CN103421155A - Preparation method for novel PS-co-PVEA@SiO2 - Google Patents
Preparation method for novel PS-co-PVEA@SiO2 Download PDFInfo
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- CN103421155A CN103421155A CN2013101743859A CN201310174385A CN103421155A CN 103421155 A CN103421155 A CN 103421155A CN 2013101743859 A CN2013101743859 A CN 2013101743859A CN 201310174385 A CN201310174385 A CN 201310174385A CN 103421155 A CN103421155 A CN 103421155A
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Abstract
The invention discloses a preparation method for PS-co-PVEA@SiO2, which is mainly characterized in that phenethylene, tetraphenylethylene-N, N-ethylethanamine (VEA), and divinyl benzene are used as raw materials, and MPS-SiO2 is used as seed to prepare PS-co-PVEA@SiO2 composite microsphere through the dispersion polymerization reaction principle. According to the invention, the average particle diameter of the PS-co-PVEA@SiO2 composite microsphere is 180 nm; the chelation function of a polymer layer and the advantage of mechanical stability of the silicon dioxide particle are combined; heavy metal can be efficiently absorbed, and recycling is adopted. The technical preparation process is relatively simple, and is without post-modified treating process. The manufactured PS-co-PVEA@SiO2 composite microsphere has uniform particle diameter, lager specific surface area, and can be widely used in the fields of electron, textiles, medical treatment and health, food, paint, plastic and the like.
Description
Technical field
The present invention relates to a kind of novel amino polymer graft modification nano silicon (PS-
Co-PVEA@SiO
2) preparation method, belong to nano material and technical field.
Background technology
The world today, along with social economy's develop rapidly, the heavy metal contamination thereupon brought is day by day serious.In heavy metal contamination, it is again the most important thing that water pollutes.Water is the indispensable material of people's daily life, for heavy metal ion enters human body, provides approach.In great heavy metal contamination event, propagation medium is all water basically in the world.The minamata disease that for example nineteen fifty-three Japan occurs.In the removal heavy metal method, adsorption method studied person is gradually praised highly, but existing heavy metal absorbent is synthetic simple, and building-up process easily causes secondary pollution, after absorption, the heavy metal ion recycling is more difficult, and to concentration, lower polluted water is processed and is difficult to reach comparatively desirable effect.
Composite nano-microsphere has the advantages such as specific surface area is large, adsorption point is many, dispersiveness is better, is subject to pursuing of more and more investigators.At present, the investigator has synthesized sulfhydryl modified complex microsphere and amino modified complex microsphere, and has specifically studied its effect aspect heavy metal adsorption.But sulfhydryl modified complex microsphere percentage of grafting is lower, corresponding adsorption effect is not obvious.Amino modified complex microsphere building-up process is comparatively complicated, is at first the modification of nano silicon, and secondly GMA further is grafted on nano-silica surface again, is finally carrying out aminating reaction, the process complexity, and influence factor is more.The present invention is grafted to nano-silica surface by monomer one step with amino group, and process is simple.
Summary of the invention
The object of the present invention is to provide the preparation method of above-mentioned this novel amino polymer graft modification nano silicon.
The object of the present invention is achieved like this: the preparation of (1) two key modified manometer silicon dioxides, at first by ammoniacal liquor 8 ml, tetraethoxy 0.04 mol, deionized water 20 ml, dehydrated alcohol 180 ml, join in 500 ml single port flasks, regulating magnetic stirring apparatus speed is 900 r/min, after reacting 12 h, to continuing to drip 1.1 ml(3 mmol in reaction soln) γ-methacryloxypropyl trimethoxy silane (MPS), after stirring 12 h, solution centrifugal is precipitated, and disperse to wash, finally by the nano silicon (MPS-SiO of MPS modification
2) constant volume is scattered in dehydrated alcohol.(2) the synthetic purifying that reaches of monomer, p-chloromethyl styrene 0.1-0.2 mol, diethylamine 0.2-0.4 mol, chloroform 200-300 mL, Anhydrous potassium carbonate 30-50 g are mixed, 30-50 ℃ of temperature lower magnetic force stirring reaction 20 h, until react completely, with a large amount of deionized water repetitive scrubbings, until the reactant water is colourless.Under 0.098 MPa condition, by the reactant monomer of gained, by the neutral alumina chromatography column, the underpressure distillation at 90-160 ℃ of temperature of the monomer after chromatography, finally obtain pure monomer 4-vinyl phenyl
N,
N-diethylamide (VEA).Styrene monomer (Ps) is at 30-60 ℃ of lower underpressure distillation purifying, and Vinylstyrene (DVB), at 40-80 ℃ of lower underpressure distillation purifying, is finally sealed three kinds of monomers up for safekeeping refrigeration.(3) MPS modified Nano SiO
2Ultrasonic dispersion, after disperseing fully, is to add successively above-mentioned prepared 4-vinyl phenyl under 900 r/min states in magnetic stirring apparatus speed
N,
N-diethylamide monomer, vinylbenzene, Vinylstyrene, polyvinylpyrrolidone, initiator azo-bis-isobutyl cyanide.After dispersed with stirring; reaction flask is repeatedly bled and filled nitrogen 5 times; then under 70 ℃ of temperature condition of nitrogen protection, normal pressure stirs 20 h; form organic polymeric layer on the nano silicon spheres surface; finally adopt centrifugation ultra-sonic dispersion method repetitive scrubbing, obtain having the composite nanoparticle PS-of nucleocapsid structure
Co-PVEA@SiO
2.
The present invention has following characteristics: a preparation process is relatively simple, does not have the post-modification treating processes.The 2nd, the novel amino polymer graft modification nano silicon of preparation has the advantage advantages such as for example specific surface area is large, better dispersed, and action site is many of nanoparticle, can greatly improve adsorptive power.The 3rd, novel amino polymer graft modification nano silicon particle diameter 180 nm that the present invention is prepared, have good stability, mechanical stability advantage.
The accompanying drawing explanation
Fig. 1: the FT-IR collection of illustrative plates of novel amino polymer graft modification nano silicon
Fig. 1 is the organic-inorganic nano composite particles of 3 kinds of different ingredients and the TF-IR spectrogram of sterling nano silicon.Wherein at 1100 cm
-1The absorption peak at place can belong to the antisymmetric stretching vibration peak of Si-O-Si, 798 cm
-1With 464 cm
-1The absorption peak at place can belong to respectively Si-O-Si rocking vibration and flexural vibration peak, and these three absorption peaks all belong to the characteristic peak of silicon-dioxide.And at 3400 cm
-1The stretching vibration peak of can the belong to-OH of absorption peak at place; At 1633 cm
-1The absorption peak at place can belong to the flexural vibration peak of H-O-H.The amended silicon dioxide microsphere that MPS passes through, find several new peaks, i.e. 2855 cm
-1Place and 2920 cm
-1Methylene peak, 1632 cm at place
-1Place's vinyl stretching vibration peak and 1715 cm
-1The carbonylic stretching vibration peak at place, the MPS that has been expressed as the merit grafting.In the organic-inorganic nano particle spectrum of 3 kinds of different ingredients, except typical silicon-dioxide peak value, 1600,1492,1451,757, and 699 cm
-1Place belongs to peak PS, at 1000-1350 cm
-1The peak at place belongs to the C-N stretching vibration, 2855 cm
-1Place and 2920 cm-1 places are methylene radical stretching vibration peaks, and these peaks all show to successfully synthesize the 4-vinyl phenyl
N,
N-diethylamide monomer graft modification nano-silicon dioxide particle.
Fig. 2: the TEM figure of novel amino polymer graft modification nanometer titanium dioxide silicon sample under embodiment 1.Obvious nucleocapsid structure has all appearred in composite particles as seen from the figure, and the mean thickness of polymer layer is about 40nm through measurement.
Fig. 3: the TEM figure of novel amino polymer graft modification nanometer titanium dioxide silicon sample under embodiment 2.Obvious nucleocapsid structure has all appearred in composite particles as seen from the figure, and the mean thickness of polymer layer is about 40nm through measurement.
Fig. 4: the TEM figure of novel amino polymer graft modification nanometer titanium dioxide silicon sample under embodiment 3.Obvious nucleocapsid structure has all appearred in composite particles as seen from the figure, and the mean thickness of polymer layer is about 40nm through measurement.
Specific implementation method
Below provide example so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as the restriction to the invention protection domain; some nonessential improvement and adjustment that the person skilled in the art in this field makes the present invention according to the foregoing invention content, must belong to protection scope of the present invention.
Specific implementation method
Below provide example so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as the restriction to the invention protection domain; some nonessential improvement and adjustment that the person skilled in the art in this field makes the present invention according to the foregoing invention content, must belong to protection scope of the present invention.
Nano silicon (the MPS-SiO of the two key modifications of at first ultrasonic dispersion
2) alcoholic solution 20 min, get 20 ml(0.4 g) be placed in 50 ml there-necked flasks, then add successively vinylbenzene 1 g, 4-vinyl phenyl N, N-diethylamide monomer 1 g, Vinylstyrene 40 mg, azo-bis-isobutyl cyanide 60 mg, ultrasonic dispersion 5 min.Fill the nitrogen deoxygenation 5 times repeatedly, the system sealing, be placed in 70 ℃ of water-bath reaction 20 h.Reaction finishes, by final product centrifugal ultrasonic dispersion washing repeatedly, 40 ℃ of vacuum-dryings.
Embodiment 2
Nano silicon (the MPS-SiO of the two key modifications of at first ultrasonic dispersion
2) alcoholic solution 20 min, get 20 ml(0.4 g) be placed in 50 ml there-necked flasks, add successively again vinylbenzene 1g, 4-vinyl phenyl N, N-diethylamide monomer 1g, Vinylstyrene 40 mg, polyvinylpyrrolidone 0.2 g, azo-bis-isobutyl cyanide 60 mg, ultrasonic dispersion 5 min.Fill the nitrogen deoxygenation 5 times repeatedly, the system sealing, be placed in 70 ℃ of water-bath reaction 20 h.Reaction finishes, by final product centrifugal ultrasonic dispersion washing repeatedly, 40 ℃ of vacuum-dryings.
Nano silicon (the MPS-SiO of the two key modifications of at first ultrasonic dispersion
2) alcoholic solution 20 min, get 20 ml(0.4 g) be placed in 50 ml there-necked flasks, add successively again vinylbenzene 1 g, 4-vinyl phenyl N, N-diethylamide monomer 1 g, Vinylstyrene 20 mg, polyvinylpyrrolidone 0.2 g, azo-bis-isobutyl cyanide 60 mg, ultrasonic dispersion 5 min.Fill the nitrogen deoxygenation 5 times repeatedly, the system sealing, be placed in 70 ℃ of water-bath reaction 20 h.Reaction finishes, by final product centrifugal ultrasonic dispersion washing repeatedly, 40 ℃ of vacuum-dryings.
Claims (8)
1. a novel amino polymer graft modification nano silicon (PS-
Co-PVEA@SiO
2) the preparation method, it is characterized in that with vinylbenzene, 4-vinyl phenyl
N,
N-diethylamide (VEA), Vinylstyrene are raw material, MPS-SiO
2As seed, by dispersion polymerization Grafted Nano-scale silicon-dioxide, successfully prepared PS-
Co-PVEA@SiO
2Complex microsphere.
2. according to the preparation method of claim 1 an amino polymer Grafted Nano-scale SiO 2 composite microsphere, it is characterized in that silane coupling agent is γ-methacryloxypropyl trimethoxy silane (MPS).
3. according to the preparation method of claim 1 an amino polymer Grafted Nano-scale SiO 2 composite microsphere, it is characterized in that polymkeric substance be vinylbenzene, 4-vinyl phenyl with
N,
NThe combination of-diethylamide (VEA).
4. according to the preparation method of claim 1 an amino polymer Grafted Nano-scale SiO 2 composite microsphere, it is characterized in that solution solvent is dehydrated alcohol.
5. according to the preparation method of claim 1 an amino polymer Grafted Nano-scale SiO 2 composite microsphere, it is characterized in that stablizer is that polyvinylpyrrolidone (PVP), linking agent are Vinylstyrene (DVB).
6. according to the preparation method of claim 1 an amino polymer Grafted Nano-scale SiO 2 composite microsphere, it is characterized in that the particle diameter of nano silicon is in 100 nm left and right, preparing environment is nitrogen protection, and 60 ℃-70 ℃, the reaction times is 20 h.
7. according to the preparation method of claim 1 an amino polymer Grafted Nano-scale SiO 2 composite microsphere, it is characterized in that adopting " grafting from " method graft modification, preparation process is relatively simple, does not have the post-modification treating processes.
8. according to the preparation method of claim 1 an amino polymer Grafted Nano-scale SiO 2 composite microsphere, it is characterized in that the PS-of gained
Co-PVEA@SiO
2Complex microsphere combines the chelating function of polymer layer and the mechanical stability advantage of nano-silicon dioxide particle.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105606486A (en) * | 2016-01-27 | 2016-05-25 | 浙江理工大学 | Testing method for modified nano-silica surface grafting state |
| CN110564405A (en) * | 2019-09-20 | 2019-12-13 | 复旦大学 | Rare earth nano material containing polystyrene shell and biological coupling and application thereof |
| CN111282594A (en) * | 2018-12-06 | 2020-06-16 | 中国石油天然气股份有限公司 | Thickened oil hydrothermal cracking catalyst, preparation and application thereof |
| CN113105289A (en) * | 2021-04-13 | 2021-07-13 | 安徽珍硒农业科技有限责任公司 | Selenium-rich organic nutrient solution for fruit crop cultivation and preparation method thereof |
-
2013
- 2013-05-13 CN CN2013101743859A patent/CN103421155A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105606486A (en) * | 2016-01-27 | 2016-05-25 | 浙江理工大学 | Testing method for modified nano-silica surface grafting state |
| CN111282594A (en) * | 2018-12-06 | 2020-06-16 | 中国石油天然气股份有限公司 | Thickened oil hydrothermal cracking catalyst, preparation and application thereof |
| CN110564405A (en) * | 2019-09-20 | 2019-12-13 | 复旦大学 | Rare earth nano material containing polystyrene shell and biological coupling and application thereof |
| CN113105289A (en) * | 2021-04-13 | 2021-07-13 | 安徽珍硒农业科技有限责任公司 | Selenium-rich organic nutrient solution for fruit crop cultivation and preparation method thereof |
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Application publication date: 20131204 |