CN1300191C - Process for preparing nano silicon dioxide-acrylate composite emulsion - Google Patents
Process for preparing nano silicon dioxide-acrylate composite emulsion Download PDFInfo
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- CN1300191C CN1300191C CNB2005100382740A CN200510038274A CN1300191C CN 1300191 C CN1300191 C CN 1300191C CN B2005100382740 A CNB2005100382740 A CN B2005100382740A CN 200510038274 A CN200510038274 A CN 200510038274A CN 1300191 C CN1300191 C CN 1300191C
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Abstract
The present invention relates to a method of preparing nano silicon dioxide-acrylate composite emulsion. The method comprises the following steps that: firstly, small-molecule alcohol, a silane coupling agent, deionized water and an acidic solution are mixed and are stirred; secondly, hydrolysate products of nano silicon dioxide and the silane coupling agent are added in a derivate solvent of benzene and are stirred under the condition of the protection of inert gas; the obtained solvent is centrifugally separated, is cleaned by the small-molecule alcohol or acetone and is dried in a vacuum mode to obtain modified nano silicon dioxide; thirdly, monomers in the class of acrylic are dispersed into fine monomer emulsion of the in the class of acrylic; the modified silicon dioxide, an anionic or nonionic emulsifying agent, lipophilic alkane or alcohol liquor as a stabilizing agent and water are mixed together and are emulsified; soluble persulphate or oil-soluble peroxide is added; the temperature is kept; the monomer fine emulsion in the class of acrylic is dropped into the mixed liquor; the temperature is kept; finally, the nano silicon dioxide-acrylate composite emulsion is obtained. The present invention has the advantage of small environmental pollution and is convenient to future industrialization.
Description
Technical field
The present invention relates to the preparation of nano silicon dioxide-acrylate, relate in particular to a kind of preparation method of nano silicon dioxide-acrylate composite emulsion.
Technical background
Carried out the research of a lot of organic/inorganic composite materials recently.Polyacrylic ester is the polymer materials that a class has extensive use, usually low, the poor mechanical property of hardness.When during to its modification, often being difficult to prove effective because of being separated of inorganic materials with inorganic materials.Sol-gel technique is a reasonable method of improving some character of polyacrylic ester with inorganic nano mutually, wherein typical material modified is polymethylmethacrylate, its transparency is high, it is outstanding organic optical materials, have that density is little, price is low, be easy to advantages such as machine-shaping, but, cause optical property to descend, thereby limited its use because its surface easily scratches.SiO
2The structure of glass is quite similar to the superpolymer synthetic glass in many aspects, sol-gel method is the two bonded effective way, the inorganic nano phase material will be mixed in the synthetic glass matrix, or organic functional molecular or polymkeric substance mixed in the inorganic polymer network, just can synthesize inorganic-organic hybridization matrix material with property.
Usually, directly with TEOS and methyl methacrylate in solvent when hydrolysis and polycondensation, inorganic SiO
2To form macrobead and disperse phase, and cause on the microcosmic to be separated, influence the optical transparence of polymethylmethacrylate, and when improving, performance of composites will be made moderate progress with the siloxanes coupling agent.When organic constituent and inorganic component two aspects are improved jointly, effect is far better.In the collosol-gelatum system of methyl methacrylate and TEOS, be aided with glytidyl methacrylate and aminopropyl triethoxysilane properties-correcting agent, by epoxy group(ing) and amino chemical reaction, the effect of chemical bond has been arranged between inorganic component and organic constituent, suppress inorganic SiO
2The increase of nanophase makes the transparency of matrix material not have substantially to reduce than organic matrix.
At present, prepared organic/inorganic composite material, what great majority adopted all is to adopt mass polymerization, promptly directly nano silicon is directly added in the methyl methacrylate monomer, thereby obtains the uniform matrix material of phase.But also very serious to the pollution of environment, and after the industrialization, also very strict to operator's requirement, the present invention is except beginning to carry out in solvent system, and other step all can be carried out at aqueous phase, must pollute little, and simple to operate to environment.When the present invention has inquired into nano silicon simultaneously carry out surface modification in the different solvents system,, thereby found contact between the two, can obtain stable solution system the influence of the reactive behavior of silica sphere hydroxyl.
Summary of the invention
The invention provides a kind of low cost, pollute the little method that mini-emulsion polymerization obtains nano silicon dioxide-acrylate composite emulsion of passing through.
The present invention adopts following technical scheme:
A kind of preparation method of nano silicon dioxide-acrylate composite emulsion may further comprise the steps:
The first step: the small molecular alcohol of 10～100 parts of quality, the silane coupling agent of 100-800 part quality and the deionized water of 10～100 parts of quality and the acidic solution of 1～10 part of quality are mixed, and under 100～800 rev/mins speed churning time 2～16 hours, obtain the silane coupling agent hydrolysate;
Second step: under protection of inert gas, the above-mentioned silane coupling agent hydrolysate of the nano silicon of 10～200 parts of quality and 1-20 part quality is joined in the derivative solvent of benzene of 100～2000 parts of quality and stir, stirring velocity is 100-800 rev/min, churning time is 2～16 hours, obtain the silicon-dioxide of modification by centrifugation, and small molecular alcohol or acetone rinsing with 100-800 part quality, thereby remove unnecessary silane coupling agent hydrolysate, dry under vacuum then, obtain modified manometer silicon dioxide;
The 3rd step: acrylic ester monomer is dispersed into the acrylic ester monomer miniemulsion that median size is 50～500nm,
The 4th step: with the above-mentioned improved silica of 10-100 part quality, mixing of the negatively charged ion of 2-20 part quality or nonionic emulsifying agent and 1-30 part quality as the liquid lipophilic alkane of stablizer or the water of pure and mild 10-1000 part quality, then with above-mentioned mixed solution emulsification, make modified manometer silicon dioxide be dispersed in the aqueous solution, solubility persulphate or the oil-soluble superoxide that add 2-20 part quality then as initiator, temperature with mixed solution remains in the 70-80 ℃ of scope again, with 0.01-20 part quality/minute speed the aforesaid propylene esters of gallic acid monomer miniemulsion of 20-600 part quality is added drop-wise in the above-mentioned mixed solution, continue to make mixed solution in 70-80 ℃ of scope, to be incubated after dropwising, its soaking time is more than 1 hour, obtains nano silicon dioxide-acrylate composite emulsion at last.
Ultimate principle of the present invention: utilize the free hydroxyl group of nano-silica surface and coupling agent to react, thereby make silica sphere by the hydrophilic lipophilicity that becomes, under the initiator effect, the acrylate monomer after the emulsification received on the silica sphere and (acrylate monomer is carried out ultrasonic emulsification, make it be divided into the stable pre-emulsion that particle diameter is 200nm, thereby control later rate of growth), by adding control agent, be the nano silicon dioxide-acrylate composite emulsion of 50～500nm thereby generate particle diameter through mini-emulsion polymerization.
Compare with existing nano silicon dioxide-acrylate composite emulsion technology of preparing, have the following advantages:
1. the present invention carries out the access point that linked reaction can improve nano-silica surface in the derivative solvent of benzene, after the nano-silica surface modification, by the hydrophilic oleophylic that becomes, thereby can be dissolved into through in the acrylate monomer miniemulsion after the ultrasonic emulsification.
2. the method for employing ultrasonic emulsification and high-speed stirring can be controlled preferably and give particle size of emulsion size and distribution, thereby the acrylic ester monomer mean drop diameter can be controlled to be 50～500nm from 1000nm, forms the miniemulsion of acrylic ester monomer;
3. ultrasonic emulsification or high-speed stirring can be dispersed in modified manometer silicon dioxide in the aqueous solution, and wherein the effect of ultrasonic emulsification is better than other alr mode.
4. no material transfer and exchange between particle during owing to polymerization, particle diameter number and composition maintenance original appearance mainly are under ultrasound condition, because cavitation, vibration, under the strong energy, emulsion becomes small-particle by macroparticle, and the particle diameter of silicon-dioxide still remains on below the 100nm after the modification, because silica sphere has group, (unsaturated group), under the free radical effect, the acrylate monomer of 50-500nm, be connected on silica sphere, thereby form stable composite emulsion.And the composite emulsion that generates also can keep particle diameter between 50-500nm.
5. the present invention adopts n-hexadecane as the lipophilicity stablizer, and with respect to other stablizer, it possesses complete oil soluble, and its lipophilicity is more obvious than other lipophilicity stablizer effect, thereby makes miniemulsion form stable drop, stable carrying out in late phase reaction.
6. with respect to oil-soluble initiator, the present invention adopts water soluble starter, and its velocity of initiation is fast, cost is low.
7. adopt strong acid and acid stronger solution can make that the silane coupling agent hydrolysis is more abundant, thereby can improve the access point of nano-silica surface, and then in reaction afterwards, improve monomeric participation amount.
8. use the organic solvent except silica modified, all the other all carry out in the aqueous solution, and environmental pollution is little like this, and industrialization after being convenient to.
9. the silane coupling agent that adopts of the present invention, the isocyanates coupling agent with respect to prior art adopts has the low advantage of toxicity.
The nano silicon dioxide-acrylate composite emulsion of the present invention's preparation has excellent comprehensive performances, in many departments such as wood working, packing, medicine, weaving, papermaking, building, machineries, can be widely used as coating, tackiness agent and seal gum etc.
Embodiment
Embodiment 1:
A kind of preparation method of nano silicon dioxide-acrylate composite emulsion comprises following step:
The first step: the small molecular alcohol of 10～100 parts of quality, the silane coupling agent of 100-800 part quality and the deionized water of 10～100 parts of quality and the acidic solution of 1～10 part of quality are mixed, and under 100～800 rev/mins speed churning time 2～16 hours, obtain the silane coupling agent hydrolysate;
In the present embodiment, small molecule alcohol is meant carbonatoms less than 5 alcohol, for example can be methyl alcohol, ethanol, propyl alcohol, butanols, its mass fraction can be 20 parts of quality, 32 parts of quality, 45 parts of quality, 52 parts of quality, 70 parts of quality, 81 parts of quality, 90 parts of quality, silane coupling agent can be the methacryloyl propyl trimethoxy silicane, vinyltriethoxysilane, isocyanato oxypropyl trimethyl silane, aminopropyltriethoxywerene werene, vinyltrimethoxy silane, a kind of in the silane such as vinyl three (2-methoxy ethoxy) silane, its mass fraction can be 15 parts of quality, 22 parts of quality, 35 parts of quality, 43 parts of quality, 55 parts of quality, 64 parts of quality, 72 parts of quality, 85 parts of quality, 220 parts of quality, 350 parts of quality, 420 parts of quality, 550 parts of quality, 660 parts of quality, 740 parts of quality, acidic solution can be hydrochloric acid, sulfuric acid, phosphoric acid or be the tart salts solution is as sodium pyrosulfate etc., its quality can be 3 parts of quality, 4.2 part quality, 5.7 parts of quality, 6.3 parts of quality, 7.5 part quality, 8.4 part quality, 9.2 parts of quality, its pH value can be 1,1.5,2,2.3,3,4, can adopt induction stirring or mechanical stirring, mixing speed is 300rpm, 460rpm, 530rpm, 750rpm, churning time can be 13 hours, 10 hours, 7.5 hour, 3 hours;
Second step: under protection of inert gas, the above-mentioned silane coupling agent hydrolysate of the nano silicon of 10-200 part quality and 1-20 part quality is joined in the derivative solvent of 100-2000 part benzene and stir, stirring velocity is 100-800 rev/min, churning time 2-16 hour, obtain the silicon-dioxide of modification by centrifugation, the rotating speed of centrifugation is 1000-8000 rev/min, and remove unnecessary hydrolysate with 100-800 part small molecular alcohol or acetone rinsing, then under 60-80 ℃, (can not be higher than under the 0.01Mpa) drying under the vacuum condition, obtain modified manometer silicon dioxide;
In the present embodiment, rare gas element can be a nitrogen, argon gas, nano silicon are meant that particle diameter is the mixture of the non-homogeneous size of 20-40 nanometer, can prepare nano silicon by TEOS alkaline hydrolysis, its mass fraction can be 15 parts, 30 parts, 42 parts, 55 parts, 68 parts, 80 parts, 95 parts, 110 parts, 125 parts, 133 parts, 146 parts, 166 parts, 180 parts, 191 parts, the mass fraction of silane coupling agent hydrolysate can be 3 parts, 4.5 parts, and 5.2 parts, 6.3 part, 7 parts, 8.5 parts, 11 parts, 15 parts, 16.4 parts, 18.5 part, 19.2 parts, the derivative solvent of benzene can be toluene, the derivative liquid of benzene such as dimethylbenzene, its mass fraction can be 150 parts, 260 parts, and 320 parts, 480 parts, 560 parts, 800 parts, 1200 parts, 1350 parts, 1720 parts, 1910 parts, stirring velocity can be 300rpm, 460rpm, 530rpm, 750rpm, churning time can be 13 hours, 10 hours, and 7.5 hours, 3 hours, small molecule alcohol is meant that monomolecular carbonatoms less than 5 alcohol, can be a methyl alcohol, ethanol, propyl alcohol, butanols, drying temperature can be 63 ℃, 72 ℃, 78 ℃.
The 3rd step: acrylic ester monomer is dispersed into the acrylic ester monomer miniemulsion that median size is 50～500nm, emulsification can be adopted ultrasonic emulsification, also can adopt high-speed stirring, wherein, ultrasound condition is: ultrasonic frequency is 200kHz～300kHz, ultrasonic power 200-1600W, the ultrasonic emulsification time is 1-30 minute; Wherein, ultrasonic power can be chosen for 1400W, 1000W, and 500W, the ultrasonic emulsification time can be chosen for 10min, 18min, 28min; The condition of high-speed stirring is: rotating speed is 10000～20000 rev/mins;
The 4th step: with the above-mentioned improved silica of 10-100 part quality, mixing of the negatively charged ion of 2-20 part quality or nonionic emulsifying agent and 1-30 part quality as the liquid lipophilic alkane of stablizer or the water of pure and mild 10-1000 part quality, then with above-mentioned mixed solution emulsification, make modified manometer silicon dioxide be dispersed in the aqueous solution, solubility persulphate or the oil-soluble superoxide that add 2-20 part quality then as initiator, temperature with mixed solution remains in the 70-80 ℃ of scope again, with 0.01-20 part quality/minute speed the aforesaid propylene esters of gallic acid monomer miniemulsion of 20-600 part quality is added drop-wise in the above-mentioned mixed solution, continue to make mixed solution in 70-80 ℃ of scope, to be incubated after dropwising, its soaking time is more than 1 hour, obtains nano silicon dioxide-acrylate composite emulsion at last.
Wherein mixed solution emulsive method can be adopted the method emulsification of ultrasonic emulsification or high-speed stirring, the ultrasonic emulsification condition: ultrasonic frequency is 200kHz～300kHz, ultrasonic power 200-1600W, the ultrasonic emulsification time is 1-30min, high-speed stirring emulsification: induction stirring or mechanical stirring, 10000～20000 rev/mins of rotating speeds; The mass fraction of improved silica can be 25 parts, 38 parts, 45 parts, 60 parts, 80 parts, 90 parts, negatively charged ion or nonionic emulsifying agent can be polyoxyethylene nonylphenol ether and Succinic Acid modification polyxyethylated alkylphenol, sodium lauryl sulphate, sodium laurylsulfonate, Triton X-405 (market can be buied), if Triton X-100 TritonX-165 negatively charged ion such as (market can be buied) and nonionogenic tenside one or more mixture wherein is mixture, its proportioning can be any proportioning, the mass fraction of negatively charged ion or nonionic emulsifying agent can be 3 parts, 4.5 parts, and 5.3 parts, 6 parts, 7.5 part, 9 minutes, 10 parts, 13.2 part, 16.7 part, 18.5 parts, 19.2 parts; The lipophilicity stablizer can be in n-hexadecane, positive hexadecanol, the methacrylic acid hexadecanol a kind of, its mass fraction can be 3 parts, 4.5 parts, 5.3 parts, 6 parts, 7.5 parts, 9 parts, 10 parts, 13.2 part, 16.7 parts, 18.5 parts, 19.2 part, 23 parts, 26.2 parts, 28 parts, 29 parts, ultrasonic power can be 300W, 500W, 850W, 1000W, 1050W, 1350W, 1450W, 1520W, the ultrasonic emulsification time can be 29 minutes, 27 minutes, 23.5 minute, 20 minutes, 15 minutes, 12.5 minute, 8 minutes, 3 minutes; The solubility persulphate can be in Potassium Persulphate, the ammonium persulphate a kind of, it also can be the oil soluble superoxide, promptly can be a kind of in Diisopropyl azodicarboxylate, benzoyl peroxide, laurylperoxide base acyl, the tert-butyl peroxide, its mass fraction is 3 parts, 7 parts, and 12.5 parts, 14.2 part, 16 parts, 18.5 parts, 19 parts; The temperature of mixed solution can be 75 ℃, 78 ℃, acrylic ester monomer can be a methacrylate monomer, the ethyl propenoate monomer, the Octyl acrylate monomer, the Isooctyl acrylate monomer monomer, methyl methacrylate monomer, the hydroxyethyl methylacrylate monomer, the Rocryl 410 monomer, the Hydroxyethyl acrylate monomer, the Propylene glycol monoacrylate monomer, glycidyl methacrylate monomer one or more mixture wherein, the proportioning of mixture can be any proportioning, the mass fraction of acrylic ester monomer can be 30 parts, 85 parts, 120 parts, 200 parts, 350 parts, 460 parts, 520 parts; The speed that drips can for 0.02 part of quality/minute, 0.05 part of quality/minute, 0.08 part of quality/minute, 0.1 part quality/minute, 0.3 part of quality/minute, 0.85 part of quality/minute, 1 part of quality/minute, 1.8 parts of quality/minute, 2.8 parts of quality/minute, 3.5 part quality/minute, 4.2 part quality/minute, 5 parts of quality/minute, 6.2 parts of quality/minute, 7.5 part quality/minute, 8 parts of quality/minute, 9 parts of quality/minute, 10 parts of quality/minute, 11 parts of quality/minute, 13 parts of quality/minute, 15 parts of quality/minute, 17 parts of quality/minute, 19 parts of quality/minute, 20 parts of quality/minute; Soaking time can be 1 hour, and 5 hours, 15 hours, 24 hours, time upper limit exceeded not influence production efficiency;
In the present embodiment, n-hexadecane is best as the effect of lipophilicity stablizer;
Embodiment 2:
(1) preparation of modified manometer silicon dioxide:
In the Erlenmeyer flask of magnetic stirring apparatus, add 20g methyl alcohol, 15g methacryloyl propyl trimethoxy silicane and 20g water; and add the hydrochloric acid that 3g pH value equals 1; 300 rev/mins of rotating speeds, 13 hours time, thereby preparation methacryloyl propyl group ortho-siliformic acid.The 15g nano silicon is added in the 150g toluene solution, and nitrogen protection, add 3g methacryloyl propyl group ortho-siliformic acid.Induction stirring, 300 rev/mins of rotating speeds, 10 hours time.Obtain the silicon-dioxide of modification by centrifugation, and use alcohol flushing, then 63 ℃ of following vacuum-dryings.
(2) nano silicon dioxide-acrylate composite emulsion preparation:
Add improved silica 25g in the four-hole bottle, add 3g polyoxyethylene nonylphenol ether and 3g Succinic Acid modification polyxyethylated alkylphenol then, add 100g water simultaneously, after adding n-Hexadecane 3g, ultrasonic emulsification, ultrasonic frequency is 200kHz～300kHz, output rating 300W, 29 minutes time added the 3g ammonium persulphate then, after temperature rises to 70 ℃, begin to drip 30g methyl methacrylate monomer miniemulsion, rate of addition 0.02g/ branch is incubated 2 hours down at 70 ℃ then, obtains nano silicon dioxide-acrylate composite emulsion.The ultrasonic emulsification condition that obtains the methyl methacrylate monomer miniemulsion is: ultrasonic frequency is 200kHz～300kHz, ultrasonic power 200-1600W, and the ultrasonic emulsification time is 1-30min.
Proportioning:
A nano silicon 15 grams
B methacryloyl propyl trimethoxy silicane 15 grams
C methyl methacrylate 30 grams
D Succinic Acid modification polyxyethylated alkylphenol OS 3 grams
E polyoxyethylene nonylphenol ether OP 3 grams
F ammonium persulphate 3 grams
G water 100 grams
Embodiment 3:
(1) preparation of modified manometer silicon dioxide:
In the Erlenmeyer flask of magnetic stirring apparatus, add 32g methyl alcohol, 35g methacryloyl propyl trimethoxy silicane and 46g water, and add the sulfuric acid that 4.2g pH value equals 1.5,460 rev/mins of rotating speeds, 10 hours time, thereby preparation vinyltriethoxysilane.The 30g nano silicon is added in the 260g toluene solution; and nitrogen protection; add excessive 4.5g vinyl ortho-siliformic acid; induction stirring; 460 rev/mins of rotating speeds, 7.5 hours time is by the silicon-dioxide of centrifugation acquisition modification; and remove unnecessary hydrolysate with the propyl alcohol flushing, then 72 ℃ of following vacuum-dryings.
(2) nano silicon dioxide-acrylate composite emulsion preparation:
Add improved silica 38g in the four-hole bottle, add the 4.5g sodium lauryl sulphate then, behind the adding 4.5g hexadecanol, water 250g, ultrasonic emulsification, ultrasonic frequency are 200kHz～300kHz, output rating 500W, 27 minutes time added the 7g Potassium Persulphate then, after temperature rises to 70 ℃, begin to drip 85g Hydroxyethyl acrylate and butyl acrylate mixed solution, rate of addition 0.05 Grams Per Minute is incubated 3 hours down at 70 ℃ then, obtains nano silicon dioxide-acrylate composite emulsion.The ultrasonic emulsification condition that obtains the miniemulsion of Hydroxyethyl acrylate and Butyl Acrylate Monomer mixed solution is: ultrasonic frequency is 200kHz～300kHz, ultrasonic power 200-1600W, and the ultrasonic emulsification time is 1-30min.
A nano silicon 30 grams
B vinyltriethoxysilane 35 grams
C Hydroxyethyl acrylate 30 grams
D butyl acrylate 55 grams
E sodium lauryl sulphate 4.5 grams
F Potassium Persulphate 7 grams
G water 250 grams
Embodiment 4:
(1) preparation of modified manometer silicon dioxide:
In the Erlenmeyer flask of magnetic stirring apparatus, add 90g methyl alcohol, 740g methacryloyl propyl trimethoxy silicane and 90g water; and add the sodium pyrosulfate that 9.2g pH value equals 4; 750 rev/mins of rotating speeds, 3 hours time, thereby preparation methacryloyl propyl group ortho-siliformic acid.The 191g nano silicon is added in the 1910g toluene solution, and nitrogen protection, add excessive 19.2g methacryloyl propyl group ortho-siliformic acid.Induction stirring, 750 rev/mins of rotating speeds, 3 hours time.Obtain the silicon-dioxide of modification by centrifugation, and remove unnecessary hydrolysate, then 78 ℃ of following vacuum-dryings with alcohol flushing.
(2) nano silicon dioxide-acrylate composite emulsion preparation:
Add improved silica 60g in the four-hole bottle, add the 9g sodium lauryl sulphate then, behind adding 10g n-Hexadecane, the water 500g, ultrasonic emulsification, ultrasonic frequency is 200kHz～300kHz, output rating 1000W, 20 minutes time, add the 16g Potassium Persulphate then, after temperature rises to 70 ℃, begin to drip 200g methyl methacrylate and butyl acrylate mixed solution, rate of addition 0.1g/ branch, be incubated 5 hours down at 70 ℃ then, obtain nano silicon dioxide-acrylate composite emulsion.The ultrasonic emulsification condition that obtains the miniemulsion of methyl methacrylate and Butyl Acrylate Monomer mixed solution is: ultrasonic frequency is 200kHz～300kHz, ultrasonic power 200-1600W, and the ultrasonic emulsification time is 1-30min.
A nano silicon 191 grams
B methacryloyl propyl trimethoxy silicane 740 grams
C methyl methacrylate 100 grams
D butyl acrylate 100 grams
E sodium lauryl sulphate 9 grams
F Potassium Persulphate 16 grams
G water 500 grams
Embodiment 5:
(1) preparation of modified manometer silicon dioxide:
In the Erlenmeyer flask of magnetic stirring apparatus, add 70g methyl alcohol, 220g isocyanato oxypropyl trimethyl silane and 86g water, and add the phosphoric acid that 6.3gpH equals 2.3,530 rev/mins of rotating speeds, 7.5 hours time, thereby preparation isocyanato propyl group ortho-siliformic acid.The 80g nano silicon is added in the 480g toluene solution, and nitrogen protection, add excessive 8.5g methacryloyl propyl group ortho-siliformic acid.Induction stirring, 460 rev/mins of rotating speeds, 10 hours time.Obtain the silicon-dioxide of modification by centrifugation, and remove unnecessary hydrolysate, then 72 ℃ of following vacuum-dryings with the propyl alcohol flushing.
(2) nano silicon dioxide-acrylate composite emulsion preparation:
Add improved silica 90g in the four-hole bottle, add the 19.2g sodium lauryl sulphate then, ultrasonic emulsification behind adding 29g n-Hexadecane, the water 750g, ultrasonic frequency is 200kHz～300kHz, output rating 1520W, 8 minutes time added the 19g ammonium persulphate then, after temperature rises to 70 ℃, the mixed solution of beginning Dropwise 5 20g methyl methacrylate and butyl acrylate, rate of addition 6.2 Grams Per Minutes are incubated 1.5 hours down at 70 ℃ then, obtain nano silicon dioxide-acrylate composite emulsion.The ultrasonic emulsification condition of the miniemulsion of the monomer mixed solution of acquisition methyl methacrylate and butyl acrylate is: ultrasonic frequency is 200kHz～300kHz, ultrasonic power 200-1600W, and the ultrasonic emulsification time is 1-30min.
A nano silicon 80 grams
B isocyanato oxypropyl trimethyl silane 220 grams
C methyl methacrylate 300 grams
D butyl acrylate 220 grams
E sodium lauryl sulphate 19.2 grams
F ammonium persulphate 19 grams
G water 750 grams
Obtain 200nm at last and contain the 20%-40% nano silicon dioxide-acrylate composite emulsion admittedly.
Claims (6)
1, a kind of preparation method of nano silicon dioxide-acrylate composite emulsion is characterized in that may further comprise the steps:
The first step: the small molecular alcohol of 10～100 parts of quality, the silane coupling agent of 100-800 part quality and the deionized water of 10～100 parts of quality and the acidic solution of 1～10 part of quality are mixed, and under 100～800 rev/mins speed churning time 2～16 hours, obtain the silane coupling agent hydrolysate;
Second step: under protection of inert gas, the above-mentioned silane coupling agent hydrolysate of the nano silicon of 10～200 parts of quality and 1-20 part quality is joined in the derivative solvent of benzene of 100～2000 parts of quality and stir, stirring velocity is 100-800 rev/min, churning time is 2～16 hours, obtain the silicon-dioxide of modification by centrifugation, and small molecular alcohol or acetone rinsing with 100-800 part quality, thereby remove unnecessary silane coupling agent hydrolysate, dry under vacuum then, obtain modified manometer silicon dioxide;
The 3rd step: acrylic ester monomer is dispersed into the acrylic ester monomer miniemulsion that median size is 50～500nm;
The 4th step: with the above-mentioned improved silica of 10-100 part quality, mixing of the negatively charged ion of 2-20 part quality or nonionic emulsifying agent and 1-30 part quality as the liquid lipophilic alkane of stablizer or the water of pure and mild 10-1000 part quality, then with above-mentioned mixed solution emulsification, make modified manometer silicon dioxide be dispersed in the aqueous solution, solubility persulphate or the oil-soluble superoxide that add 2-20 part quality then as initiator, and the temperature of mixed solution remained in the 70-80 ℃ of scope, with 0.01-20 part quality/minute speed the aforesaid propylene esters of gallic acid monomer miniemulsion of 20-600 part quality is added drop-wise in the above-mentioned mixed solution, continue to make mixed solution in 70-80 ℃ of scope, to be incubated after dropwising, its soaking time is more than 1 hour, obtain nano silicon dioxide-acrylate composite emulsion at last
Aforesaid propylene esters of gallic acid monomer is methacrylate monomer, ethyl propenoate monomer, Octyl acrylate monomer, Isooctyl acrylate monomer monomer, methyl methacrylate monomer, hydroxyethyl methylacrylate monomer, Rocryl 410 monomer, Hydroxyethyl acrylate monomer, Propylene glycol monoacrylate monomer, glycidyl methacrylate monomer one or more mixture wherein.
2. the preparation method of nano silicon dioxide-acrylate composite emulsion according to claim 1, it is characterized in that above-mentioned mixed solution emulsive method can being adopted supersound method in the 4th step, wherein ultrasonic frequency is 200kHz～300kHz, ultrasonic power 200-1600W, the ultrasonic emulsification time is 1-30min.
3. the preparation method of nano silicon dioxide-acrylate composite emulsion according to claim 1 is characterized in that as a kind of in n-hexadecane, positive hexadecanol, the methacrylic acid hexadecanol of the liquid lipophilic alkane of stablizer or alcohol.
4. the preparation method of nano silicon dioxide-acrylate composite emulsion according to claim 1, the pH value of the acidic solution that it is characterized in that is less than 5.
5. the preparation method of nano silicon dioxide-acrylate composite emulsion according to claim 1 is characterized in that solubility persulphate as initiator can be a kind of in Potassium Persulphate, the ammonium persulphate.
6. the preparation method of nano silicon dioxide-acrylate composite emulsion according to claim 1, it is characterized in that as the oil-soluble superoxide of initiator can be in Diisopropyl azodicarboxylate, benzoyl peroxide, laurylperoxide base acyl, the tert-butyl peroxide a kind of.
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