 2010-05-12 | 2013-04-24 | 武汉大学 | Silica gel fixed phase of mixed model as well as preparation method and application thereof |
| CN102814058A (en) * | 2012-09-17 | 2012-12-12 | 工信华鑫科技有限公司 | Method for implementing nickel-magnesium separation, enrichment and purification by using heavy metal adsorbing material |
| CN103007905A (en) * | 2012-11-15 | 2013-04-03 | 郑州大学 | Tetraazacalix [2] arene [2] triazine bonded silica gel solid phase extraction material, preparation method and application thereof |
| CN103028383A (en) * | 2012-12-31 | 2013-04-10 | 浙江月旭材料科技有限公司 | Silica gel chromatography packing and preparation method thereof |
| CN103028383B (en) * | 2012-12-31 | 2014-12-10 | 浙江月旭材料科技有限公司 | Silica gel chromatography packing and preparation method thereof |
| CN111954468A (en) * | 2018-03-29 | 2020-11-17 | 日挥触媒化成株式会社 | Pest repellent composition |
| CN113694907A (en) * | 2020-05-22 | 2021-11-26 | 中国科学院大连化学物理研究所 | Pure water-resistant chromatographic stationary phase and preparation method and application thereof |
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