CN104262530A - Unmodified silica sol/polystyrene-acrylate nano core-shell emulsion and preparation method thereof - Google Patents
Unmodified silica sol/polystyrene-acrylate nano core-shell emulsion and preparation method thereof Download PDFInfo
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- 239000000839 emulsion Substances 0.000 title claims abstract description 75
- 239000011258 core-shell material Substances 0.000 title claims abstract description 36
- 229920005553 polystyrene-acrylate Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000004945 emulsification Methods 0.000 title description 3
- 239000000178 monomer Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- -1 acrylic ester Chemical class 0.000 claims description 34
- 150000003376 silicon Chemical class 0.000 claims description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 229960001866 silicon dioxide Drugs 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 238000004448 titration Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 239000004160 Ammonium persulphate Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000012874 anionic emulsifier Substances 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 125000005336 allyloxy group Chemical group 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 210000000481 breast Anatomy 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- FIHPJYMQCLZZJG-UHFFFAOYSA-N diazanium ethenoxyethene sulfate Chemical compound S(=O)(=O)([O-])[O-].[NH4+].C(=C)OC=C.[NH4+] FIHPJYMQCLZZJG-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000012875 nonionic emulsifier Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000004100 electronic packaging Methods 0.000 abstract 1
- 239000003063 flame retardant Substances 0.000 abstract 1
- 239000005543 nano-size silicon particle Substances 0.000 abstract 1
- 239000005022 packaging material Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses an unmodified silica sol/polystyrene-acrylate nano core-shell emulsion and a preparation method thereof. Commercially available alkaline silica sol, styrene and acrylate monomers are taken as main raw materials, nano particles are not required to be subjected to tedious surface modification, and under the action of a reactive emulsifier, a seed monomer is subjected to in-situ polymerization on the surface of nano-SiO2, and then subjected to shell monomer polymerization, so that a high silica sol/polystyrene-acrylate nano core-shell polymer emulsion is formed, and the emulsion has various characteristics of small particle size, high silicon content, high covering rate, high stability and the like. The method is simple in production process and rapid in synthesis, and the obtained composite emulsion has an obvious nano core-shell composite structure, takes nano silicon dioxide as a core and takes acrylate as a shell; and the emulsion has good water resistance, stain resistance, heat resistance, acid and alkali resistance and the like, is environmental-friendly and fire-retardant, and has good transparency. The emulsion can be widely applied to various fields of coatings such as high-grade architectural coatings, electronic packaging materials, anti-corrosion coatings for ships, and the like.
Description
Technical field
The invention belongs to environment-protection nano nucleocapsid water-based emulsion field, particularly relate to a kind of unmodified silicon sol/Polystyrene-acrylate nano core-shell emulsion and preparation method thereof.
Background technology
About the nano-material modified and existing many research of benzene emulsion preparation, but the effective ways of nano-material modified benzene emulsion are also less.Prepare composite emulsion by the method for physical blending in early days, coating is prepared as film forming binder, as: " nano inner wall coating " (application number 200810147407.1 publication date 2009-01-07), " a kind of nanometer silica sol modified exterior wall coating and preparation method thereof " (application number 201310331019.X publication date 2013-10-23), " a kind of antifouling imitative porcelain four-in-one coating " (application number 201310460051.8 publication date 2014-02-05), " a kind of Silica sol high-permeability multifunctional transparent finish-coat paint " (application number 201310688008.7 publication date 2014-04-16).This method technique is simple, but SiO
2particle can not form effective interaction with polymer latex particles, and the package stability of blending emulsion is poor, to the improvement poor effect of emulsion property, mainly because nano particle can not get dispersed in benzene emulsion matrix.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of production technique is simple, the unmodified silicon sol/Polystyrene-acrylate nano core-shell emulsion of high-performance and low-cost, high clad ratio and preparation method thereof.
For solving the problems of the technologies described above, the present invention is by the following technical solutions: unmodified silicon sol/Polystyrene-acrylate nano core-shell emulsion, and unmodified silicon sol/Polystyrene-acrylate nano-core-shell structure take nanometer silicon dioxide particle as core, copolymer in cinnamic acrylic ester is shell; The solid content of emulsion is 30 ~ 60%, in silicon-dioxide, and SiO in emulsion
2mass content be 10 ~ 25%.
Above-mentioned unmodified silicon sol/Polystyrene-acrylate nano core-shell emulsion, makes primarily of commercial available alkaline silicon sol, vinylbenzene and acrylic ester monomer.
The preparation method of above-mentioned unmodified silicon sol/Polystyrene-acrylate nano core-shell emulsion, with commercial available alkaline silicon sol, vinylbenzene and acrylic ester monomer for main raw material, under reactive emulsifier effect, make vinylbenzene and acrylic ester monomer at the SiO of non-modified
2particle surface generation in-situ polymerization, obtains with SiO
2for the seed emulsion of core, then carry out the polymerization of cinnamic acrylic ester shell on seed emulsion breast grain surface, to obtain final product.
The preparation method of above-mentioned unmodified silicon sol/Polystyrene-acrylate nano core-shell emulsion, comprises the following steps:
The preparation of <1> silicon sol/cinnamic acrylic ester seed emulsion
With commercial available alkaline silicon sol, vinylbenzene and acrylic ester monomer for main raw material, under reactive emulsifier effect, make vinylbenzene and acrylic ester monomer at the SiO of non-modified
2particle surface generation in-situ polymerization, obtains seed emulsion;
The synthesis of the unmodified silicon sol of <2>/Polystyrene-acrylate nano core-shell emulsion
In seed emulsion, add non-reacted emulsifying agent, sodium carbonate, initiator, start at the uniform velocity to drip cinnamic acrylic ester class mix monomer and carry out shell polymerization, obtain unmodified silicon sol/Polystyrene-acrylate nano core-shell emulsion.
Commercial available alkaline silicon sol, in silicon-dioxide, the weight content of silicon is 30 ~ 50%, and median size is 10 ~ 30nm, and pH value is 9 ~ 10;
Acrylic ester monomer is two or more in methyl methacrylate, n-butyl acrylate, methacrylic acid, β-dimethyl-aminoethylmethacrylate, vinylformic acid;
Reactive emulsifier is one or both in allyloxy Nonylphenoxy propyl alcohol Soxylat A 25-7, allyloxy hydroxypropyl azochlorosulfonate acid sodium, allyloxy fatty alcohol oxygen Vinyl Ether ammonium sulfate, allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether ammonium sulfate;
Non-reacted emulsifying agent is anionic or nonionic emulsifier, and anionic emulsifier is one or both in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate;
Initiator is ammonium persulphate.
The preparation method of above-mentioned unmodified silicon sol/Polystyrene-acrylate nano core-shell emulsion, is undertaken by following operation:
<1> seeded emulsion polymerization: the four-hole boiling flask that agitator, reflux condensing tube, thermometer and titration funnel are housed is placed in thermostat water bath, stirs, at N with 300 ~ 400r/min constant speed
2under protection, count by weight, add 100 ~ 140 parts of deionized waters, 3 ~ 5 parts of reactive emulsifiers, add the commercial available alkaline silicon sol of 150 ~ 300 parts after 10 minutes, be uniformly dispersed; Be warming up to 75 DEG C gradually, and keep constant temperature, add 0.20 ~ 0.50 part of initiator, start titration 8 ~ 20 parts of cinnamic acrylic ester class mix monomers, within 10 ~ 30 minutes, drip off, and be incubated 1 hour, obtain seed emulsion;
<2> shell monomer polymerization: add 3 ~ 5 parts of non-reacted emulsifying agents in seed emulsion, 0.8 ~ 2.0 part of sodium carbonate, 0.4 ~ 0.8 part of initiator, start at the uniform velocity to drip 100 ~ 150 parts of cinnamic acrylic ester class mix monomers, within 2.5 ~ 3 hours, dropwise; Be warming up to 80 DEG C, insulation 1h after be cooled to room temperature, adjust pH to 8 ~ 8.5, filter discharging, the unmodified silicon sol of shallow white blueing/Polystyrene-acrylate nano core-shell emulsion.
Non-reacted emulsifying agent is dissolved in 10 parts of distilled water and makes solution and add, and sodium carbonate is dissolved in 10 parts of distilled water and makes solution and add, and initiator is dissolved in 10 parts of distilled water and makes solution and add.
For current environment-protection nano nucleocapsid water-based emulsion and prepare Problems existing, we have established the preparation method of a kind of unmodified silicon sol/Polystyrene-acrylate nano core-shell emulsion, that is: with commercial available alkaline silicon sol, vinylbenzene and acrylic ester monomer for main raw material, without the need to carrying out loaded down with trivial details surface modification treatment to nanoparticle, under reactive emulsifier effect, based on multiple mechanisms such as interface medium, electrostatic adhesion, adopt special seeding polymerization technique, make vinylbenzene and acrylic ester monomer at the SiO of non-modified
2particle surface generation in-situ polymerization, obtains with SiO
2for the seed emulsion of core, then the polymerization of cinnamic acrylic ester shell is carried out on seed emulsion breast grain surface, the composite polymer particle that to obtain take nanometer silicon dioxide particle as core, copolymer in cinnamic acrylic ester is shell, synthesizes the unmodified silicon sol/Polystyrene-acrylate nano core-shell emulsion of excellent performance.
Method production technique of the present invention is simple, synthesis fast, composite polymer particle has obvious nano core-shell composite structure, the little and narrowly distributing (60 ~ 80nm) of particle diameter.Unmodified silicon sol/Polystyrene-acrylate nano core-shell the emulsion of synthesis is due to features such as particle diameter is little, silicone content high (accounting for the 40-50% of total dry film quality), nucleocapsid covering property are good, good stabilities, its film is had performances such as high transparent, water tolerance, hardness are high, strong adhesion, there is the performances such as good contamination resistance, thermotolerance, acid and alkali-resistance simultaneously, and environmental protection, difficult combustion, be a kind of high-performance, low cost new environment-protection nano nucleocapsid water-based emulsion.Therefore, this emulsion is widely used in the multiple coating fields such as top-grade building coating, metal protection coating, boats and ships protective system as filmogen.The novel nano composite water soluble exterior coating product properties developed accordingly meets the technical requirements in water-based exterior wall paint GB GB/T9755-2001 more than premium grads, especially water-fast, resistance to acids and bases, resistance to soiling, artificial ageing resistance are extremely excellent.Due to the use of high content silicon colloidal sol, the present invention greatly saves petroleum resources, with low cost, not only meets the requirement of performance but also meet the demand of modern environmental protection development.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the unmodified silicon sol of the present invention/Polystyrene-acrylate nano core-shell composite polymer particle.
Embodiment
Embodiment 1
<1> seeded emulsion polymerization: the four-hole boiling flask that agitator, reflux condensing tube, thermometer and titration funnel are housed is placed in thermostat water bath, stirs, at N with 400r/min constant speed
2under protection, count by weight, add 100g deionized water, 3g reactive emulsifier allyloxy Nonylphenoxy propyl alcohol Soxylat A 25-7, the commercial available alkaline silicon sol of 150g is added (in silicon-dioxide after 10 minutes, the weight content of silicon is 30%, median size is 10nm, and pH value is 9), be uniformly dispersed; Be warming up to 75 DEG C gradually, and keep constant temperature, add 0.20g ammonium persulphate (be dissolved in 10g distilled water make solution add), start titration 8g cinnamic acrylic ester class mix monomer (positive butyl ester/methyl methacrylate/acrylic acid=47/49/3/1 of styrene/acrylic, mass ratio), within 10 minutes, drip off, and be incubated 1 hour, obtain seed emulsion;
<2> shell monomer polymerization: add the non-reacted emulsifier sodium lauryl sulfate of 3g (be dissolved in 10g distilled water make solution add) in seed emulsion, 0.8g sodium carbonate (be dissolved in 10g distilled water make solution add), 0.4g ammonium persulphate (be dissolved in 10g distilled water make solution add), start at the uniform velocity to drip 100g cinnamic acrylic ester class mix monomer (positive butyl ester/methyl methacrylate/acrylic acid=47/49/3/1 of styrene/acrylic, mass ratio), within 2.5 hours, dropwise; Be warming up to 80 DEG C, insulation 1h after be cooled to room temperature, adjust pH to 8, filter discharging, the unmodified silicon sol of shallow white blueing/Polystyrene-acrylate nano core-shell emulsion.
After testing, this routine emulsion appearance is that blueing is translucent, and median size is 30nm.
Embodiment 2
<1> seeded emulsion polymerization: the four-hole boiling flask that agitator, reflux condensing tube, thermometer and titration funnel are housed is placed in thermostat water bath, stirs, at N with 300r/min constant speed
2under protection, count by weight, add 140g deionized water, 5g reactive emulsifier allyloxy hydroxypropyl azochlorosulfonate acid sodium, the commercial available alkaline silicon sol of 300g is added (in silicon-dioxide after 10 minutes, the weight content of silicon is 50%, median size is 30nm, and pH value is 10), be uniformly dispersed; Be warming up to 75 DEG C gradually, and keep constant temperature, add 0.50g ammonium persulphate (be dissolved in 10g distilled water make solution add), start titration 20g cinnamic acrylic ester class mix monomer (positive butyl ester/β-dimethyl-aminoethylmethacrylate/methacrylic acid=46/47/4/3 of styrene/acrylic, mass ratio), within 20 minutes, drip off, and be incubated 1 hour, obtain seed emulsion;
<2> shell monomer polymerization: add the non-reacted emulsifying agent Sodium dodecylbenzene sulfonate of 6g (be dissolved in 10g distilled water make solution add) in seed emulsion, 2.5g sodium carbonate (be dissolved in 10g distilled water make solution add), 0.8g ammonium persulphate (be dissolved in 10g distilled water make solution add), start at the uniform velocity to drip 150g cinnamic acrylic ester class mix monomer (positive butyl ester/β-dimethyl-aminoethylmethacrylate/methacrylic acid=46/47/4/3 of styrene/acrylic, mass ratio), within 3 hours, dropwise; Be warming up to 80 DEG C, insulation 1h after be cooled to room temperature, adjust pH to 8, filter discharging, the unmodified silicon sol of shallow white blueing/Polystyrene-acrylate nano core-shell emulsion.
Embodiment 3
<1> seeded emulsion polymerization: the four-hole boiling flask that agitator, reflux condensing tube, thermometer and titration funnel are housed is placed in thermostat water bath, stirs, at N with 300r/min constant speed
2under protection, count by weight, add 120g deionized water, 4g reactive emulsifier allyloxy fatty alcohol oxygen Vinyl Ether ammonium sulfate, the commercial available alkaline silicon sol of 250g is added (in silicon-dioxide after 10 minutes, the weight content of silicon is 40%, median size is 20nm, and pH value is 9), be uniformly dispersed; Be warming up to 75 DEG C gradually, and keep constant temperature, add 0.30g ammonium persulphate (be dissolved in 10g distilled water make solution add), start titration 15g cinnamic acrylic ester class mix monomer (positive butyl ester/vinylformic acid=48/48/4 of styrene/acrylic, mass ratio), within 20 minutes, drip off, and be incubated 1 hour, obtain seed emulsion;
<2> shell monomer polymerization: mixture (the mass ratio 1:1 adding the non-reacted emulsifying agent sodium laurylsulfonate of 4g and Sodium dodecylbenzene sulfonate in seed emulsion, be dissolved in 10g distilled water to make solution and add), 1.3g sodium carbonate (be dissolved in 10g distilled water make solution add), 0.6g ammonium persulphate (be dissolved in 10g distilled water make solution add), start at the uniform velocity to drip 130g cinnamic acrylic ester class mix monomer (positive butyl ester/vinylformic acid=48/48/4 of styrene/acrylic, mass ratio), within 2.5 hours, dropwise, be warming up to 80 DEG C, insulation 1h after be cooled to room temperature, adjust pH to 8, filter discharging, the unmodified silicon sol of shallow white blueing/Polystyrene-acrylate nano core-shell emulsion.
After testing, this routine emulsion appearance is that blueing is translucent, and median size is 65nm.
Embodiment 4
Substantially the same manner as Example 1, in the seeded emulsion polymerization of only step <1>, reactive emulsifier changes allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether ammonium sulfate into.
Embodiment 5
Substantially the same manner as Example 1, in the shell monomer polymerization of only step <2>, non-reacted emulsifying agent changes Sodium dodecylbenzene sulfonate into.
Embodiment 6
Substantially the same manner as Example 1, in the shell monomer polymerization of only step <2>, non-reacted emulsifying agent changes the mixture (mass ratio 1:1) of sodium lauryl sulphate and sodium laurylsulfonate into.
Carry out fundamental property detection to the unmodified silicon sol of embodiment 1-6 gained/Polystyrene-acrylate nano core-shell product emulsion, result is as table 1 and Fig. 1.
Table 1 emulsion fundamental property index
Fig. 1 shows, and the particle size analysis in composite emulsion of the present invention is 60 ~ 80nm, is take nanometer silicon dioxide particle as core (internal layer aterrimus), the clad structure that polymkeric substance (outer light grey) is shell, dispersed splendid.
Claims (7)
1. unmodified silicon sol/Polystyrene-acrylate nano core-shell emulsion, is characterized in that: described unmodified silicon sol/Polystyrene-acrylate nano-core-shell structure take nanometer silicon dioxide particle as core, copolymer in cinnamic acrylic ester is shell; The solid content of described emulsion is 30 ~ 60%, in silicon-dioxide, and SiO in emulsion
2mass content be 10 ~ 25%.
2. unmodified silicon sol according to claim 1/Polystyrene-acrylate nano core-shell emulsion, is characterized in that: make primarily of commercial available alkaline silicon sol, vinylbenzene and acrylic ester monomer.
3. the preparation method of unmodified silicon sol described in claim 1/Polystyrene-acrylate nano core-shell emulsion, it is characterized in that: with commercial available alkaline silicon sol, vinylbenzene and acrylic ester monomer for main raw material, under reactive emulsifier effect, make vinylbenzene and acrylic ester monomer at the SiO of non-modified
2particle surface generation in-situ polymerization, obtains with SiO
2for the seed emulsion of core, then carry out the polymerization of cinnamic acrylic ester shell on seed emulsion breast grain surface, to obtain final product.
4. the preparation method of unmodified silicon sol according to claim 3/Polystyrene-acrylate nano core-shell emulsion, is characterized in that comprising the following steps:
The preparation of <1> silicon sol/cinnamic acrylic ester seed emulsion
With commercial available alkaline silicon sol, vinylbenzene and acrylic ester monomer for main raw material, under reactive emulsifier effect, make vinylbenzene and acrylic ester monomer at the SiO of non-modified
2particle surface generation in-situ polymerization, obtains seed emulsion;
The synthesis of the unmodified silicon sol of <2>/Polystyrene-acrylate nano core-shell emulsion
In seed emulsion, add non-reacted emulsifying agent, sodium carbonate, initiator, start at the uniform velocity to drip cinnamic acrylic ester class mix monomer and carry out shell polymerization, obtain unmodified silicon sol/Polystyrene-acrylate nano core-shell emulsion.
5. the preparation method of unmodified silicon sol according to claim 4/Polystyrene-acrylate nano core-shell emulsion, is characterized in that:
Described commercial available alkaline silicon sol, in silicon-dioxide, the weight content of silicon is 30 ~ 50%, and median size is 10 ~ 30nm, and pH value is 9 ~ 10;
Described acrylic ester monomer is two or more in methyl methacrylate, n-butyl acrylate, methacrylic acid, β-dimethyl-aminoethylmethacrylate, vinylformic acid;
Described reactive emulsifier is one or both in allyloxy Nonylphenoxy propyl alcohol Soxylat A 25-7, allyloxy hydroxypropyl azochlorosulfonate acid sodium, allyloxy fatty alcohol oxygen Vinyl Ether ammonium sulfate, allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether ammonium sulfate;
Described non-reacted emulsifying agent is anionic or nonionic emulsifier, and anionic emulsifier is one or both in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate;
Described initiator is ammonium persulphate.
6. the preparation method of unmodified silicon sol according to claim 5/Polystyrene-acrylate nano core-shell emulsion, is characterized in that being undertaken by following operation:
The four-hole boiling flask that agitator, reflux condensing tube, thermometer and titration funnel are housed is placed in thermostat water bath by <1>, stirs, at N with 300 ~ 400r/min constant speed
2under protection, count by weight, add 100 ~ 140 parts of deionized waters, 3 ~ 5 parts of reactive emulsifiers, add the commercial available alkaline silicon sol of 150 ~ 300 parts after 10 minutes, be uniformly dispersed; Be warming up to 75 DEG C gradually, and keep constant temperature, add 0.20 ~ 0.50 part of initiator, start titration 8 ~ 20 parts of cinnamic acrylic ester class mix monomers, within 10 ~ 30 minutes, drip off, and be incubated 1 hour, obtain seed emulsion;
<2> adds 3 ~ 5 parts of non-reacted emulsifying agents in seed emulsion, 0.8 ~ 2.0 part of sodium carbonate, 0.4 ~ 0.8 part of initiator, starts at the uniform velocity to drip 100 ~ 150 parts of cinnamic acrylic ester class mix monomers, within 2.5 ~ 3 hours, dropwises; Be warming up to 80 DEG C, insulation 1h after be cooled to room temperature, adjust pH to 8 ~ 8.5, filter discharging, the unmodified silicon sol of shallow white blueing/Polystyrene-acrylate nano core-shell emulsion.
7. the preparation method of unmodified silicon sol according to claim 5/Polystyrene-acrylate nano core-shell emulsion, it is characterized in that: described non-reacted emulsifying agent is dissolved in 10 parts of distilled water and makes solution and add, described sodium carbonate is dissolved in 10 parts of distilled water and makes solution and add, and described initiator is dissolved in 10 parts of distilled water and makes solution and add.
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