CN105001576B - A kind of preparation method of hud typed cationic microgel nano-noble metal composite - Google Patents
A kind of preparation method of hud typed cationic microgel nano-noble metal composite Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of hud typed cationic microgel nano-noble metal composite, hydrophilic sex differernce using two kinds of monomers, the hud typed cationic microgel of pH response is prepared by a step emulsion polymerization, and with it as reducing agent, by electrostatic interaction, noble metal precursor body is complexed in the network structure of cationic microgel, using the confinement effect of microgel and the reproducibility of microgel shell tertiary amine groups, prepare, with heating autoreduction method, the hud typed cationic microgel nano-noble metal composite to have good pH response and stability.Present invention reaction is quick, is not required to separately add reducing agent, and the composite of preparation has using value in fields such as catalysis, medical diagnosiss, bio-imaging, medicine controlled releasing, surface-enhanced fluorescence, surface plasma body resonant vibration and sensors.
Description
Technical field
The invention belongs to the technical field of composite materials of nano-noble-metal-loaded microgranule, it is related to a kind of pH sensitivity hud typed
The preparation method of cationic microgel nano-noble-metal-loaded composite.
Background technology
Nano-noble metal has that specific surface area is big, surface energy is high, high adsorption capacity the features such as, be widely used in optics,
Electricity, magnetics, physicss, the chemically and thermally various fields such as mechanics.But just because of having very high surface energy, the expensive gold of nanometer
Belong to and there is a problem of being easy to assemble again, need to add macromolecule stabilizer as template or microreactor, to overcome nano metal
The problem reunited.
With respect to templates such as a shape, block and star polymers, the network structure of microgel provides nanometer heavy metal and becomes
The space (confinement effect) of core and growth, it is easy to obtain the nanoparticle of particle diameter, morphology controllable, effectively prevent nanoparticle group
The generation of poly- effect.By changing monomer component, dosage of crosslinking agent and preparation condition it is easy to obtain particle diameter and species etc. controlled
Nanometer heavy metal.
The microgel of environmental sensitivity nucleocapsid structure is that parcel gel layer is constituted outside emulsion particle daughter nucleus, and it can be same
When there is the property of core and shell.By introducing the macromolecular material with higher force strength and stability in kernel, permissible
Effectively improve mechanical strength and the stability of gel.And when environmental condition (temperature, pH etc.) changes, because its nucleocapsid is swelling
The difference of performance, gives it and is better than some performances of response homopolymer, therefore suffer from widely paying close attention to.
In recent years, based on temperature sensitivity nucleocapsid type microgel in-situ control synthesis nano-noble metal achieve very big
Progress.Ballauff M [The Journal of Physical Chemistry B, 2006, 110(9): 3930-
3937] pass through seeded emulsion polymerization, be prepared for the Thermo-sensitive nucleocapsid that polystyrene is that core, NIPA make shell
Type microgel, and by introducing AgNO3, in NaBH4Under effect, it is prepared for loading the hud typed composite microgel of nanometer Ag.But value
It is noted that due to NaBH4Rate of reduction too fast, reaction controlling is bad, and BH4 -Hydrogen atom in anion participates in
The reduction process of metal, [Science of the Total is easily polluted by boride in the metal surface resulting in
Environment, 2010, 408(5): 999-1006].Zhang Ying etc. [chemical journal, 2011,69 (20): 2385-
2392] P (St-NIPAM)/hud typed composite microgel of PNIPAM-Ag has been synthesized with two-step method, except that have selected ethanol
As reducing agent, reacted under ammonia environment, the benefit of this selection is not introduce BH4 -Ion, and ethanol can make
For a kind of dispersant of microgel, but operating procedure is loaded down with trivial details.
Introduce ionic groups (as carboxyl and amino etc.) in microgel, microgel pH response performance can be given, make
When using for mould material, using the chemical bond cooperation to noble metal precursor body of cross-linked structure and functional group of microgel
With particle diameter and the easily controllable nano-noble metal composite of form can be obtained.PH response nucleocapsid type microgel is main at present
Concentrate on hud typed anion (carboxyl) microgel, and such as Zhang etc. [Journal of Catalysis, 2007,250 (2):
324-330] nano Pd particle has been loaded on hud typed anion microgel, the composite microgel of formation is to Suzuki reaction and Heck
Reaction has good catalytic performance.
Nagasaki etc. [Macromolecular Chemistry and Physics, 2007,208 (11): 1176-
1182] using have pH response polymethylacrylic acid diethylamino ethyl ester (PDEAMA) cationic microgel be template,
With HAuCl4For presoma, the reproducibility one-step method using PDEAMA microgel prepares nanometer Au.Its shortcoming is the glass of PDEAMA
Glass temperature is low, easy film forming, and heat stability is poor, and polymer is weaker as the reproducibility of reducing agent, the mistake of preparation nanometer Au
Journey needs 24h, expends the time longer.
Content of the invention
It is an object of the invention to provide a kind of preparation side of hud typed cationic microgel-nano-noble metal composite
Method it is not necessary to hud typed cationic microgel simply can be obtained by seeded emulsion polymerization, and without adding reducing agent, only
Reproducibility by microgel itself can synthesize the hud typed cationic microgel of pH sensitivity-nano-noble metal composite.
The present invention utilizes the hydrophilic difference of two kinds of monomers, and a step emulsion polymerization prepares the pH that shell is cationic polymer
Response nucleocapsid type microgel, and introduce heavy metal presoma, under conditions of being added without reducing agent, heating autoreduction is prepared
It is dispersed in shell in the layer nano-noble metal, had both avoided the impact to nano-noble metal performance for the additional reducing agent, shorten again
Distance is reached between nano-noble metal and reaction substrate.
The concrete preparation side of hud typed cationic microgel-nano-noble metal composite of the present invention presented below
Method.
1) by the Surfactant SDS (SDS) of monomer mass 3～4% and monomer mass 15～20%
Macromolecular stabilizer agent is soluble in water to make emulsion.
Preferably, in described emulsion, surfactant accounts for the 0.5 of emulsion quality with the gross mass of macromolecular stabilizer agent
～2%.
2) cross-linking agent of monomer mass 1～2% is added to obtain monomer mixed solution in monomer, described monomer is by nuclear layer monomer
Methyl methacrylate and cationic monomer in mass ratio 1: 1～3 are mixed to get.
3), under inert gas shielding, described monomer mixed solution is added dropwise in described emulsion and stirs, be warming up to 25
～70 DEG C, the reactant aqueous solution 10～15h of Deca initiator, obtain pH response hud typed cationic microgel dispersion liquid, its
The addition of middle initiator is the 0.5～1.5% of monomer mass.
4) described microgel dispersion is dialysed, removed unreacted monomer, macromolecular stabilizer agent and surface activity
Agent, the pH value adjusting microgel dispersion is 4.0～8.0, and stirring makes it fully swelling.
5) mol ratio according to the N atom in described microgel dispersion and heavy metal presoma is 3～8: 1, will be described
Heavy metal presoma and swelling microgel dispersion mix and blend, obtain microgel-presoma compound system.
6) under conditions of being added without reducing agent, described microgel-presoma compound system is stirred in 20～40 DEG C of insulations
Mix reaction 3～24h, generate the hud typed cationic microgel-nano-noble metal composite of load nanometer heavy metal particles.
In the above-mentioned preparation method of the present invention, described macromolecular stabilizer agent be polyethylene glycol methacrylate-styrene polymer (PEGMA) or
Polymethylacrylic acid 2- (dimethylamino) ethyl ester (PDMA of styrene end-blocking50-St).Preferably, described Polyethylene Glycol methyl-prop
The equal relative molecular mass of number of olefin(e) acid ester is 475～8000, polymethylacrylic acid 2- (dimethylamino) ethyl ester of styrene end-blocking
The equal relative molecular mass of number be 8000～8500.
In the above-mentioned preparation method of the present invention, described cationic monomer is diethyl aminoethyl methacrylate
(DEAMA), methacrylic acid diisopropylaminoethyl ethyl ester (DPA) or NVP (VP), preferably DEAMA.
Cross-linking agent of the present invention is Ethylene glycol dimethacrylate (EGDMA), polypropylene glycol dimethacrylate
Any one in ester (PPGDA) or divinylbenzene (DVB), preferably EGDMA.
Described initiator is azo-bis-isobutyrate hydrochloride (V-50), azo two isobutyl imidazoline hydrochloride (VA-
044), Ammonium persulfate., potassium peroxydisulfate, Ammonium persulfate .-N, N, N', N'- tetramethylethylenediamine compound system (AP-TEMED), over cure
Sour potassium-N, any one in N, N', N'- tetramethylethylenediamine compound system (KP-TEMED), preferably Ammonium persulfate..
In preparation method of the present invention, described heavy metal presoma is salt or the acid of palladium, gold or platinum.
Further, described heavy metal presoma is tetrachloro-palladium acid sodium (Na2PdCl4), gold chloride (HAuCl4) or six
Hydration chloroplatinic acid (H2PtCl6·6H2One of O), preferably gold chloride.
Wherein, described adjust microgel dispersion pH value step in, it is preferred to use the HCl solution of 0.01mol/L or
NaOH solution adjusts the pH value of microgel dispersion.
The present invention considers that nuclear layer monomer PMMA glass temperature is higher, cationic monomers thing glass
The relatively low feature of glass temperature, using the difference of hydrophilic and reactivity ratio between two kinds of monomers, by a step emulsion polymerization, makes
Standby obtain the hud typed cationic microgel of sphericity good pH sensitivity.The core of microgel is mechanical strength and heat stability
Preferably polymethyl methacrylate polymer microsphere, the table with pH response that shell is formed for cationic monomers
Layer, while remaining hydrogel good pH sensitivity, improves its mechanical strength and heat stability.And then, the present invention
With described hud typed cationic microgel as template, under electrostatic interaction, noble metal precursor body is fully complexed to cationic microgel and coagulates
In glue, using the confinement effect of cationic microgel three-dimensional net structure and the reproducibility of microgel shell tertiary amine groups, not another
Under conditions of outer addition reducing agent, prepared with heating autoreduction method and there is the hud typed of good pH response and stability
Microgel-nano-noble metal composite.
Preparation method of the present invention is simple to operate, and wherein nano-noble metal is distributed in shell, can by adjust microgel and
Proportioning of noble metal precursor body etc., realizes the size of nano-noble metal and form are regulated and controled.
That hud typed cationic microgel-nano-noble metal composite is considered class to the pH response of present invention preparation is homogeneous
Catalyst, it combines the high activity of homogeneous catalyst and heterogeneous catalysis and feature easy to be recycled, has micro- simultaneously
The distinctive sensitive property of gel and the distinctive catalytic property of nano-noble metal.Its cationic microgel-nano-noble metal can be in acid
Property under the conditions of formed homogeneous phase, effectively improve catalytic efficiency, and can in the basic conditions pass through centrifugation etc. method recycle.Its
Catalytic reaction can be carried out in aqueous phase or organic system, and the enforcement for " Green Chemistry " provides probability, in catalyst, biology
The fields such as probe, Chemical Decomposition have broad application prospects.
The composite of present invention preparation is also on medical diagnosiss, bio-imaging, medicine controlled releasing, surface-enhanced fluorescence, surface
The field such as plasma resonance and sensor has using value.
Brief description
Fig. 1 is the TEM picture of the microgel of embodiment 1 preparation.
Fig. 2 is the TEM picture of the microgel-nano-Au composite material of embodiment 1 preparation.
Fig. 3 is the microgel of embodiment 1 preparation and the automatic potentiometric titration curve chart of microgel-nano-Au composite material.
Fig. 4 is microgel-nano-Au composite material particle diameter at various ph values and the maximum absorption wave of embodiment 1 preparation
Long change curve.
Fig. 5 is the microgel of embodiment 1 preparation and the X-ray diffraction spectra figure of microgel-nano-Au composite material.
Fig. 6 is the microgel of embodiment 1 preparation and the weight-loss curve figure of microgel-nano-Au composite material.
Specific embodiment
Embodiment 1
Weigh 0.09g SDS, add in 45mL water, ultrasonic 10min, it is transferred in the four-hole bottle with agitating device, plus
Enter 0.6g PEGMA (Mn ≈ 2080), logical N2, 250r/min stirring and emulsifying 20min.
Weigh 0.03g DVB, mix with 2g DEAMA, 1g MMA, ultrasonic make its mix homogeneously.Mixed liquor is added constant voltage
In Dropping funnel, make it uniformly with the stirring 2h in speed instillation four-hole bottle that drips of 0.3mL/min, be warming up to 65 DEG C.
By 0.03g (NH4)2S2O8It is dissolved in 5mL water, add in constant pressure funnel, dripped with the speed of 0.25mL/min
Enter in four-hole bottle.React 12h after completion of dropping, generate PMMA/PDEAMA microgel white emulsion.
The PMMA/PDEAMA microgel deionized water dialysis of preparation, until the electrical conductivity of aqueous solution of dialysing no longer occurs
Change, to remove unreacted monomer, macromolecular stabilizer agent and surfactant.
Take the PMMA/PDEAMA microgel after dialysis, with 0.01mol/L HCl solution regulation pH value to 6.0, magnetic agitation
2h so as to fully swelling, makes the PMMA/PDEAMA microgel of protonation.
By the PMMA/PDEAMA microgel dispersion of protonation and HAuCl4Press [N]: the mol ratio of [Au]=8: 1 is prepared into
Mixed liquor, stirs 2h, obtains microgel-presoma compound system.Under conditions of being added without reducing agent, it is incubated anti-at 30 DEG C
Answer 24h, stablized and outward appearance be claret hud typed cationic microgel-nano-Au composite material dispersion liquid.
The deionized water dilution microgel of above-mentioned preparation and the dispersion liquid of microgel-nano-Au composite material, obtain
Concentration is the dispersion liquid of 0.02wt%.Draw a dispersant liquid drop on copper mesh, after spontaneously drying 24h under room temperature, carried out with TEM
Observe, result is shown in Fig. 1, Fig. 2.It is seen that the mean diameter of microgel is 235nm, the particle diameter of nanometer Au is about
5.92nm, uniform in micro-gel surface or inner dispersion, and monodispersity is good.
The microgel of preparation and microgel-nano-Au composite material are dispersed in the NaCl solution of 0.01mol/L respectively
Obtain microgel dispersion and the microgel-nano-Au composite material dispersion liquid of 0.02wt%, adjusted with the HCl solution of 0.1mol/L
Saving its pH value is 3, and magnetic agitation 12h under room temperature, using ZDJ-4A type automatical potentiometric titrimeter, with 0.01mol/L NaOH standard
Solution carries out current potential-conductimetric titration to dispersion liquid, obtains the automatic potentiometric titration figure shown in Fig. 3.
Titration curve is divided into I, II, III 3 regions, wherein, Ith area represents with 0.01mol/L NaOH solution and positive
Excessive H in ion microgel+, IIth area represents the-N (CH in microgel2CH3)2Deprotonation, IIIth area represents OH-Excessive.According to
Degree of neutralization α and pKRelation between a, can be calculated the p of microgelKA value is 6.5.Microgel dispersion and microgel-receive
The constant-current titration figure of rice Au composite dispersion liquid is almost consistent, illustrates that the microgel after composite Nano Au remains microgel special
Some pH responses.
Fig. 4 is microgel-nano-Au composite material manufactured in the present embodiment particle diameter (a) at various ph values and maximum suction
The changing trend diagram of luminosity (b).It can be seen that with the rising of pH value, the absorption of microgel-nano-Au composite material
The mobile 6nm of spike length about, there is red shift；With the change of pH value, the volume of composite changes, and particle diameter diminishes.Study carefully
Its reason, the change of nanometer Au surface plasmon absorption peak and composite particle diameter be all due to polymer hydrophilicity with
The change of pH value causes.
Fig. 5 is microgel manufactured in the present embodiment and the X-ray diffraction spectra figure of microgel-nano-Au composite material.From
It is 38.2,44.4,64.5,77.5 at 2 θ angles respectively that in figure can be seen that the position of main diffraction peak, represents Au's respectively
The diffraction maximum of (110), (200), (220) and (311) crystal face in face-centered cubic crystal.Thus explanation microgel-nanometer Au is combined
With the presence of crystalline state Au in material.
After microgel manufactured in the present embodiment and microgel-nano-Au composite material dialysis, it is vacuum dried at 40 DEG C, uses
German NETZSCH TG 209 F3 type thermogravimetric analyzer carries out thermogravimetric analysiss.According to Fig. 6 data, calculate microgel-nanometer Au
Nanometer gold content in composite is 32.3%.
Embodiment 2
Weigh 0.10g SDS, add in 45mL water, ultrasonic 10min, it is transferred in the four-hole bottle with agitating device, plus
Enter 0.5g PEGMA (Mn ≈ 2080), logical N2, with 180r/min stirring and emulsifying 30min.
Weigh 0.06g DVB, mix with 2g VP, 1g MMA, ultrasonic make its mix homogeneously.Mixed liquor addition constant voltage is dripped
In liquid funnel, make it uniformly with the stirring 2h in speed instillation four-hole bottle that drips of 0.3mL/min, be warming up to 65 DEG C.
By 0.045g K2S2O8It is dissolved in 5mL water, add in constant pressure funnel, instill four with the speed of 0.25mL/min
In mouth bottle.React 12h after completion of dropping, generate PMMA/PVP microgel emulsion.
The PMMA/PVP microgel deionized water dialysis of preparation, until the electrical conductivity of aqueous solution of dialysing no longer becomes
Change, to remove unreacted monomer, macromolecular stabilizer agent and surfactant.
Take the PMMA/PVP microgel after dialysis, pH value is adjusted to 5.0 with 0.01mol/L HCl solution, magnetic agitation 2h,
Make it fully swelling, make the PMMA/PVP microgel dispersion of protonation.
By the PMMA/PPVP microgel dispersion of protonation and Na2PdCl4Press [N]: the mol ratio of [Pd]=8: 1 is prepared into
Mixed liquor, stirs 2h, obtains microgel-presoma compound system.Under conditions of being added without reducing agent, it is incubated anti-at 40 DEG C
Answer 3h, stablized and outward appearance be black microgel-nano Pd particle composite dispersion liquid.
Embodiment 3
Weigh 0.12g SDS, add in 50mL water, ultrasonic 10min, it is transferred in the four-hole bottle with agitating device, plus
Enter 0.6g PEGMA (Mn ≈ 475), logical N2, with 180r/min stirring and emulsifying 20min.
Weigh 0.03g EGDMA, mix with 2g DEAMA, 1g MMA, ultrasonic make its mix homogeneously.Mixed liquor is added permanent
In pressure Dropping funnel, make it uniformly with the stirring 2h in speed instillation four-hole bottle that drips of 0.3mL/min, be warming up to 65 DEG C.
0.03g V-50 is dissolved in 5mL water, adds in constant pressure funnel, instill four mouthfuls with the speed of 0.25mL/min
In bottle.React 12h after completion of dropping, generate PMMA/PDEAMA microgel white emulsion.
The PMMA/PDEAMA microgel deionized water dialysis of preparation, until the electrical conductivity of aqueous solution of dialysing no longer occurs
Change, to remove unreacted monomer, macromolecular stabilizer agent and surfactant.
Take the PMMA/PDEAMA microgel after dialysis, with 0.01mol/L HCl solution regulation pH value to 6.0, magnetic agitation
2h so as to fully swelling, makes the PMMA/PDEAMA microgel dispersion of protonation.
By the PMMA/PDEAMA microgel dispersion of protonation and H4Cl6OPt presses [N]: the mol ratio preparation of [Pt]=8: 1
Become mixed liquor, stir 2h, obtain microgel-presoma compound system.Under conditions of being added without reducing agent, it is incubated at 35 DEG C
Reaction 24h, obtains the dispersion liquid of stable microgel-Pt nano particle composite.
Embodiment 4
Weigh 0.09g SDS, add in 45mL water, ultrasonic 10min, it is transferred in the four-hole bottle with agitating device, plus
Enter 0.6g PEGMA (Mn ≈ 2080), logical N2, with speed stirring and emulsifying 20min of 200r/min.
Weigh 0.04g PPGDA, mix with 1.5g DPA, 1.5g MMA, ultrasonic make its mix homogeneously.Mixed liquor is added
In constant pressure funnel, make it uniformly with the stirring 2h in speed instillation four-hole bottle that drips of 0.3mL/min, be warming up to 35 DEG C.
0.015g KP-TEMED is dissolved in 5 mL water, adds in constant pressure funnel, dripped with the speed of 0.3mL/min
Enter in four-hole bottle.React 10 h after completion of dropping, generate PMMA/PDPA microgel emulsion.Other is such as embodiment 1.
Embodiment 5
Weigh 0.09g SDS, add in 45mL water, ultrasonic 10min, it is transferred in the four-hole bottle with agitating device, plus
Enter 0.6g PDMA50- St, logical N2, with speed stirring and emulsifying 20min of 200r/min.
Weigh 0.03g PPGDA, mix with 2g DEAMA, 1g MMA, ultrasonic make its mix homogeneously.Mixed liquor is added permanent
In pressure Dropping funnel, make it uniformly with the stirring 2h in speed instillation four-hole bottle that drips of 0.3mL/min, be warming up to 65 DEG C.
0.03g VA-044 is dissolved in 5mL water, adds in constant pressure funnel, instill four with the speed of 0.25mL/min
In mouth bottle.React 12h after completion of dropping, generate PMMA/PDEAMA microgel white emulsion.
The PMMA/PDEAMA microgel deionized water dialysis of preparation, until the electrical conductivity of aqueous solution of dialysing no longer occurs
Change, to remove unreacted monomer, macromolecular stabilizer agent and surfactant.
Take the PMMA/PDEAMA microgel after dialysis, with 0.01mol/L HCl solution regulation pH value to 4.0, magnetic agitation
2h so as to fully swelling, makes the PMMA/PDEAMA microgel dispersion of protonation.
By the PMMA/PDEAMA microgel dispersion of protonation and HAuCl4Press [N]: [Au]=6: 1 mol ratio is prepared into
Mixed liquor, stirs 2h, obtains microgel-presoma compound system.Under conditions of being added without reducing agent, it is incubated anti-at 35 DEG C
Answer 12h, stablized and outward appearance be claret hud typed cationic microgel-nano-Au composite material dispersion liquid.
Embodiment 6
Weigh 0.09g SDS, add in 45mL water, ultrasonic 10min, it is transferred in the four-hole bottle with agitating device, plus
Enter 0.6g PEGMA (Mn ≈ 8000), logical N2, with speed stirring and emulsifying 20min of 200r/min.
Weigh 0.03g EGDMA, mix with 2g DEAMA, 1g MMA, ultrasonic make its mix homogeneously.Mixed liquor is added permanent
In pressure Dropping funnel, make it uniformly with the stirring 2h in speed instillation four-hole bottle that drips of 0.3mL/min, be warming up to 25 DEG C.
0.03g AP-TEMED is dissolved in 5mL water, adds in constant pressure funnel, instilled with the speed of 0.25mL/min
In four-hole bottle.React 12h after completion of dropping, generate PMMA/PDEAMA microgel white emulsion.
The PMMA/PDEAMA microgel deionized water dialysis of preparation, until the electrical conductivity of aqueous solution of dialysing no longer occurs
Change, to remove unreacted monomer, macromolecular stabilizer agent and surfactant.
Take the PMMA/PDEAMA microgel after dialysis, with 0.01mol/L NaOH solution regulation pH value to 8.0, magnetic force stirs
Mix 2h.
By PMMA/PDEAMA microgel dispersion and slaine (Na2PdCl4) press [N]: [Au]=8: 1 mol ratio is prepared into
Mixed liquor, stirs 2h, obtains microgel-presoma compound system.Under conditions of being added without reducing agent, it is incubated anti-at 35 DEG C
Answer 18h, stablized and outward appearance be claret hud typed cationic microgel-nano-Au composite material dispersion liquid.
Embodiment 7
Weigh 0.09g SDS, add in 45mL water, ultrasonic 10min, it is transferred in the four-hole bottle with agitating device, plus
Enter 0.6g PEGMA (Mn ≈ 2080), logical N2, with speed stirring and emulsifying 20min of 250r/min.
Weigh 0.03g DVB, mix with 3g DEAMA, 1g MMA, ultrasonic make its mix homogeneously.Mixed liquor is added constant voltage
In Dropping funnel, make it uniformly with the stirring 2h in speed instillation four-hole bottle that drips of 0.3mL/min, be warming up to 65 DEG C.
By 0.03g (NH4)2S2O8It is dissolved in 5mL water, add in constant pressure funnel, dripped with the speed of 0.25mL/min
Enter in four-hole bottle.React 12h after completion of dropping, generate PMMA/PDEAMA microgel white emulsion.
The PMMA/PDEAMA microgel deionized water dialysis of preparation, until the electrical conductivity of aqueous solution of dialysing no longer occurs
Change, to remove unreacted monomer, macromolecular stabilizer agent and surfactant.
Take the PMMA/PDEAMA microgel after dialysis, with 0.01mol/L HCl solution regulation pH value to 6.0, magnetic agitation
2h so as to fully swelling, makes the PMMA/PDEAMA microgel dispersion of protonation.
By the PMMA/PDEAMA microgel dispersion of protonation and HAuCl4Press [N]: [Au]=7: 1 mol ratio is prepared into
Mixed liquor, stirs 2h, obtains microgel-presoma compound system.Under conditions of being added without reducing agent, it is incubated anti-at 30 DEG C
Answer 24h, stablized and outward appearance be claret hud typed cationic microgel-nano-Au composite material dispersion liquid.
Embodiment 8
Weigh 0.09g SDS, add in 45mL water, ultrasonic 10min, it is transferred in the four-hole bottle with agitating device, plus
Enter 0.45g PEGMA (Mn ≈ 475), logical N2, with speed stirring and emulsifying 20min of 250r/min.
Weigh 0.03g DVB, mix with 1.5g DEAMA, 1.5g MMA, ultrasonic make its mix homogeneously.Mixed liquor is added
In constant pressure funnel, make it uniformly with the stirring 2h in speed instillation four-hole bottle that drips of 0.3mL/min, be warming up to 65 DEG C.
By 0.03g (NH4)2S2O8It is dissolved in 5mL water, add in constant pressure funnel, dripped with the speed of 0.25mL/min
Enter in four-hole bottle.React 12 h after completion of dropping, generate PMMA/PDEAMA microgel white emulsion.
The PMMA/PDEAMA microgel deionized water dialysis of preparation, until the electrical conductivity of aqueous solution of dialysing no longer occurs
Change, to remove unreacted monomer, macromolecular stabilizer agent and surfactant.
Take the PMMA/PDEAMA microgel dispersion after dialysis, with 0.01mol/L HCl solution regulation pH value to 6.0, magnetic
Power stirring 2h so as to fully swelling, makes the PMMA/PDEAMA microgel dispersion of protonation.
By the PMMA/PDEAMA microgel dispersion of protonation and HAuCl4Press [N]: [Au]=3: 1 mol ratio is prepared into
Mixed liquor, stirs 2h, obtains microgel-presoma compound system.Under conditions of being added without reducing agent, it is incubated anti-at 20 DEG C
Answer 24h, stablized and outward appearance be claret hud typed cationic microgel-nano-Au composite material dispersion liquid.
Claims (7)
1. a kind of preparation method of hud typed cationic microgel-nano-noble metal composite, is characterized in that：
1) by the macromolecular stabilizer of the Surfactant SDS of monomer mass 3～4% and monomer mass 15～20%
Agent is soluble in water to make emulsion, and described macromolecular stabilizer agent is polyethylene glycol methacrylate-styrene polymer or the poly- first of styrene end-blocking
Base acrylic acid 2- (dimethylamino) ethyl ester；
2) cross-linking agent of monomer mass 1～2% is added to obtain monomer mixed solution in monomer, described monomer is by nuclear layer monomer methyl
Acrylic acid methyl ester. and cationic monomer in mass ratio 1: 1～3 are mixed to get, and described cationic monomer is methacrylic acid
Diethylamino ethyl ester, methacrylic acid diisopropylaminoethyl ethyl ester or NVP；
3), under inert gas shielding, described monomer mixed solution is added dropwise in described emulsion and stirs, be warming up to 25～70
DEG C, the reactant aqueous solution 10～15h of Deca initiator, obtain pH response hud typed cationic microgel dispersion liquid, wherein draw
The addition sending out agent is the 0.5～1.5% of monomer mass；
4) described microgel dispersion is dialysed, is removed unreacted monomer, macromolecular stabilizer agent and surfactant,
The pH value adjusting microgel dispersion is 4.0～8.0, and stirring makes it fully swelling；
5) mol ratio according to the N atom in described microgel dispersion and heavy metal presoma is 3～8: 1, by a described huge sum of money
Belong to presoma and swelling microgel dispersion mix and blend, obtain microgel-presoma compound system；
6) described microgel-presoma compound system is reacted 3～24h in 20～40 DEG C of insulated and stirred, generate load nanometer weight
Hud typed cationic microgel-nano-noble metal the composite of metallic.
2. the preparation method of hud typed cationic microgel-nano-noble metal composite according to claim 1, it is special
Levy be described polyethylene glycol methacrylate-styrene polymer the equal relative molecular mass of number be 475～8000, styrene end-blocking poly- methyl
The equal relative molecular mass of number of acrylic acid 2- (dimethylamino) ethyl ester is 8000～8500.
3. the preparation method of hud typed cationic microgel-nano-noble metal composite according to claim 1, it is special
Levy be described cross-linking agent be Ethylene glycol dimethacrylate, polypropylene glycol dimethacrylate or divinylbenzene.
4. the preparation method of hud typed cationic microgel-nano-noble metal composite according to claim 1, it is special
Levy be described initiator be azo-bis-isobutyrate hydrochloride, azo two isobutyl imidazoline hydrochloride, Ammonium persulfate., persulfuric acid
Potassium, Ammonium persulfate .-N, N, N', N'- tetramethylethylenediamine compound system, potassium peroxydisulfate-N, N, N', N'- tetramethylethylenediamine is multiple
Fit system.
5. the preparation method of hud typed cationic microgel-nano-noble metal composite according to claim 1, it is special
Levy the pH value being to adjust microgel dispersion with the HCl solution of 0.01mol/L or NaOH solution.
6. the preparation method of hud typed cationic microgel-nano-noble metal composite according to claim 1, it is special
Levying is the salt or acid that described heavy metal presoma is palladium, gold or platinum.
7. the preparation method of hud typed cationic microgel-nano-noble metal composite according to claim 6, it is special
Levy be described heavy metal presoma be tetrachloro-palladium acid sodium, gold chloride or six hydration one of chloroplatinic acids.
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