CN109422846A - Polymethyl methacrylate-maleic acid fatty alcohol ester sodium salt-argentum nano composite material and preparation method thereof - Google Patents
Polymethyl methacrylate-maleic acid fatty alcohol ester sodium salt-argentum nano composite material and preparation method thereof Download PDFInfo
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- CN109422846A CN109422846A CN201710764712.4A CN201710764712A CN109422846A CN 109422846 A CN109422846 A CN 109422846A CN 201710764712 A CN201710764712 A CN 201710764712A CN 109422846 A CN109422846 A CN 109422846A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention provides polymethyl methacrylate-maleic acid fatty alcohol ester sodium salt-argentum nano composite material and preparation method thereof, using PMMA and maleic acid fatty alcohol ester sodium salt as comonomer, maleic acid fatty alcohol ester sodium salt is added initiator, prepares pre-emulsion as emulsifier；It is using maleic acid fatty alcohol ester sodium salt as dispersing agent, nanometer Ag is pre-dispersed in aqueous solution, PMMA is added in Xiang Shangshu dispersion liquid, forms emulsion polymerization systems；After above-mentioned emulsion polymerization system is warming up to initiation temperature, initiator is added gradually to be added dropwise to pre-emulsion prepared by step 1 in emulsion polymerization systems in polymerization process, sufficiently reaction, obtains polymethyl methacrylate-maleic acid fatty alcohol ester sodium salt-silver copolymer emulsion.In copolymer emulsion and copolymer microsphere powder, silver is nano-dispersion, and dispersity is uniformly and stable, solves the problems, such as the serious agglomeration of nanoparticle in polymethyl methacrylate-silver composite material.
Description
Technical field
The present invention relates to technical field of composite materials, more specifically to a kind of polymethyl methacrylate-maleic acid
Aliphatic alcohol ester sodium salt-argentum nano composite material and preparation method thereof passes through yin with polymethyl methacrylate (PMMA) for substrate
Ion monomer maleic acid decylene glycol ester sodium salt (MAMS) is by electrostatic interaction and steric hindrance interaction dispersion and stablizes
Nano silver grain prepares the PMMA based nano composite material of high dispersive.
Background technique
Polymer based nanocomposites refer to that, using polymer as matrix, dispersed phase size is at least less than in one-dimensional direction
The composite material of 100nm.Polymer based nanocomposites combine the advantages of polymer and nano material, realize in performance
Optimization it is complementary, have wide research and application prospect.However, since nano particle diameter is small, large specific surface area, surface energy
Greatly, surface action is strong, causes its easy to reunite, bad dispersibility.Nano particle surface modifying method reported at present, big multioperation
Complexity, complex steps are made troubles to the preparation of polymer based nanocomposites.
Summary of the invention
The present invention overcomes deficiencies in the prior art, with polymethyl methacrylate (PMMA) for substrate, using lotion
The method of polymerization prepares PMMA based nano composite material, it is therefore an objective to use simple, efficient, environmental protection the method for one kind by Ag nanoparticle
It is scattered in polymeric matrix, prepares high-dispersion nano composite material.Ring-opening reaction synthetic anionic monomer maleic acid of the present invention
Decylene glycol ester sodium salt (MAMS).The anionic monomer can be used as dispersing agent, realize nanoparticle in water phase and polymer phase
It is evenly dispersed, and can be used as polymerisable emulsifier, participate in emulsion polymerization process.On the one hand, anionic monomer passes through electrostatic phase
Interaction and steric hindrance interaction dispersion and stable nanoparticle, which carries out in water, easy to operate, is not necessarily to
Carrying out complicated interminable graft modification to nanoparticle can be realized the dispersion effect of Nano grade；On the other hand, anion list
Body can react after polymerization as polymerisable emulsifier, avoid and introduce new ingredient into system, lotion is anti-in phase participation
Stable polymerizing microballoons lotion should be can be obtained without demulsification afterwards, be a kind of environmentally protective New-type emulsifier.This method can be with
It is used to prepare polymethyl methacrylate-maleic acid decylene glycol ester sodium salt-silver (P (MMA-co-MAMS)/Ag) nanometer of high dispersive
Composite material.
The purpose of the present invention is achieved by following technical proposals.
Polymethyl methacrylate-maleic acid fatty alcohol ester sodium salt-argentum nano composite material and preparation method thereof, under
State step progress:
Step 1, using methyl methacrylate and maleic acid fatty alcohol ester sodium salt as comonomer, maleic acid fatty alcohol ester sodium
Salt is used as emulsifier simultaneously, and initiator is added, prepares pre-emulsion, wherein oil is mutually by methyl methacrylate and maleic acid rouge
Fatty alcohol sodium salt composition, water phase are made of water and initiator；
Step 2, using maleic acid fatty alcohol ester sodium salt as dispersing agent, nano silver is pre-dispersed in aqueous solution, obtain nanometer
After silver particles dispersion liquid, be added methyl methacrylate in Xiang Shangshu dispersion liquid, form emulsion polymerization systems, wherein oil mutually by
Methyl methacrylate and maleic acid fatty alcohol ester sodium salt composition, water phase are made of water and nano silver；
Step 3, after above-mentioned emulsion polymerization system being warming up to the initiation temperature of initiator, it is poly- to cause that initiator is added
It closes, in polymerization process, pre-emulsion prepared by step 1 is gradually added dropwise in emulsion polymerization systems, sufficiently react, obtain
To polymethyl methacrylate-maleic acid fatty alcohol ester sodium salt-silver copolymer emulsion.
In step 1, the mass ratio of water phase and oily phase is (4-8): 1, preferably 5:1, methyl methacrylate monomer
Dosage is the 90.0-99.9wt% of oily phase quality, and preferably 92-95wt%, the dosage of maleic acid fatty alcohol ester sodium salt is oily phase
The 0.1-10.0wt% of quality, preferably 5-8wt%, the dosage of initiator is the 0.1-1.0wt% of two kinds of monomer mass sums, excellent
It is selected as 0.2-0.5wt%.
In step 2, the mass ratio of water phase and oily phase is (4-8): 1, preferably 5:1, methyl methacrylate monomer
Dosage is the 90.0-99.9wt% of oily phase quality, and preferably 92-95wt%, the dosage of maleic acid fatty alcohol ester sodium salt is oily phase
The 0.1-10.0wt% of quality, preferably 5-8wt%, nano silver are 0.1-5.0wt%, the preferably 2-3wt% of oily phase quality,
The dosage of initiator is the 0.1-1.0wt%, preferably 0.2-0.5wt% of two kinds of monomer mass sums.
The mass ratio of methyl methacrylate is (40-50): (50- in methyl methacrylate and step 2 in step 1
60), preferably 1:1, the mass ratio of maleic acid fatty alcohol ester sodium salt is in maleic acid fatty alcohol ester sodium salt and step 2 in step 1
(40-50): (50-60), preferably 1:1.
The time for adding of pre-emulsion is 1-1.5h in the step 3, and the emulsion polymerisation time in the step 3 is 3-
3.5h。
Initiator is azodiisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), benzoyl peroxide (BPO) or mistake
One of potassium sulfate (KPS), preferably potassium peroxydisulfate (KPS).
In step 1, maleic acid fatty alcohol ester sodium salt and initiator are dissolved in deionized water, add methacrylic acid
Methyl esters prepares pre-emulsion, and wherein maleic acid fatty alcohol ester sodium salt and the mass volume ratio of deionized water are (8-12): 1, preferably
10:1.
In step 2, nano silver and maleic acid fatty alcohol ester sodium salt ultrasonic disperse are added into methyl in deionized water
Methyl acrylate, wherein maleic acid fatty alcohol ester sodium salt and the mass volume ratio of deionized water are (8-12): 1, preferably 10:1.
In polymethyl methacrylate-maleic acid fatty alcohol ester sodium salt-silver copolymer emulsion, nano silver is evenly dispersed, cream
Change micellar particle size is 68-72nm, and particle size distribution index 0.30-0.33, nano silver partial size is 6-10nm.
The copolymer emulsion that step 3 is prepared is filtered and washed, and polymethyl methacrylate-is obtained after drying
Maleic acid fatty alcohol ester sodium salt-silver copolymer powder.
In polymethyl methacrylate-maleic acid fatty alcohol ester sodium salt-silver copolymer powder, nano silver is evenly dispersed, receives
Rice silver granuel diameter is 6-10nm.
Maleic acid fatty alcohol ester sodium salt uses maleic acid decylene glycol ester sodium salt.
The application of maleic acid fatty alcohol ester sodium salt evenly dispersed nano silver in methyl methacrylate based polyalcohol, by horse
Carry out sour aliphatic alcohol ester sodium salt to be copolymerized as comonomer and emulsifier with methyl methacrylate, while as cation
Monomer is by electrostatic interaction and steric hindrance interaction dispersion and stablizes nano silver particles.
The copolymer powder heat pressing forming machines that step 3 is prepared are hot-forming, hot pressing condition are as follows: pressure 3-
18MPa, 150-250 DEG C of temperature, time 8-32min.
Hot pressing condition is preferred are as follows: pressure 5-15MPa, 170-230 DEG C of temperature, and time 10-30min.
The invention has the benefit that can be applied through polymethyl methacrylate-silver composite material made of emulsion polymerization
In optical thin film, proton exchange membrane and catalysis material.Technical solution of the present invention synthesis has the yin of positive charge and long alkyl chain
Ion monomer maleic acid decylene glycol ester sodium salt realizes the evenly dispersed of nano silver, so first using anionic monomer as dispersing agent
Afterwards using anionic monomer as emulsifier, emulsion polymerization is realized, after polymerisation the phase, anionic monomer and methyl methacrylate are total
It is poly-, obtain stable copolymer multiple emulsion.The copolymer emulsion that technical solution of the present invention is prepared after emulsion polymerization meets
The basic demand of catalysis material, the copolymer powder after drying substantially meet the requirement of proton exchange membrane, optical thin film.Altogether
In copolymer emulsion and copolymer microsphere powder, nano silver is nano-dispersion, and dispersity is uniformly and stable, solves poly- first
The serious agglomeration problem of nanoparticle in base methyl acrylate-silver composite material.
Detailed description of the invention
Fig. 1 is anionic monomer maleic acid decylene glycol ester sodium salt1H-NMR spectrum；
Fig. 2 is dynamic light scattering (DLS) test of anionic monomer maleic acid decylene glycol ester sodium salt dispersion nano silver particles
Figure；
Fig. 3 is polymethyl methacrylate-silver composite material TEM photo, wherein (a) is P (MMA-SDS)/Ag, (b)
For P (MMA-co-MAMS)/Ag lotion, (c) P (the MMA-co-MAMS)/Ag ultra-thin section being prepared for embodiment 1.
Specific embodiment
Below by specific embodiment, further description of the technical solution of the present invention.
The key instrument and drug that embodiment is selected are as shown in the table:
1 primary raw material of table
2 key instrument equipment of table
Prepare maleic acid decylene glycol ester sodium salt (MAMS):
(1) 0.5mol n-dodecanol and maleic anhydride 0.5mol are added in 500mL three-necked flask, is stirred and heated to
50-60 DEG C, after reactant melts completely, it is warming up to 80 DEG C.After reacting 1h, it is slowly added into 150mL normal heptane, continues to stir
To after at homogeneous phase transparent liquid, (25 DEG C or so) stirring 3h, are added appropriate cold water or ice cube cool the temperature to 15 DEG C at room temperature,
Continue to stir 2h, white crystal is precipitated, filters to obtain product, i.e. maleic acid decylene glycol ester.
(2) maleic acid monoester fatty alcohol made from 0.1mol and 50mL acetone, stirring are added in the three-necked flask of 100mL
And 60 DEG C are heated to, it is completely dissolved maleic acid monoester fatty alcohol.The NaOH solution that mass fraction is 40% is prepared, and to above-mentioned
The NaOH solution of 10g 40% is added in reaction system, while accelerating to stir, makes the solid being precipitated dispersion.Drip NaOH solution
Afterwards, continue to stir 0.5h, it is cooling, filter to obtain white solid, dry white powder product, i.e. maleic acid lauryl alcohol under vacuum
Ester sodium salt MAMS.
For the structure of the anionic monomer maleic acid decylene glycol ester sodium salt of characterization synthesis, about 15mg anionic monomer is weighed
MAMS is dissolved in deuterated water (D2O) reagent is placed in sample preparation in nuclear magnetic tube, and solvent liquid level is not less than 4cm, and benefit carries out nucleus magnetic hydrogen spectrum inspection
It surveys.The nucleus magnetic hydrogen spectrum of anionic monomer is as shown in Figure 1.1H-NMR(D2O): δ=5.60 (d, 1H), δ=6.41 (d, 1H), δ=
3.94 (t, 2H), δ=1.47 (m, 2H), δ=1.16 (s, 2H), δ=0.74 (t, 3H).From MAMS's1H-NMR nuclear magnetic spectrogram can
To see: the absorption peak of chemical shift δ 4.79 is D2The internal standard peak of O；The absorption peak of chemical shift δ 5.60 and δ 6.41 correspond to C=
Two hydrogen in C double bond；It is two hydrogen on the carbon atom being connected directly with oxygen atom that the absorption peak of δ 3.94 is corresponding；δ1.47
Corresponding with two absorption peaks of δ 1.16 is chain alkyl close to second of oxygen atom side and four on third methylene
A hydrogen；It is three hydrogen on chain alkyl tail end methyl that the absorption peak of δ 0.74 is corresponding.The peak area on nuclear-magnetism figure known to analysis
It is directly proportional to the proton number in molecule, it was demonstrated that successfully synthesize target product maleic acid decylene glycol ester sodium salt and products pure.
The determination of the optimum addition of maleic acid decylene glycol ester sodium salt:
Anionic monomer MAMS disperses dynamic light scattering (DLS) test chart of Ag nanoparticle as shown in Fig. 2, test result
Table is as shown in table 3, and experimental results reflect the increase with anionic monomer MAMS concentration, the partial size of Ag nanoparticle and
The variation of polydispersity.The critical micelle concentration (cmc) of MAMS is 3.07mmol/L, i.e. 0.941g/L, indicates MAMS in water
Concentration be 0.941g/L when, initially form micella.Anionic monomer is negatively charged in water, and Ag nanoparticle is electric in water
From surface is positively charged, passes through the space bit of electrostatic interaction and MAMS chain alkyl between MAMS and Ag nanoparticle
Resistance interaction, keeps Ag nanoparticle evenly dispersed.DLS test result is shown, the Ag of MAMS is not added due to skin effect etc.
Keep its surface action strong, agglomeration occurs, partial size is larger.The addition of anionic monomer MAMS makes Ag nanoparticle in water more
Disperse well, partial size has more apparent downward trend, but polydispersity variation is unobvious.In general, the addition pair of MAMS
The Dispersion rules of Ag nanoparticle are complex, but it can also be seen that, the promotion that is dispersed with of Ag nanoparticle is made in the addition of MAMS
With.When the concentration of MAMS is 10g/L, the partial size of Ag nanoparticle reaches minimum value 57.2nm.Comprehensively consider anionic monomer
The factors such as amount, particle size and the polydispersity that MAMS is added are dispersion Ag when the final concentration for determining MAMS is 10g/L
The optimum value of nanoparticle.
The DLS test result table of 3 anionic monomer MAMS of table dispersion Ag nanoparticle
| MAMS concentration (g/L) | Partial size (nm) | PDI |
| 0 | 106.0 | 0.318 |
| 2 | 95.5 | 0.337 |
| 4 | 90.1 | 0.334 |
| 6 | 93.2 | 0.333 |
| 8 | 102.2 | 0.326 |
| 10 | 57.2 | 0.338 |
| 12 | 86.7 | 0.340 |
| 14 | 60.3 | 0.328 |
Embodiment 1
(1) preparation is using anionic monomer MAMS as the polymethyl methacrylate of emulsifier-silver nanoparticle multiple emulsion: weighing
0.5g MAMS, 0.057g initiator KPS, is dissolved in 50mL deionized water, then weigh 10g monomers methyl methacrylate, adds
Enter into 250mL four-hole boiling flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, pre-emulsion is added in constant pressure funnel
For use；
(2) it again disperses 0.5g Ag nanoparticle and 0.5g anionic monomer MAMS in 50mL deionized water, uses
JY92-II N-type ultrasonic cell disruptor ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time
2s, ultrasound 30min under ice bath environment, ultrasonic disperse liquid is added in 250mL four-hole boiling flask；10g methacrylic acid is weighed again
Methyl esters is added in 250mL four-hole boiling flask, room temperature water-bath pre-emulsification 0.5h, and setting mixing speed is 700rpm, after 0.5h, is opened
Begin to heat up；Temperature reaches 70 DEG C, weighs 0.057g KPS, is dissolved in a small amount of deionized water, is added in four-hole boiling flask, starts
Heating；Temperature reaches 75 DEG C, after insulation reaction 0.5h, starts that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask, and continue
React 1h；After 1h, pre-emulsion is added dropwise, and is started to warm up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stop heating, no
Stop stirring, is cooled to room temperature；
(3) it discharges, is filtered with the nylon leaching net of 300 mesh, and its pH value is adjusted to 7-8 with ammonium hydroxide, is i.e. acquisition polymer matrix
Nano-composite emulsion is denoted as P (MMA-co-MAMS)/Ag.
(4) P (MMA-co-MAMS)/Ag multiple emulsion is dried under vacuum to constant weight at 60 DEG C, obtains nano-complex
Powder；P (MMA-co-MAMS)/Ag powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 10MPa, temperature 190
DEG C, time 15min.
Embodiment 2
(1) preparation is using anionic monomer MAMS as the polymethyl methacrylate of emulsifier-silver nanoparticle multiple emulsion: weighing
0.4g MAMS, 0.057g initiator A IBN, is dissolved in 50mL deionized water, then weigh 10g monomers methyl methacrylate,
It is added in 250mL four-hole boiling flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, pre-emulsion is added to constant pressure funnel
In it is stand-by；
(2) it again disperses 0.5g Ag nanoparticle and 0.6g anionic monomer MAMS in 50mL deionized water, uses
JY92-II N-type ultrasonic cell disruptor ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time
2s, ultrasound 30min under ice bath environment, ultrasonic disperse liquid is added in 250mL four-hole boiling flask；10g methacrylic acid is weighed again
Methyl esters is added in 250mL four-hole boiling flask, room temperature water-bath pre-emulsification 0.5h, and setting mixing speed is 700rpm, after 0.5h, is opened
Begin to heat up；Temperature reaches 70 DEG C, weighs 0.057g initiator A IBN, is dissolved in a small amount of deionized water, is added to four-hole boiling flask
In, it starts to warm up；Temperature reaches 75 DEG C, after insulation reaction 0.5h, starts that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask,
And the reaction was continued 1h；After 1h, pre-emulsion is added dropwise, and is started to warm up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stop adding
Heat does not stop stirring, be cooled to room temperature；
(3) it discharges, is filtered with the nylon leaching net of 300 mesh, and its pH value is adjusted to 7-8 with ammonium hydroxide, is i.e. acquisition polymer matrix
Nano-composite emulsion is denoted as P (MMA-co-MAMS)/Ag.
(4) P (MMA-co-MAMS)/Ag multiple emulsion is dried under vacuum to constant weight at 60 DEG C, obtains nano-complex
Powder；P (MMA-co-MAMS)/Ag powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 3MPa, 150 DEG C of temperature,
Time 32min.
Embodiment 3
(1) preparation is using anionic monomer MAMS as the polymethyl methacrylate of emulsifier-silver nanoparticle multiple emulsion: weighing
0.6g MAMS, 0.057g initiator A BVN, is dissolved in 50mL deionized water, then weigh 10g monomers methyl methacrylate,
It is added in 250mL four-hole boiling flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, pre-emulsion is added to constant pressure funnel
In it is stand-by；
(2) it again disperses 0.5g Ag nanoparticle and 0.4g anionic monomer MAMS in 50mL deionized water, uses
JY92-II N-type ultrasonic cell disruptor ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time
2s, ultrasound 30min under ice bath environment, ultrasonic disperse liquid is added in 250mL four-hole boiling flask；10g methacrylic acid is weighed again
Methyl esters is added in 250mL four-hole boiling flask, room temperature water-bath pre-emulsification 0.5h, and setting mixing speed is 700rpm, after 0.5h, is opened
Begin to heat up；Temperature reaches 70 DEG C, weighs 0.057g initiator A BVN, is dissolved in a small amount of deionized water, is added to four-hole boiling flask
In, it starts to warm up；Temperature reaches 75 DEG C, after insulation reaction 0.5h, starts that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask,
And the reaction was continued 1h；After 1h, pre-emulsion is added dropwise, and is started to warm up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stop adding
Heat does not stop stirring, be cooled to room temperature；
(3) it discharges, is filtered with the nylon leaching net of 300 mesh, and its pH value is adjusted to 7-8 with ammonium hydroxide, is i.e. acquisition polymer matrix
Nano-composite emulsion is denoted as P (MMA-co-MAMS)/Ag.
(4) P (MMA-co-MAMS)/Ag multiple emulsion is dried under vacuum to constant weight at 60 DEG C, obtains nano-complex
Powder；P (MMA-co-MAMS)/Ag powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 18MPa, temperature 250
DEG C, time 8min.
Embodiment 4
(1) preparation is using anionic monomer MAMS as the polymethyl methacrylate of emulsifier-silver nanoparticle multiple emulsion: weighing
0.5g MAMS, 0.057g initiator B PO, is dissolved in 50mL deionized water, then weigh 5g monomers methyl methacrylate, adds
Enter into 250mL four-hole boiling flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, pre-emulsion is added in constant pressure funnel
For use；
(2) it again disperses 0.5g Ag nanoparticle and 0.5g anionic monomer MAMS in 50mL deionized water, uses
JY92-II N-type ultrasonic cell disruptor ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time
2s, ultrasound 30min under ice bath environment, ultrasonic disperse liquid is added in 250mL four-hole boiling flask；15g methacrylic acid is weighed again
Methyl esters is added in 250mL four-hole boiling flask, room temperature water-bath pre-emulsification 0.5h, and setting mixing speed is 700rpm, after 0.5h, is opened
Begin to heat up；Temperature reaches 70 DEG C, weighs 0.057g initiator B PO, is dissolved in a small amount of deionized water, is added to four-hole boiling flask
In, it starts to warm up；Temperature reaches 75 DEG C, after insulation reaction 0.5h, starts that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask,
And the reaction was continued 1h；After 1h, pre-emulsion is added dropwise, and is started to warm up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stop adding
Heat does not stop stirring, be cooled to room temperature；
(3) it discharges, is filtered with the nylon leaching net of 300 mesh, and its pH value is adjusted to 7-8 with ammonium hydroxide, is i.e. acquisition polymer matrix
Nano-composite emulsion is denoted as P (MMA-co-MAMS)/Ag.
(4) P (MMA-co-MAMS)/Ag multiple emulsion is dried under vacuum to constant weight at 60 DEG C, obtains nano-complex
Powder；P (MMA-co-MAMS)/Ag powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 5MPa, 170 DEG C of temperature,
Time 30min.
Embodiment 5
(1) preparation is using anionic monomer MAMS as the polymethyl methacrylate of emulsifier-silver nanoparticle multiple emulsion: weighing
0.5g MAMS, 0.057g initiator KPS, is dissolved in 50mL deionized water, then weigh 15g monomers methyl methacrylate, adds
Enter into 250mL four-hole boiling flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, pre-emulsion is added in constant pressure funnel
For use；
(2) it again disperses 0.5g Ag nanoparticle and 0.5g anionic monomer MAMS in 50mL deionized water, uses
JY92-II N-type ultrasonic cell disruptor ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time
2s, ultrasound 30min under ice bath environment, ultrasonic disperse liquid is added in 250mL four-hole boiling flask；5g methyl methacrylate is weighed again
Ester is added in 250mL four-hole boiling flask, room temperature water-bath pre-emulsification 0.5h, and setting mixing speed is 700rpm, after 0.5h, is started
Heating；Temperature reaches 70 DEG C, weighs 0.057g KPS, is dissolved in a small amount of deionized water, is added in four-hole boiling flask, starts to rise
Temperature；Temperature reaches 75 DEG C, after insulation reaction 0.5h, starts that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask, and continues anti-
Answer 1h；After 1h, pre-emulsion is added dropwise, and is started to warm up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stops heating, do not stop
It only stirs, is cooled to room temperature；
(3) it discharges, is filtered with the nylon leaching net of 300 mesh, and its pH value is adjusted to 7-8 with ammonium hydroxide, is i.e. acquisition polymer matrix
Nano-composite emulsion is denoted as P (MMA-co-MAMS)/Ag.
(4) P (MMA-co-MAMS)/Ag multiple emulsion is dried under vacuum to constant weight at 60 DEG C, obtains nano-complex
Powder；P (MMA-co-MAMS)/Ag powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 15MPa, temperature 230
DEG C, time 10min.
Embodiment 6
(1) preparation is using anionic monomer MAMS as the polymethyl methacrylate of emulsifier-silver nanoparticle multiple emulsion: weighing
0.5g MAMS, 0.057g initiator B PO, is dissolved in 50mL deionized water, then weigh 10g monomers methyl methacrylate, adds
Enter into 250mL four-hole boiling flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, pre-emulsion is added in constant pressure funnel
For use；
(2) it again disperses 1.0g Ag nanoparticle and 0.5g anionic monomer MAMS in 50mL deionized water, uses
JY92-II N-type ultrasonic cell disruptor ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time
2s, ultrasound 30min under ice bath environment, ultrasonic disperse liquid is added in 250mL four-hole boiling flask；10g methacrylic acid is weighed again
Methyl esters is added in 250mL four-hole boiling flask, room temperature water-bath pre-emulsification 0.5h, and setting mixing speed is 700rpm, after 0.5h, is opened
Begin to heat up；Temperature reaches 70 DEG C, weighs 0.057g initiator B PO, is dissolved in a small amount of deionized water, is added to four-hole boiling flask
In, it starts to warm up；Temperature reaches 75 DEG C, after insulation reaction 0.5h, starts that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask,
And the reaction was continued 1h；After 1h, pre-emulsion is added dropwise, and is started to warm up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stop adding
Heat does not stop stirring, be cooled to room temperature；
(3) it discharges, is filtered with the nylon leaching net of 300 mesh, and its pH value is adjusted to 7-8 with ammonium hydroxide, is i.e. acquisition polymer matrix
Nano-composite emulsion is denoted as P (MMA-co-MAMS)/Ag.
(4) P (MMA-co-MAMS)/Ag multiple emulsion is dried under vacuum to constant weight at 60 DEG C, obtains nano-complex
Powder；P (MMA-co-MAMS)/Ag powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 12MPa, temperature 210
DEG C, time 20min.
Comparative example 1
(1) preparation is using traditional lauryl sodium sulfate SDS as the polymethyl methacrylate of emulsifier-silver nanoparticle Composite Milk
Liquid: weighing 0.5g SDS, and 0.057g initiator KPS is dissolved in 50mL deionized water, then weighs 10g monomer methacrylic acid
Methyl esters MMA is added in 250mL four-hole boiling flask, stirs pre-emulsification 2h with the revolving speed of 700rpm, pre-emulsion is added to constant pressure
It is stand-by in dropping funel；Again disperse 0.5g Ag nanoparticle in 50mL deionized water, it is thin with JY92-II N-type ultrasonic wave
Born of the same parents' pulverizer ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time 2s, ultrasound under ice bath environment
Ultrasonic disperse liquid is added in 250mL four-hole boiling flask by 30min；0.5g SDS and 10g methyl methacrylate is weighed again, is added
Enter into 250mL four-hole boiling flask, room temperature water-bath pre-emulsification 0.5h, setting mixing speed is 700rpm, after 0.5h, is started to warm up；
Temperature reaches 70 DEG C, weighs 0.057g KPS, is dissolved in a small amount of deionized water, is added in four-hole boiling flask, starts to warm up；Temperature
Degree reaches 75 DEG C, after insulation reaction 0.5h, starts that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask, and the reaction was continued 1h；
After 1h, pre-emulsion is added dropwise, and is started to warm up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stops heating, do not stop stirring
It mixes, is cooled to room temperature；Discharging is filtered with the nylon leaching net of 300 mesh, and its pH value is adjusted to 7-8 with ammonium hydroxide, i.e. acquisition polymer
Base nano-composite emulsion is denoted as P (MMA-SDS)/Ag.
(2) P (MMA-SDS)/Ag multiple emulsion is dried under vacuum to constant weight at 60 DEG C, obtains nano-complex powder
End；P (MMA-SDS)/Ag powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 10MPa, 190 DEG C of temperature, the time
5min。
Comparative example 2
(1) preparation is using traditional lauryl sodium sulfate SDS as the polymethyl methacrylate of emulsifier-silver nanoparticle Composite Milk
Liquid: weighing 0.6g SDS, and 0.057g initiator KPS is dissolved in 50mL deionized water, then weighs 10g monomer methacrylic acid
Methyl esters MMA is added in 250mL four-hole boiling flask, stirs pre-emulsification 2h with the revolving speed of 700rpm, pre-emulsion is added to constant pressure
It is stand-by in dropping funel；Again disperse 0.5g Ag nanoparticle in 50mL deionized water, it is thin with JY92-II N-type ultrasonic wave
Born of the same parents' pulverizer ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time 2s, ultrasound under ice bath environment
Ultrasonic disperse liquid is added in 250mL four-hole boiling flask by 30min；0.4g SDS and 10g methyl methacrylate is weighed again, is added
Enter into 250mL four-hole boiling flask, room temperature water-bath pre-emulsification 0.5h, setting mixing speed is 700rpm, after 0.5h, is started to warm up；
Temperature reaches 70 DEG C, weighs 0.057g KPS, is dissolved in a small amount of deionized water, is added in four-hole boiling flask, starts to warm up；Temperature
Degree reaches 75 DEG C, after insulation reaction 0.5h, starts that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask, and the reaction was continued 1h；
After 1h, pre-emulsion is added dropwise, and is started to warm up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stops heating, do not stop stirring
It mixes, is cooled to room temperature；Discharging is filtered with the nylon leaching net of 300 mesh, and its pH value is adjusted to 7-8 with ammonium hydroxide, i.e. acquisition polymer
Base nano-composite emulsion is denoted as P (MMA-SDS)/Ag.
(2) P (MMA-SDS)/Ag multiple emulsion is dried under vacuum to constant weight at 60 DEG C, obtains nano-complex powder
End；P (MMA-SDS)/Ag powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 10MPa, 190 DEG C of temperature, the time
5min。
Comparative example 3
(1) preparation is using traditional lauryl sodium sulfate SDS as the polymethyl methacrylate of emulsifier-silver nanoparticle Composite Milk
Liquid: weighing 0.4g SDS, and 0.057g initiator KPS is dissolved in 50mL deionized water, then weighs 10g monomer methacrylic acid
Methyl esters MMA is added in 250mL four-hole boiling flask, stirs pre-emulsification 2h with the revolving speed of 700rpm, pre-emulsion is added to constant pressure
It is stand-by in dropping funel；Again disperse 0.5g Ag nanoparticle in 50mL deionized water, it is thin with JY92-II N-type ultrasonic wave
Born of the same parents' pulverizer ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time 2s, ultrasound under ice bath environment
Ultrasonic disperse liquid is added in 250mL four-hole boiling flask by 30min；0.6g SDS and 10g methyl methacrylate is weighed again, is added
Enter into 250mL four-hole boiling flask, room temperature water-bath pre-emulsification 0.5h, setting mixing speed is 700rpm, after 0.5h, is started to warm up；
Temperature reaches 70 DEG C, weighs 0.057g KPS, is dissolved in a small amount of deionized water, is added in four-hole boiling flask, starts to warm up；Temperature
Degree reaches 75 DEG C, after insulation reaction 0.5h, starts that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask, and the reaction was continued 1h；
After 1h, pre-emulsion is added dropwise, and is started to warm up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stops heating, do not stop stirring
It mixes, is cooled to room temperature；Discharging is filtered with the nylon leaching net of 300 mesh, and its pH value is adjusted to 7-8 with ammonium hydroxide, i.e. acquisition polymer
Base nano-composite emulsion is denoted as P (MMA-SDS)/Ag.
(2) P (MMA-SDS)/Ag multiple emulsion is dried under vacuum to constant weight at 60 DEG C, obtains nano-complex powder
End；P (MMA-SDS)/Ag powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 10MPa, 190 DEG C of temperature, the time
5min。
Dynamic light scattering test (DLS) is also referred to as photon correlation spectroscopy (PCS) or quasi-elastic light scattering, the Brownian movement of particle
Lead to the fluctuation of light intensity, DLS test is that the fluctuation of light intensity changes with time.DLS test can accurately and effectively test particle
Partial size and polydispersity.The DLS test result of pure PMMA lotion and its polymer-based nano multiple emulsion is as shown in table 4.From
The partial size that result can be seen that the polymer-based nano multiple emulsion that nanoparticle is added compared with pure PMMA lotion in table has
A degree of increase, the reason is that nanoparticle itself has the partial size of ten a few nanometers to tens of nanometers, with polymer matrix bluk recombination
Afterwards, there is the partial size of polymer-based nano complex microsphere to increase by a small margin.Although partial size is increased slightly, still in nanoscale
Not.The partial size and to use MAMS be polymerisable emulsifier that SDS is the polymer-based nano multiple emulsion of emulsifier synthesis will be used
The partial size of the polymer-based nano multiple emulsion of synthesis compares, it can be found that the variation of microspherulite diameter is little in lotion.Point
Analyse reason: the partial size of nanoparticle is more much smaller than the partial size of polymer microballoon, and the influence to microspherulite diameter is smaller, will not be to microballoon
Partial size cause very big variation.Meanwhile this result shows that, influence of the type of emulsifier to partial size be not also significant, shows
Compared with conventional emulsifier SDS, polymerisable emulsifier MAMS can also play good emulsifying effectiveness, and then prepare nanoscale
Polymer-based nano multiple emulsion is a kind of emulsifier of function admirable.
The DLS test result table of 4 polymer-based nano multiple emulsion of table
Fig. 3 is polymethyl methacrylate-silver composite material TEM photo.In TEM photo, contrast is smaller and partial size
Biggish is PMMA, and contrast is larger and partial size is lesser for Ag nanoparticle.As can be seen that polymer microballoon from TEM photo
Partial size is 50nm or so, and well dispersed Ag partial size is average up to 6-10nm (concentrating on 8-10nm), and the Ag partial size reunited
For 30nm or so.As can be seen that the use of SDS being polymer-based nano multiple emulsion prepared by emulsifier, Ag receives from TEM photo
Rice corpuscles is not compound with polymeric matrix success and obvious agglomeration occurs；It the use of MAMS is polymerizable emulsification
The polymer-based nano multiple emulsion of agent preparation, Ag nanoparticle and polymeric matrix success are compound, meanwhile, Ag nanoparticle point
It dissipates well, there is no agglomerations.Since the relatively macro aggregate of Ag is removed in high speed centrifugation operation mostly, therefore in TEM
Can only observe that the content of the lesser aggregate in part and Ag nanoparticle is not high in photo, thus can explain using SDS as
When emulsifier, Ag nanoparticle and polymer matrix bluk recombination is unsuccessful and agglomeration is serious；And using MAMS is polymerizable cream
The polymer-based nano multiple emulsion particle of agent preparation is with the compound success of matrix and without nanoparticle agglomeration.By hot pressing
After molding, P (MMA-co-MAMS)/Ag ultra-thin section TEM is shown, silver-colored dispersity obtains good holding, and partial size is flat
Up to 6-10nm.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. polymethyl methacrylate-maleic acid fatty alcohol ester sodium salt-argentum nano composite material preparation method, feature exist
In: it carries out as steps described below:
Step 1, using methyl methacrylate and maleic acid fatty alcohol ester sodium salt as comonomer, maleic acid fatty alcohol ester sodium salt is same
Shi Zuowei emulsifier is added initiator, prepares pre-emulsion, wherein oil is mutually by methyl methacrylate and maleic acid fatty alcohol
Ester sodium salt composition, water phase are made of water and initiator；
Step 2, using maleic acid fatty alcohol ester sodium salt as dispersing agent, nano silver is pre-dispersed in aqueous solution, obtain a nanometer silver granuel
After sub- dispersion liquid, methyl methacrylate is added in Xiang Shangshu dispersion liquid, forms emulsion polymerization systems, wherein oil is mutually by methyl
Methyl acrylate and maleic acid fatty alcohol ester sodium salt composition, water phase are made of water and nano silver；
Step 3, after above-mentioned emulsion polymerization system being warming up to the initiation temperature of initiator, initiator is added and is polymerize with causing,
In polymerization process, pre-emulsion prepared by step 1 is gradually added dropwise in emulsion polymerization systems, sufficiently reacts, is gathered
Methyl methacrylate-maleic acid fatty alcohol ester sodium salt-silver copolymer emulsion；
Wherein, in step 1, the mass ratio of water phase and oily phase is (4-8): 1, preferably 5:1, methyl methacrylate monomer
Dosage is the 90.0-99.9wt% of oily phase quality, and preferably 92-95wt%, the dosage of maleic acid fatty alcohol ester sodium salt is oily phase
The 0.1-10.0wt% of quality, preferably 5-8wt%, the dosage of initiator is the 0.1-1.0wt% of two kinds of monomer mass sums, excellent
It is selected as 0.2-0.5wt%；
In step 2, the mass ratio of water phase and oily phase is (4-8): 1, preferably 5:1, the dosage of methyl methacrylate monomer
For the 90.0-99.9wt% of oily phase quality, preferably 92-95wt%, the dosage of maleic acid fatty alcohol ester sodium salt is oily phase quality
0.1-10.0wt%, preferably 5-8wt%, nano silver is 0.1-5.0wt%, the preferably 2-3wt% of oily phase quality, is caused
The dosage of agent is the 0.1-1.0wt%, preferably 0.2-0.5wt% of two kinds of monomer mass sums；
The mass ratio of methyl methacrylate is (40-50): (50-60), step in methyl methacrylate and step 2 in step 1
The mass ratio of maleic acid fatty alcohol ester sodium salt is (40-50): (50-60) in maleic acid fatty alcohol ester sodium salt and step 2 in rapid 1.
2. polymethyl methacrylate according to claim 1-maleic acid fatty alcohol ester sodium salt-argentum nano composite material
Preparation method, it is characterised in that: the mass ratio of methyl methacrylate is 1 in methyl methacrylate and step 2 in step 1:
1, the mass ratio of maleic acid fatty alcohol ester sodium salt is 1:1 in maleic acid fatty alcohol ester sodium salt and step 2 in step 1；The step 3
The time for adding of middle pre-emulsion is 1-1.5h, and the emulsion polymerisation time in the step 3 is 3-3.5h.
3. polymethyl methacrylate according to claim 1-maleic acid fatty alcohol ester sodium salt-argentum nano composite material
Preparation method, it is characterised in that: the copolymer emulsion that step 3 is prepared is filtered and washed, and poly- first is obtained after drying
Base methyl acrylate-maleic acid fatty alcohol ester sodium salt-silver copolymer powder.
4. polymethyl methacrylate according to claim 1-maleic acid fatty alcohol ester sodium salt-argentum nano composite material
Preparation method, it is characterised in that: in step 1, maleic acid fatty alcohol ester sodium salt and initiator are dissolved in deionized water, then plus
Enter methyl methacrylate, prepare pre-emulsion, wherein maleic acid fatty alcohol ester sodium salt and the mass volume ratio of deionized water are
(8-12): 1, preferably 10:1；In step 2, by nano silver and maleic acid fatty alcohol ester sodium salt ultrasonic disperse in deionized water,
Add methyl methacrylate, wherein maleic acid fatty alcohol ester sodium salt and the mass volume ratio of deionized water are (8-12): 1,
It is preferred that 10:1.
5. polymethyl methacrylate according to claim 1-maleic acid fatty alcohol ester sodium salt-argentum nano composite material
Preparation method, it is characterised in that: initiator is azodiisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), benzoyl peroxide first
One of acyl (BPO) or potassium peroxydisulfate (KPS), preferably potassium peroxydisulfate (KPS).
6. polymethyl methacrylate described in accordance with the claim 1-maleic acid fatty alcohol ester sodium salt-argentum nano composite material
The polymethyl methacrylate that preparation method is prepared-maleic acid fatty alcohol ester sodium salt-silver copolymer emulsion.
7. polymethyl methacrylate according to claim 6-maleic acid fatty alcohol ester sodium salt-silver copolymer emulsion,
Be characterized in that: in polymethyl methacrylate-maleic acid fatty alcohol ester sodium salt-silver copolymer emulsion, nano silver is evenly dispersed, cream
Change micellar particle size is 68-72nm, and particle size distribution index 0.30-0.33, nano silver partial size is 6-10nm.
8. the polymethyl methacrylate that preparation method according to claim 3 is prepared-maleic acid fatty alcohol ester sodium
Salt-silver copolymer powder, it is characterised in that: polymethyl methacrylate-maleic acid fatty alcohol ester sodium salt-silver copolymer powder
In, nano silver is evenly dispersed, and nano silver partial size is 6-10nm.
9. polymethyl methacrylate according to claim 1-maleic acid fatty alcohol ester sodium salt-argentum nano composite material
Preparation method, it is characterised in that: maleic acid fatty alcohol ester sodium salt uses maleic acid decylene glycol ester sodium salt.
10. the application of maleic acid fatty alcohol ester sodium salt evenly dispersed nano silver in methyl methacrylate based polyalcohol, special
Sign is: using maleic acid fatty alcohol ester sodium salt as comonomer and emulsifier, being copolymerized with methyl methacrylate, simultaneously
By electrostatic interaction and steric hindrance interaction dispersion and stablize nano silver particles as cationic monomer.
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