CN102627285B - Novel montmorillonite nanometer complex and preparation method thereof - Google Patents
Novel montmorillonite nanometer complex and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a novel montmorillonite nanometer complex, in particular to the montmorillonite nanometer complex consisting of a polyether ammonium cation, Ti4<+> or/and Sb3<+> ions and montmorillonite as well as a preparation method of the montmorillonite nanometer complex. According to the montmorillonite nanometer complex, the polyether ammonium cation accounts for 5-80 percent by weight of the total amount of the polyether ammonium cation, and the Ti4<+> ion or the Sb3<+> ion or the Ti4<+> and the Sb3<+> ions account for 0.00001-2 percent by weight of the total amount of the montmorillonite nanometer complex. Under the conditions of normal pressure and room temperature of 100DEG C, polyether ammonium salt, titanium tetrachloride or/and antimony trichloride ion are intercalated into the montmorillonite to obtain the montmorillonite nanometer complex. The montmorillonite nanometer complex is simple in preparation process, is mild in conditions and easy in industrial production.
Description
Technical field
The present invention relates to a kind of new modified polynite, particularly a kind of by polyethers ammonium cation, Ti
4+or/and Sb
3+common modified montmorillonoid complex body forming of ion and polynite and preparation method thereof.
Background technology
Inorganic column clay specific surface area is large, thermostability is high, is a class porous new function material that is subject in recent decades extensive concern and obtains developing rapidly.They are to natural clay and the large specific surface area of Yan Yougeng and unique pore structure, thereby as selected adsorbent, catalyzer and support of the catalyst etc., have shown wide application potential in petrochemical complex and field of Environment Protection.In the 1980s, having prepared at first aluminium is intercalated montmorillonite, but its specific surface area is not ideal enough.Afterwards, it is found that titanium pillared montmorillonite has larger duct, higher heat or hydrothermal stability, and good photocatalytic activity, be widely used.
Publication number be the patent system of CN102258993A standby titanium oxide polynite photocatalyst, polynite is compared, the porosity of this photocatalyst, specific surface area and pore volume significantly improve.Publication number is that the patent of CN1872908A is inserted polynite by titanium tetrachloride, has prepared titanium-montmorillonite catalyst, for the preparation of the matrix material of polyethylene and multipolymer and polynite.Publication number is that the patent of CN1330101A is also that titanium tetrachloride is inserted to polynite, has prepared montmorillonite load titanium catalyst, for the preparation of the matrix material of the polyolefine such as polyethylene, polypropylene and polynite.BJ University of Aeronautics & Astronautics developed antimony pillared montmorillonite in 2010, and used it in the preparation of polyester/Nano composite material of montmorillonite, had obtained good effect.Yet, less for the patent report of antimony pillared montmorillonite.
The feature of polyethers ammonium salt modified montmorillonoid is that the interlamellar spacing of polynite is larger, more than can reaching 8nm.As calendar year 2001 Lin J.J. adopts polyetheramine D2000 salt manufacturing, the polyethers ammonium modified montmorillonoid that intercalation obtains.Within 2004, Salahuddin N.A. adopts polyetheramine T5000 salt manufacturing intercalated montmorillonite, and the preparation for high-performance epoxy resin by modified montmorillonoid.Yet, less about the patent of polyethers ammonium modified montmorillonoid.Publication number is the modified by polyether glycol polynite of the patent of CN1693549A, for the preparation of montmorillonite/polyurethane nano composite material.
Yet, about polyethers ammonium cation, Ti
4+or/and Sb
3+modified montmorillonoid prepared by common intercalated montmorillonite, will have polyethers ammonium modified montmorillonoid and Ti concurrently
4+ion is or/and Sb
3+the performance of ion modification polynite, the research of this respect and Patents there is not yet report at home and abroad.
Summary of the invention
One of object of the present invention is to provide a kind of by polyethers ammonium cation, Ti
4+or/and Sb
3+the common montmorillonite-based nano complex body forming of ion and polynite.
Another object of the present invention is to provide a kind of preparation by polyethers ammonium cation, Ti
4+or/and Sb
3+the method of the common montmorillonite-based nano complex body forming of ion and polynite.
Novel montmorillonite-based nano complex body involved in the present invention is by polyethers ammonium cation, Ti
4+or/and Sb
3+ion and polynite form jointly.Wherein, polyethers ammonium cation accounts for the 5wt%～80wt% of montmorillonite-based nano complex body total amount, Ti
4+ion or Sb
3+the summation of ion or this two metal ion species accounts for the 0.00001wt%～2wt% of montmorillonite-based nano complex body total amount.
The preparation method of novel montmorillonite-based nano complex body involved in the present invention is: under the temperature condition of normal pressure, room temperature～100 ℃, with polyethers ammonium salt, titanium tetrachloride or/and butter of antimony under certain kind and a certain amount of solvent condition, intercalated montmorillonite, reflux 0.5-8 hour, obtains montmorillonite-based nano complex body.
Described novel montmorillonite-based nano complex body, polyethers ammonium cation accounts for the 10wt%～40wt% of montmorillonite-based nano complex body total amount, Ti
4+ion or Sb
3+the total amount of ion or this two metal ion species accounts for the 0.001wt%～1wt% of montmorillonite-based nano complex body total amount.
Described polyethers ammonium salt reacts preparation by polyether diamine or polyethers triamine with hydrochloride aqueous solution.The molecular-weight average of described polyether diamine or polyethers triamine is 400～6000.Fig. 1 is several commodity polyether diamines and polyethers triamine.
Described polyethers ammonium cation reacts with polynite and adopts the mixing solutions of water or acetone or water and acetone as dispersion medium, and temperature of reaction is 60～80 ℃.
Described Ti
4+ion or Sb
3+when ion or this two metal ion species react with polynite jointly, adopt the mixing solutions of ethanol or water or water and ethanol as dispersion medium, temperature of reaction is 60～80 ℃.
Described positively charged ion and the intercalation of polynite are: first use polyethers ammonium salt intercalated montmorillonite, then use titanium tetrachloride or/and butter of antimony intercalated montmorillonite; Or first use titanium tetrachloride or/and butter of antimony intercalated montmorillonite, then use polyethers ammonium salt intercalated montmorillonite.
Novel montmorillonite-based nano complex body of the present invention, there is the features such as specific surface area is large, Heat stability is good, can be used as the additive of sorbent material, catalyzer and high-performance nano polymkeric substance, under the temperature condition of 200-300 ℃, still there is certain stability, can meet harsher practical service environment or high temperature adding technology condition.And the preparation technology of this novel montmorillonite-based nano complex body is simple, mild condition, does not use the more difficult fatty alcohol of removing, and does not relate to complicated aftertreatment technology, is easy to suitability for industrialized production.
Accompanying drawing explanation
Accompanying drawing 1 is structural formula schematic diagram, the polymerization degree and the molecular weight of different polyetheramine molecules.
Embodiment
Embodiment 1
5.6g titanium tetrachloride is dissolved in the dilute hydrochloric acid that 100ml concentration is 1mol/L, is configured to titanium intercalation solution.15g sodium-based montmorillonite is dispersed in the deionized water of 750ml, is mixed with montmorillonite suspension liquid.Under the condition of room temperature, magnetic agitation, titanium intercalation solution is slowly splashed in montmorillonite suspension liquid, dropwise rear reaction system and be warming up to 80 ℃, under magnetic agitation, reflux 0.5 hour, obtain titanium intercalated montmorillonite mixed solution.Reaction mixture is centrifugal, obtain titanium-polynite.
1.7g polyetheramine D400 is dissolved in 36ml acetone, 1.5g hydrochloric acid soln (37wt%) mixes with 12ml deionized water, under magnetic agitation, in D400 acetone soln, drips hydrochloric acid soln, dropwise rear continuation magnetic agitation 3h, obtain polyethers ammonium salt D400 solution.Above-mentioned titanium-polynite is dispersed in the deionized water of 1000ml, under room temperature, drips while stirring D400 polyethers ammonium salt solution, after dropwising, reaction system is warming up to 80 ℃, under magnetic agitation, reflux 0.5 hour.Reaction mixture is centrifugal, and separation obtains D400 polyethers ammonium cation and Ti
4+the montmorillonite-based nano complex body of modified synergic.
Embodiment 2
2.8g titanium tetrachloride is dissolved in the dilute hydrochloric acid that 100ml concentration is 1mol/L, is configured to titanium intercalation solution.15g sodium-based montmorillonite is dispersed in the dehydrated alcohol of 100ml, is mixed with montmorillonite suspension liquid.Under the condition of room temperature, magnetic agitation, titanium intercalation solution is slowly splashed in montmorillonite suspension liquid, dropwise rear reaction system and be warming up to 60 ℃, under magnetic agitation, reflux 8 hours, obtain titanium intercalated montmorillonite mixed solution.Reaction mixture is centrifugal, isolate titanium intercalated montmorillonite.
After 25g polyetheramine D2000,2.6g hydrochloric acid soln (37wt%) are mixed with 20mL deionized water, magnetic agitation 3h, obtains D2000 polyethers ammonium salt.Titanium intercalated montmorillonite is dispersed in the deionized water of 1000ml and the mixed solvent of acetone (volume ratio 1: 1), under room temperature, drip while stirring D2000 polyethers ammonium salt solution, after dropwising, reaction system is warming up to 60 ℃, under magnetic agitation, refluxes 8 hours.Reaction mixture is centrifugal, and separation obtains D2000 polyethers ammonium salt and Ti
4+montmorillonite-based nano complex body.
Embodiment 3
25g polyetheramine T5000 is dissolved in 48ml acetone, under room temperature magnetic agitation, adds 1.5g hydrochloric acid soln (37wt%) and 20mL deionized water mixed solution, continue magnetic agitation 3h, obtain T5000 polyethers ammonium salt intercalation solution.15g sodium-based montmorillonite is dispersed in the acetone of 1000ml, is mixed with montmorillonite suspension liquid.Under the condition of room temperature, magnetic agitation, T5000 polyethers ammonium salt intercalation solution is slowly splashed in montmorillonite suspension liquid, after dropwising, reaction system is warming up to 70 ℃, under magnetic agitation, reflux 4 hours, obtain T5000 polyethers ammonium salt intercalated montmorillonite mixed solution.Reaction mixture is centrifugal, isolate T5000 polyethers ammonium salt intercalated montmorillonite.
0.07g titanium tetrachloride is dissolved in the dilute hydrochloric acid that 100ml concentration is 1mol/L, is configured to titanium intercalation solution.T5000 polyethers ammonium salt intercalated montmorillonite is dispersed in the mixed solvent (volume ratio 1: 1) of 1000ml deionized water and ethanol, obtains the suspension of T5000 polyethers ammonium salt intercalated montmorillonite.Under room temperature, magnetic agitation condition, titanium intercalation solution is slowly splashed in T5000 polyethers ammonium salt intercalated montmorillonite suspension, dropwise rear reaction system and be warming up to 70 ℃, under magnetic agitation, reflux 4 hours, reaction mixture is centrifugal, and separation obtains T5000 polyethers ammonium salt and Ti
4+montmorillonite-based nano complex body.
Embodiment 4
2.8g titanous chloride is dissolved in the dilute hydrochloric acid that 100ml concentration is 1mol/L, is configured to titanium intercalation solution.15g sodium-based montmorillonite is dispersed in the deionized water of 750ml, is mixed with montmorillonite suspension liquid.Under the condition of room temperature, magnetic agitation, titanium intercalation solution is slowly splashed in montmorillonite suspension liquid, dropwise rear reaction system and be warming up to 80 ℃, under magnetic agitation, reflux 1 hour, obtain titanium intercalated montmorillonite mixed solution.Reaction mixture is centrifugal, obtain titanium-polynite.
3.3g polyetheramine D400 is dissolved in 72ml acetone, and 1.5g hydrochloric acid soln (37wt%) mixes with 12ml deionized water,
Under magnetic agitation, in D400 acetone soln, drip hydrochloric acid soln, dropwise rear continuation magnetic agitation 3h, obtain polyethers ammonium salt D400 solution.Above-mentioned titanium-polynite is dispersed in the deionized water of 1000ml, under room temperature, drips while stirring D400 polyethers ammonium salt solution, after dropwising, reaction system is warming up to 80 ℃, under magnetic agitation, reflux 1 hour.Reaction mixture is centrifugal, and separation obtains D400 polyethers ammonium cation and Ti
3+the montmorillonite-based nano complex body of modified synergic.
Embodiment 5
2g titanium tetrachloride and 2g butter of antimony are dissolved in the dilute hydrochloric acid that 100ml concentration is 1mol/L, are configured to titanium/antimony intercalation solution.15g sodium-based montmorillonite is dispersed in the dehydrated alcohol of 750ml, is mixed with montmorillonite suspension liquid.Under the condition of room temperature, magnetic agitation, titanium/antimony intercalation solution is slowly splashed in montmorillonite suspension liquid, dropwise rear reaction system and be warming up to 60 ℃, under magnetic agitation, reflux 5 hours, obtain titanium/antimony intercalated montmorillonite mixed solution.Reaction mixture is centrifugal, isolate Ti
4+and Sb
3+intercalated montmorillonite.
After 25g polyetheramine T3000,2.6g hydrochloric acid soln (37wt%) are mixed with 20mL deionized water, magnetic agitation 3h, obtains T3000 polyethers ammonium salt.Titanium/antimony intercalated montmorillonite is dispersed in the deionized water of 1000ml and the mixed solvent of acetone (volume ratio 1: 1), under room temperature, drip while stirring T3000 polyethers ammonium salt solution, after dropwising, reaction system is warming up to 70 ℃, under magnetic agitation, refluxes 2 hours.Reaction mixture is centrifugal, and separation obtains T3000 polyethers ammonium salt, Ti
4+and Sb
3+montmorillonite-based nano complex body.
Embodiment 6
25g polyetheramine D4000 is dissolved in 48ml acetone, under room temperature magnetic agitation, adds 1.5g hydrochloric acid soln (37wt%) and 20mL deionized water mixed solution, continue magnetic agitation 3h, obtain D4000 polyethers ammonium salt intercalation solution.15g sodium-based montmorillonite is dispersed in the acetone of 1000ml, is mixed with montmorillonite suspension liquid.Under the condition of room temperature, magnetic agitation, D4000 polyethers ammonium salt intercalation solution is slowly splashed in montmorillonite suspension liquid, after dropwising, reaction system is warming up to 70 ℃, under magnetic agitation, reflux 6 hours, obtain D4000 polyethers ammonium salt intercalated montmorillonite mixed solution.Reaction mixture is centrifugal, isolate D4000 polyethers ammonium salt intercalated montmorillonite.
8g butter of antimony is dissolved in the dilute hydrochloric acid that 100ml concentration is 1mol/L, is configured to antimony intercalation solution.D4000 polyethers ammonium salt intercalated montmorillonite is dispersed in the mixed solvent (volume ratio 1: 1) of 1000ml deionized water and ethanol, obtains the suspension of D4000 polyethers ammonium salt intercalated montmorillonite.Under room temperature, magnetic agitation condition, antimony intercalation solution is slowly splashed in D4000 polyethers ammonium salt intercalated montmorillonite suspension, dropwise rear reaction system and be warming up to 70 ℃, under magnetic agitation, reflux 6 hours, reaction mixture is centrifugal, and separation obtains D4000 polyethers ammonium salt and Sb
3+montmorillonite-based nano complex body.
Embodiment 7
0.2g butter of antimony is dissolved in the dilute hydrochloric acid that 100ml concentration is 1mol/L, is configured to antimony intercalation solution.15g sodium-based montmorillonite is dispersed in the deionized water of 500ml, is mixed with montmorillonite suspension liquid.Under the condition of room temperature, magnetic agitation, antimony intercalation solution is slowly splashed in montmorillonite suspension liquid, dropwise rear reaction system and be warming up to 50 ℃, under magnetic agitation, reflux 5 hours, obtain antimony intercalated montmorillonite mixed solution.Reaction mixture is centrifugal, isolate Sb
3+intercalated montmorillonite.
After 25g polyetheramine D2000,2.6g hydrochloric acid soln (37wt%) are mixed with 20mL deionized water, magnetic agitation 3h, obtains D2000 polyethers ammonium salt.Antimony intercalated montmorillonite is dispersed in the deionized water of 1000ml and the mixed solvent of acetone (volume ratio 1: 1), under room temperature, drip while stirring D2000 polyethers ammonium salt solution, after dropwising, reaction system is warming up to 50 ℃, under magnetic agitation, refluxes 5 hours.Reaction mixture is centrifugal, and separation obtains D2000 polyethers ammonium salt and Sb
3+montmorillonite-based nano complex body.
Embodiment 8
6g polyetheramine D400 is dissolved in 100ml acetone, 3g hydrochloric acid soln (37wt%) mixes with 20ml deionized water, under magnetic agitation, in D400 acetone soln, drips hydrochloric acid soln, dropwise rear continuation magnetic agitation 3h, obtain polyethers ammonium salt D400 solution.15g sodium-based montmorillonite is dispersed in the deionized water of 750ml, drips while stirring D400 polyethers ammonium salt solution under room temperature, after dropwising, magnetic agitation is 7 hours at ambient temperature.Reaction mixture is centrifugal, and separation obtains D400 polyethers ammonium cation intercalated montmorillonite.
0.1g titanium tetrachloride and 8g butter of antimony are dissolved in the dilute hydrochloric acid that 100ml concentration is 1mol/L, are configured to titanium/antimony intercalation solution.D400 polyethers ammonium cation intercalated montmorillonite is dispersed in the deionized water of 750ml, is mixed with montmorillonite suspension liquid.Under the condition of room temperature, magnetic agitation, titanium/antimony intercalation solution is slowly splashed in montmorillonite suspension liquid, dropwise rear reaction system and continue to keep room temperature, magnetic agitation 7 hours, obtains polyethers ammonium salt and titanium/antimony intercalated montmorillonite mixed solution.Reaction mixture is centrifugal, isolate D400 polyethers ammonium cation, Ti
4+and Sb
3+montmorillonite-based nano complex body.
Claims (9)
1. a montmorillonite-based nano complex body, is characterized in that: this montmorillonite-based nano complex body is by polyethers ammonium cation, Ti
4+or/and Sb
3+ion and polynite form jointly, and wherein polyethers ammonium cation accounts for the 5wt%～80wt% of montmorillonite-based nano complex body total amount, Ti
4+ion or Sb
3+the total amount of ion or this two metal ion species accounts for the 0.00001wt%～2wt% of montmorillonite-based nano complex body total amount.
2. montmorillonite-based nano complex body according to claim 1, is characterized in that: polyethers ammonium cation accounts for the 10wt%～40wt% of montmorillonite-based nano complex body total amount, Ti
4+ion or Sb
3+the total amount of ion or this two metal ion species accounts for the 0.001wt%～1wt% of montmorillonite-based nano complex body total amount.
3. the preparation method of a montmorillonite-based nano complex body according to claim 1, it is characterized in that: under the temperature condition of normal pressure, room temperature～100 ℃, with polyethers ammonium salt, titanium tetrachloride or/and butter of antimony intercalated montmorillonite obtains montmorillonite-based nano complex body.
4. method according to claim 3, is characterized in that: polyethers ammonium salt reacts preparation by polyether diamine or polyethers triamine with hydrochloride aqueous solution.
5. method according to claim 4, is characterized in that: the molecular-weight average of polyether diamine or polyethers triamine is 400～6000.
6. method according to claim 3, it is characterized in that: polyethers ammonium cation reacts with polynite and adopts the mixing solutions of water or acetone or water and acetone as dispersion medium, polyethers ammonium cation is 0.5～2 with the CEC ratio of polynite, and temperature of reaction is that 60～80 ℃ of reaction times are 0.5～8 hour.
7. method according to claim 3, it is characterized in that: when metal ion reacts with polynite, adopt the mixing solutions of ethanol or water or water and ethanol as dispersion medium, metallic cation is 0.1～8 with the CEC ratio of polynite, temperature of reaction is 60～80 ℃, and the reaction times is 0.5～8 hour.
8. method according to claim 3, is characterized in that: first use polyethers ammonium salt intercalated montmorillonite, then use titanium tetrachloride or/and butter of antimony intercalated montmorillonite.
9. method according to claim 3, is characterized in that: first use titanium tetrachloride or/and butter of antimony intercalated montmorillonite, then use polyethers ammonium salt intercalated montmorillonite.
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| CN103193242B (en) * | 2013-04-09 | 2014-12-17 | 苏州旭达环保科技有限公司 | Montmorillonoid loaded polyethyleneimine water treatment agent as well as preparation method and application thereof |
| CN105419262A (en) * | 2014-09-02 | 2016-03-23 | 允友成(宿迁)复合新材料有限公司 | Polylactic acid/montmorillonite nanometer composite material preparation method |
| CN105732961B (en) * | 2014-12-11 | 2018-06-01 | 中国石油天然气股份有限公司 | The preparation method of polyethylene terephthalate nanocomposite |
| CN105732962A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of polyethylene glycol terephthalate/montmorillonite nano composite material |
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| CN1330101A (en) * | 2001-08-03 | 2002-01-09 | 中国科学院长春应用化学研究所 | Montmorillonite-TiCl4 catalyst and process for preparing polyolefin/montmorillonite composition |
| CN1872908A (en) * | 2005-05-31 | 2006-12-06 | 中国石油天然气股份有限公司 | Method for preparing catalyst of montmorillonite-titanium tetrachloride, and composite material of polyethylene/montmorillonite |
| CN101717562A (en) * | 2009-11-27 | 2010-06-02 | 北京航空航天大学 | Transparent high-barrier polyethylene glycol terephthalate composite material product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1330101A (en) * | 2001-08-03 | 2002-01-09 | 中国科学院长春应用化学研究所 | Montmorillonite-TiCl4 catalyst and process for preparing polyolefin/montmorillonite composition |
| CN1872908A (en) * | 2005-05-31 | 2006-12-06 | 中国石油天然气股份有限公司 | Method for preparing catalyst of montmorillonite-titanium tetrachloride, and composite material of polyethylene/montmorillonite |
| CN101717562A (en) * | 2009-11-27 | 2010-06-02 | 北京航空航天大学 | Transparent high-barrier polyethylene glycol terephthalate composite material product |
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