CN101864083A - Preparation method of methyl polysiloxane/SiO2 composite microsphere - Google Patents
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- CN101864083A CN101864083A CN 201010186345 CN201010186345A CN101864083A CN 101864083 A CN101864083 A CN 101864083A CN 201010186345 CN201010186345 CN 201010186345 CN 201010186345 A CN201010186345 A CN 201010186345A CN 101864083 A CN101864083 A CN 101864083A
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Abstract
The invention relates to a preparation method of methyl polysiloxane/SiO2 composite microsphere. Directing to the defects that production period is long, cost is high and environmental protection can not be realized in the prior art, industrialized sodium methyl silicate aqueous solution and sodium silicate solution are taken as raw materials, the two are mixed, stirred and diluted in certain ratio, inorganic acid is used for regulating the pH of solution to be 1.0-3.0, methyl silicic acid and silicic acid generated in the solution at the moment are crosslinked and polymerized and grow in the stirring process, stirring is continued for a period of time, then the solution is transferred into a baking oven at 60-90 DEG C to keep warm for 2-10 hours, then filtering and washing are carried out, and drying at 60-90 DEG C is carried out, thus obtaining the methyl polysiloxane/SiO2 composite microshpere. By adopting the raw materials and process in the invention, methyl polysiloxane/SiO2 composite microsphere with good dispersity and good liquidity and grain diameter of 2-5Mum can be prepared. The preparation method of the invention is simple, is low-carbon and environmentally friendly, is low in cost, is high in yield and is easy for industrialized production.
Description
Technical field
The invention belongs to the synthetic field of material, particularly is a kind of preparation good dispersity, the methyl polysiloxane/SiO of good fluidity
2The method of complex microsphere.
Background technology
The hydrophilic oleophobic of silica sphere be difficult to disperse in organic medium, and bonding force is poor between the organic matrix, easily causes boundary defect, and composite property is reduced.Solve silicon-dioxide the dispersion of organic matrix and with its compatibility problem, usual method is that it is carried out surface modification, carry out organic materials and inorganic materials compound effectively, bring into play both advantages, to reach the purpose of performance complement, raising material overall performance, weaken the polarity of silica sphere, solve silicon-dioxide combines difference with organic matrix problem.
Usually require polymer surfaces to have in inorganic particulate surface grafting polymerization thing and can supply the grafted group, reaction conditions is also comparatively harsh, is generally mass polymerization or aqueous solution polymerization, makes troubles to realization of industrialization.Usually the preparation of SiO 2 composite microsphere material mainly contains following three kinds, i.e. sol-gel method, layer assembly method, silicon dioxide gel and high polymer monomer mixing copolymerization process.But adopt the difficult particle that forms single type of sol-gel method synthetic composite microsphere material, and dispersiveness is not good; Layer assembly method preparation process complexity, the material structure of preparation is loose, and stability is not high; Silicon sol and high polymer monomer mixing copolymerization process, organic constituent and inorganic component are difficult to form the matrix material of structure-type.
Bai Hongying etc. [Bai Hongying, Jia Mengqiu, not big, Wang Jinling. nanometer SiO
2In-situ modified and application [J] in heat resisting coating. sufacing, 2003,32 (6): 59-62] adopt sol-gel method to prepare nanometer SiO
2, and with silane coupling agent as properties-correcting agent and organic phase, it is carried out in-situ modified, prepare inorganic organic composite granule.But this method use costs an arm and a leg and has certain toxic tetraethoxy to prepare SiO as inorganic sources
2
Sun Kang etc. [Sun Kang, Dou Hongjing, Zhang Pengfei, Li Wanwan. the preparation method of multifunctional macromolecule-inorganic composite microsphere [P]. publication number: CN101012312.] inorganic nano-particle is dispersed in the solvent, form inorganic nano-particle solution; Polymer microsphere is dispersed in the solvent, forms polymer microsphere solution; Again inorganic nano-particle solution is joined in the polymer microsphere solution, stir swelling under the room temperature; With the mixed solution centrifugation after the swelling or make solvent evaporates, through cleaning, drying, the macromolecule-inorganic composite microsphere that obtains.But the described solvent of this method is organic solvents such as methyl alcohol, normal hexane, dimethylbenzene, but also needs to clean 2～6 times with dehydrated alcohol.Environment is had certain pollution, and cost is higher.
Separate Xiao Ling etc. [separate the research [J] of .KH-550 modified manometer silicon dioxides such as Xiao Ling. Institutes Of Technology Of Taiyuan's journal, 2008,39 (1): 26-28.] adopt ethanol to make solvent, KH550 is a coupling agent, to sample nanometer SiO
2Modification is carried out on the surface.This method is made solvent with ethanol, and raw materials used silane coupling agent, nanometer SiO
2More expensive relatively etc. price, be not suitable for suitability for industrialized production.
Jiang Lizhong etc. [Jiang Lizhong, the good space of fighting, martial virtue treasure, Jin Riguang. methacryloxy Trimethoxy silane modification SiO
2Preparation [J]. Beijing University of Chemical Technology's journal, 2007,34 (3): 387-389.] adopt the original position single stage method to prepare the dispersed nano SiO of surperficial methacryloxypropyl trimethoxy silane modification
2Particle.The result shows, the MPS modified Nano SiO of original position single stage method preparation
2The about 75nm of particle diameter is monodisperse status basically, and contains a large amount of MPS functional groups, and its surface density is 3.45 μ mol/m
2But the selected raw material of this method is a tetraethyl silicate deleterious and that price is relatively costly, and the cycle is longer relatively.
Liu Liying etc. [Liu Liying, Wang Xiufeng, Wu Yanxia, Zhang Chuncao. the preparation of improved silica and photonic crystal self-assembly [J] thereof. silicate circular, 2008,27 (6): 1217-1220,1229]
Legal system is equipped with SiO
2Improve on the basis of microballoon, by adding a certain amount of metal Na, synthetic single SiO that disperses in ethanol medium
2Microballoon.But the used solvent of this method still is an organic solvent, and nonaqueous.
You Shuli etc. [You Shuli, Yu Zhiqiang, Yang Zhenguo. coupling agent is to nanometer SiO
2/ resin composite materials microstructure and Effect on Performance [J]. polymer material science and engineering, 2008,24 (10): 75-78.] KH550, KH560, KH570 are added respectively in the aqueous ethanolic solution, stir hydrolysis.With nanometer SiO
2Add in the solution for preparing.Ultra-sonic dispersion 10min under mechanical stirring, desolventizing, oven dry makes silane coupler modified SiO
2Sample.Silane coupling agent, the nanometer SiO of the same applied cost costliness of this method
2Deng, also need ultra-sonic dispersion, not too be suitable for suitability for industrialized production.
The patent of Degussa [Degussa. have the method for making [P] of high whiteness and ultralow hygroscopic hydrophobic precipitated silicas. publication number: CN1405239] method for preparing hydrophobic precipitated silicas is provided.The mixture for preparing organic methyl polysiloxane derivative and precipitated silica carries out oxidizing thermal treatment with oxidizing gas at 10-150 ℃ of modulated 0.5-72h with under fluid condition being higher than 300 ℃.Finally make hydrophobic precipitated silicas.This method equipment used complexity, and the production cycle is longer, and cost is high relatively.
[Hu Daodao such as Hu Daodao, Yang Juxiang, Fang Yu etc. the preparation method of surface patterned SiO 2 high molecular composite microsphere [P]. publication number CN 1864845A] by the mixed solution of preparation mixed surfactant, the synthetic template oil phase of preparation, preparation emulsion, preparation water, preparation copolymerization microgel, preparation swollen copolymerization microgel, the preparation positive silane of tetraethoxy and normal heptane, finally make the SiO 2 high molecular composite microsphere of patterned surface.Though this method reaction is to carry out at normal temperatures, processing step is more, and reaction process needs more organic solvent, needs alternately to wash complex microsphere with secondary water and acetone, also will wash 3-4 time with acetone at last again.So the cost of commercial scale production can be very high.
Summary of the invention
In view of the existing in prior technology shortcoming and defect, it is relatively low to the invention provides a kind of synthesis temperature, and preparation technology is simple, environmental protection, the surface band hydrophobic group that cost is low and the methyl polysiloxane/SiO of minor amount of silicon hydroxyl
2The preparation method of complex microsphere.
Methyl polysiloxane/SiO provided by the invention
2The preparation method's of complex microsphere ultimate principle is exactly under acidic conditions, and promptly pH generates orthosilicic acid (H in water glass and sodium methyl silicate mixing solutions in the scope of 1-3
4SiO
4) and methyl siliconic acid (CH
3Si (OH)
3).In stirring, heat-processed, four activity hydroxies of orthosilicic acid and three activity hydroxies self of methyl siliconic acid, and all can dewater between two kinds of material molecules, intermolecular polymerization caused, form a tridimensional network gradually, and then form methyl polysiloxane/SiO
2Particle is through ageing, filtration, drying, methyl polysiloxane/SiO
2Particle is understood further polymerization, is grown up, and finally forms methyl polysiloxane/SiO
2The complex microsphere powder.The lower pH that why will control in preparation process is to form gel in order to prevent to form huge network structure.In fact, low pH has the effect of stable colloid particulate.
Methyl polysiloxane/SiO of the present invention
2The preparation method of complex microsphere specifically may further comprise the steps:
(1) solution is blended in the whipping process the methyl siliconic acid sodium solution by sodium methyl silicate (solids content)/water glass (SiO
2Content) mass ratio is that 2.5～6.5: 1 ratio joins in the load weighted water glass solution, stirs 10-15 minute, adds deionized water then, and mixing solutions is diluted to SiO
2With sodium methyl silicate solid total content be 5-10wt%, continue to stir 10-15 minute, obtain mixing solutions;
(2) regulate pH value and in whipping process, mineral acid joined in the mixing solutions that step (1) obtains, reconcile the pH value, continue to stir 15-20 minute, at this moment the methyl siliconic acid that generates in the solution and silicic acid is crosslinked in whipping process, polymerization, growth to 1.0-3.0;
(3) place ageing the acidic mixed solution that step (2) obtains is placed ageing 2-10 hour in 60-90 ℃ of air;
(4) filter the solution will place after the ageing and filter, use deionized water wash, until detection less than SO
4 2-Or Cl
-
(5) product after drying will be filtered was dried 12 hours in 60-90 ℃ of air, promptly obtained 2-5 μ m methyl polysiloxane/SiO
2The complex microsphere powder.
Described mineral acid can be selected sulfuric acid or hydrochloric acid, and it should be noted that all needs before the use dilute by correct method, to avoid danger; Sulfuric acid is about 2M, and hydrochloric acid is about 4M for best.
Be used to detect SO described in the step (4)
4 2-Ionic can be selected barium chloride solution, and its concentration is 0.1g/ml; Be used to detect Cl
-Ionic can be selected silver nitrate solution, and its concentration is 0.025M.
Sodium methyl silicate described in the step (1) and water glass solution preferably adopt technical grade, and sodium methyl silicate also claims methyl silicon sodium alcoholate, the industrial 2# water-resisting agent that also claims of its aqueous solution, and water glass solution is a sodium silicate aqueous solution.
The composite granule that obtains with method provided by the present invention is implemented in the good distribution of organic phase by hydrophobic group, by the silicon hydroxyl realize and organic phase between strong interaction.
Methyl polysiloxane/SiO
2Complex microsphere had both had methyl polysiloxane and SiO
2The characteristic of bulk material has the characteristics of micro-sphere structure again, therefore studies methyl polysiloxane/SiO
2Complex microsphere not only has important scientific meaning, and has broad application prospects.
Methyl polysiloxane/SiO provided by the present invention
2The method of complex microsphere, SiO
2Be that mode with chemical bond combines between the methyl polysiloxane, be the crosslinked organic and inorganic complex microsphere of a kind of body, so it not only has the rigidity of inorganics, also have organic toughness.Because this complex microsphere surface hydrophobicity is so this spherical powder has good dispersiveness and flowability.This is easy to scatter from the electron microscopic observation of sample and can confirms.In addition, compare, on directly perceived, relatively have better flowability with traditional method of modifying.Therefore it can be widely used in fields such as rubber plastic industry, makeup, paint, printing ink, optical articles.Water glass that this invention is used and methyl siliconic acid sodium solution are common industrialization raw materials, and the raw material cheapness is easily purchased, and this technology is simple, quick, cost is low, process is easy to control, applicable to industrial-scale production.
Description of drawings
The present invention has accompanying drawing 1 width of cloth.
Fig. 1 is the methyl polysiloxane/SiO that adopts the embodiment of the invention 1 preparation
2The electron scanning micrograph of complex microsphere.
Embodiment
Embodiment 1
Take by weighing water glass solution and (contain 26wt%SiO
2Modulus 3.1-3.4, sodium oxide 8.2, Dalian dying company limited) 10.16g pours in the 150ml beaker, and magnetic agitation takes by weighing methyl siliconic acid sodium solution (solid content 25wt% again, the production of Jinan, Shandong company limited of state nation) 30.14g joins in the above-mentioned water glass solution fast, at room temperature stir 10min, get the 100g deionized water with graduated cylinder again and join in the mixing solutions, make mixing solutions be diluted to SiO
2Be about 7wt% with sodium methyl silicate solid total content, continue to stir 10min.Take by weighing 4M hydrochloric acid 38.52g again, join fast in the mixing solutions after the dilution, surveying the pH value is about 1.5, after continuing to stir 10min, takes out stirrer, beaker is put in 63 ℃ of Constant Temp. Ovens, take out after 10 hours, pour out supernatant liquid, filtration, deionization washing five times, with the check of 0.025M silver nitrate solution, no white precipitate.Take out throw out and be placed on the watch-glass, be placed in 63 ℃ the Constant Temp. Oven dry 10 hours, obtain a kind of white, dispersiveness, good fluidity, particle diameter is at methyl polysiloxane/SiO of 2-5 μ m
2The complex microsphere powder.Its microstructure as shown in Figure 1.
Embodiment 2
Take by weighing water glass solution and (contain 26wt%SiO
2Modulus 3.1-3.4, sodium oxide 8.2, Dalian dying company limited) 107.2g pours in the 2000ml beaker, and electronic stirring takes by weighing methyl siliconic acid sodium solution (solid content 25wt% again, the production of Jinan, Shandong company limited of state nation) 303.2g joins in the above-mentioned water glass solution fast, at room temperature stir 15min, get the 1000g deionized water with graduated cylinder again and join in the mixing solutions, make mixing solutions be diluted to SiO
2Be about 7wt% with sodium methyl silicate solid total content, continue to stir 10min.Take by weighing 4M hydrochloric acid 386.5g again, join fast in the mixing solutions after the dilution, surveying the pH value is about 1.2, after continuing to stir 10min, takes out stirrer, beaker is put in 65 ℃ of Constant Temp. Ovens, take out after 6 hours, pour out supernatant liquid, filtration, deionization washing six times, with the check of 0.025M silver nitrate solution, no white precipitate.Take out throw out and be placed on the watch-glass, be placed in 60 ℃ the Constant Temp. Oven dry 10 hours, obtain a kind of white, dispersiveness, good fluidity, particle diameter is at methyl polysiloxane/SiO of 1-3 μ m
2The complex microsphere powder.
Embodiment 3
Take by weighing water glass solution and (contain 26wt%SiO
2Modulus 3.1-3.4, sodium oxide 8.2, Dalian dying company limited) 10.72g pours in the 150ml beaker, and magnetic agitation takes by weighing methyl siliconic acid sodium solution (solid content 25wt% again, the production of Jinan, Shandong company limited of state nation) 30.32g joins in the above-mentioned water glass solution fast, at room temperature stir 15min, get the 100g deionized water with graduated cylinder again and join in the mixing solutions, make mixing solutions be diluted to SiO
2Be about 7wt% with sodium methyl silicate solid total content, continue to stir 10min.Take by weighing 2M sulfuric acid 34g again, join fast in the mixing solutions after the dilution, surveying the pH value is about 2.5, after continuing to stir 10min, takes out stirrer, beaker is put in 66 ℃ of Constant Temp. Ovens, take out after 10 hours, pour out supernatant liquid, filtration, deionization washing five times, with the check of 0.1g/ml barium chloride solution, no white precipitate.Take out throw out and be placed on the watch-glass, be placed in 60 ℃ the Constant Temp. Oven dry 10 hours, obtain a kind of white, dispersiveness, good fluidity, particle diameter is at methyl polysiloxane/SiO of 1.5-4 μ m
2The complex microsphere powder.
Embodiment 4
Take by weighing water glass solution and (contain 26wt%SiO
2Modulus 3.1-3.4, sodium oxide 8.2, Dalian dying company limited) 20.12g pours in the 500ml beaker, and magnetic agitation takes by weighing methyl siliconic acid sodium solution (solid content 25wt% again, the production of Jinan, Shandong company limited of state nation) 80.22g joins in the above-mentioned water glass solution fast, at room temperature stir 10min, get the 250g deionized water with graduated cylinder again and join in the mixing solutions, make mixing solutions be diluted to SiO
2Be about 7wt% with sodium methyl silicate solid total content, continue to stir 15min.Take by weighing 4M hydrochloric acid 101.14g again, join fast in the mixing solutions after the dilution, surveying the pH value is 1.1, after continuing to stir 10min, takes out stirrer, beaker is put in 66 ℃ of Constant Temp. Ovens, take out after 10 hours, pour out supernatant liquid, filtration, deionization washing five times, with the check of 0.025M silver nitrate solution, no white precipitate.Take out throw out and be placed on the watch-glass, be placed in 90 ℃ the Constant Temp. Oven dry 6 hours, obtain a kind of white, dispersiveness, good fluidity, particle diameter is at methyl polysiloxane/SiO of 1.5-3.0 μ m
2The complex microsphere powder.
Embodiment 5
Take by weighing water glass solution and (contain 26wt%SiO
2Modulus 3.1-3.4, sodium oxide 8.2, Dalian dying company limited) 10.22g pours in the 250ml beaker, and magnetic agitation takes by weighing methyl siliconic acid sodium solution (solid content 25wt% again, the production of Jinan, Shandong company limited of state nation) 30.68g joins in the above-mentioned water glass solution fast, at room temperature stir 10min, get the 160g deionized water with graduated cylinder again and join in the mixing solutions, make mixing solutions be diluted to SiO
2Be about 5wt% with sodium methyl silicate solid total content, continue to stir 10min.Take by weighing 4M hydrochloric acid 34.75g again, join fast in the mixing solutions after the dilution, surveying the pH value is 2.5, after continuing to stir 10min, takes out stirrer, beaker is put in 65 ℃ of Constant Temp. Ovens, take out after 10 hours, pour out supernatant liquid, filtration, deionization washing five times, with the check of 0.025M silver nitrate solution, no white precipitate.Take out throw out and be placed on the watch-glass, be placed in 70 ℃ the Constant Temp. Oven dry 10 hours, obtain a kind of white, dispersiveness, good fluidity, particle diameter is at methyl polysiloxane/SiO of 1.0-3.0 μ m
2The complex microsphere powder.
Claims (4)
1. methyl polysiloxane/SiO
2The preparation method of complex microsphere may further comprise the steps:
(1) solution is blended in the whipping process the methyl siliconic acid sodium solution by sodium methyl silicate (solids content)/water glass (SiO
2Content) mass ratio is that 2.5～6.5: 1 ratio joins in the load weighted water glass solution, stirs 10-15 minute, adds deionized water then, and mixing solutions is diluted to SiO
2With sodium methyl silicate solid total content be 5-10wt%, continue to stir 10-15 minute, obtain mixing solutions;
(2) regulate the pH value and in whipping process, mineral acid is joined in the mixing solutions of step (1) acquisition, reconcile the pH value, continue to stir 15-20 minute to 1.0-3.0;
(3) place ageing the acidic mixed solution that step (2) obtains is placed ageing 2-10 hour in 60-90 ℃ of air;
(4) filter the solution will place after the ageing and filter, use deionized water wash, until detection less than SO
4 2-Or Cl
-
(5) product after drying will be filtered was dried 12 hours in 60-90 ℃ of air, promptly obtained 2-5 μ m methyl polysiloxane/SiO
2The complex microsphere powder.
2. methyl polysiloxane/SiO according to claim 1
2The preparation method of complex microsphere is characterized in that the mineral acid described in the step (3) is sulfuric acid or hydrochloric acid, all needs before the use to dilute by correct method, and sulfuric acid is about 2M, and hydrochloric acid is about 4M.
3. methyl polysiloxane/SiO according to claim 1
2The preparation method of complex microsphere is characterized in that being used to detect SO described in the step (4)
4 2-Ionic is a barium chloride solution, and its concentration is 0.1g/ml; Be used to detect Cl
-Ionic silver nitrate solution, its concentration are 0.025M.
4. a kind of methyl polysiloxane/SiO according to claim 1
2The preparation method of complex microsphere is characterized in that sodium methyl silicate and the water glass solution described in the step (1) is technical grade, and sodium methyl silicate also claims methyl silicon sodium alcoholate, the industrial 2# water-resisting agent that also claims of its aqueous solution, and water glass solution is a sodium silicate aqueous solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674231A (en) * | 2017-10-20 | 2018-02-09 | 南京工程学院 | A kind of hydrophobic oleophobic high molecular composite microsphere and preparation method thereof |
| CN111618963A (en) * | 2020-05-24 | 2020-09-04 | 安信伟光(上海)木材有限公司 | Production process of water-based inorganic modification liquid for solid wood geothermal floor |
| CN115851046A (en) * | 2023-03-01 | 2023-03-28 | 青州金昊新材料有限公司 | Paper-plastic model waterproof agent and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050000388A1 (en) * | 2001-11-15 | 2005-01-06 | Cho Kyu-Ii | Preparation method of solvent-free water-dispersible hydroxypropyl methly cellulose phthalate nanoparticle |
| CN101559951A (en) * | 2009-05-15 | 2009-10-21 | 江苏大学 | Method for preparing nanoscale silica hollow microspheres |
-
2010
- 2010-05-22 CN CN2010101863452A patent/CN101864083B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050000388A1 (en) * | 2001-11-15 | 2005-01-06 | Cho Kyu-Ii | Preparation method of solvent-free water-dispersible hydroxypropyl methly cellulose phthalate nanoparticle |
| CN101559951A (en) * | 2009-05-15 | 2009-10-21 | 江苏大学 | Method for preparing nanoscale silica hollow microspheres |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674231A (en) * | 2017-10-20 | 2018-02-09 | 南京工程学院 | A kind of hydrophobic oleophobic high molecular composite microsphere and preparation method thereof |
| CN107674231B (en) * | 2017-10-20 | 2021-04-20 | 南京工程学院 | Hydrophobic and oleophobic polymer composite microsphere and preparation method thereof |
| CN111618963A (en) * | 2020-05-24 | 2020-09-04 | 安信伟光(上海)木材有限公司 | Production process of water-based inorganic modification liquid for solid wood geothermal floor |
| CN115851046A (en) * | 2023-03-01 | 2023-03-28 | 青州金昊新材料有限公司 | Paper-plastic model waterproof agent and preparation method and application thereof |
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