CN104860320A - Method for preparing modified nanosilicon dioxide - Google Patents
Method for preparing modified nanosilicon dioxide Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
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- 239000000377 silicon dioxide Substances 0.000 claims description 24
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- -1 polyoxyethylene Polymers 0.000 claims description 11
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 abstract 1
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Abstract
The invention provides a method for preparing modified nanosilicon dioxide. Firstly, nanosilicon dioxide is reunited as little as possible by adding chitosan during the nucleation process, thereby obtaining modified nanosilicon dioxide which is uniform, steady and excellent in dispersivity. Secondly, ethylene diamine tetraacetic acid and the nanosilicon dioxide react to enable the surface of the ethylene diamine tetraacetic acid to modify a certain amount of amino. Thirdly, silanol and aminosilylation are arranged on the outer layer of the nanosilicon dioxide, added stannous chloride enables the silanol and the aminosilylation to have excellent activities to epoxy groups, speeds up reaction progress, and greatly improves modified grafting ratio of surface of the nanosilicon dioxide.
Description
Technical field
The present invention relates to technical field of nano material, particularly relate to a kind of preparation method of modified manometer silicon dioxide.
Background technology
Nano silicon is unformed white powder, nontoxic, tasteless, pollution-free, is the non-metallic material that a kind of surface exists hydroxyl and planar water.The molecule of nano silicon is three-dimensional chain-like structure, have the advantages that particle diameter is little, density is low, specific surface area is large, there is superior stability, thickening property, extinction, anti-stickiness, reinforcing, thixotropy and excellent optics and mechanical property, be widely used in the fields such as pottery, rubber, plastics, electronic package material, anti-biotic material, coating, pigment and support of the catalyst.Due to the performance of material and the particle size of material and pattern closely related, many performances only the particle size of material and shape even time can macroscopically show, therefore control size and the pattern of material granule, the single dispersing material that preparation has a uniform-dimension Sum fanction pattern is the study hotspot in present material science.
At present, the preparation technology of nano silicon is divided into dry method and the large class of wet method two, and wherein, dry method mainly refers to vapor phase process, and warm therapy comprises chemical precipitation method, sol-gel method, hydrothermal method and microemulsion method.Vapor phase process is generally raw material with silicon tetrachloride, is hydrolyzed by silicon tetrachloride gas, prepares nano silicon under hydrogen, Oxygen Flow high temperature.This method can prepare that purity is high, surface hydroxyl is few, reinforcing good nano silicon, but energy consumption is large in process of production, and expensive starting materials is also higher to the requirement of equipment.
Chemical precipitation method is that silicate is obtained silica crystals that is loose, that be precipitated out with flocculent structure by acidifying.The method Production Flow Chart is simple, and energy consumption is low, but the aperture shape of wayward particle, and pore size distribution is also very wide, uneven, poor activity.Sol-gel method be with inorganic salt or metal alkoxide for precursor, through the gel gradually of hydrolytie polycondensation process, obtain nano silicon.The method is easy to operate, but cost is higher, easily causes environmental pollution, is unfavorable for industrialization.Preparing Nano-Materials in Microemulsions has the feature of processing ease, but microemulsion method is vulnerable to the impact of the factors such as test conditions in the process preparing nano silicon, and the dispersiveness of the nano silicon obtained is poor.
Summary of the invention
The technical problem that the present invention solves is the preparation method providing a kind of modified manometer silicon dioxide, and the modified manometer silicon dioxide obtained is homogeneous, stable, good dispersity.
In view of this, the invention provides a kind of preparation method of modified manometer silicon dioxide, comprise the following steps: hexanaphthene, styroyl phenol polyoxyethylene polyoxypropylene ether, n-hexyl alcohol and Unigly GO 102S a) mix by step, obtain microemulsion system after stirring; Step b) in described microemulsion system, add deionized water, 1-2 mass parts chitosan and 2-6 mass parts tetraethoxy successively, stir, dropwise drip ammoniacal liquor, add disodium ethylene diamine tetraacetate, acetone is added after stirring, then add 1,2 propylene glycol and deionized water wash, and obtain nano silicon; Step c) nano silicon that 2-8 mass parts step b obtains is added in deionized water and alcohol mixed solution, the polyoxyethylene glycol of 5-8 mass parts is added after stirring, continue to stir, drip the methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane of 1-2 mass parts, after reaction, obtain mixing solutions; Steps d) add the tindichloride of 1-2 mass parts in the mixing solutions that obtains to step c, add the glytidyl methacrylate of 5-10 mass parts after stirring, after reaction, obtain modified manometer silicon dioxide.
Preferably, step a) in, described hexanaphthene is 100-120 mass parts, and described styroyl phenol polyoxyethylene polyoxypropylene ether is 10-20 mass parts.
Preferably, step a) in, described n-hexyl alcohol is 20-30 mass parts.
Preferably, step a) in, described Unigly GO 102S is 10-15 mass parts.
Preferably, step churning time a) is 10-15 minute.
Preferably, step b) in, described ammoniacal liquor is 1-3 mass parts.
Preferably, step b) in, disodium ethylene diamine tetraacetate is 1-2 mass parts.
Preferably, step b) in, described acetone is 50-80 mass parts.
Preferably, step b) in, 1,2 propylene glycol are 5-10 mass parts.
Preferably, step c) in, described deionized water is 100 mass parts, and ethanol is 200 mass parts.
The invention provides a kind of preparation method of modified manometer silicon dioxide, hexanaphthene, styroyl phenol polyoxyethylene polyoxypropylene ether, n-hexyl alcohol and Unigly GO 102S are mixed, after stirring, obtains microemulsion system; Add deionized water, chitosan and tetraethoxy successively, stir, dropwise drip ammoniacal liquor, add disodium ethylene diamine tetraacetate, add acetone after stirring, washing, obtains nano silicon; The nano silicon obtained is added in deionized water and alcohol mixed solution, polyoxyethylene glycol is added after stirring, drip methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane, reaction, add tindichloride, add glytidyl methacrylate after stirring, after reaction, obtain modified manometer silicon dioxide.
Compared with prior art, first, the present invention adds chitosan makes the reunion that nano silicon is as far as possible few in nucleation process, thus the modified manometer silicon dioxide obtained is homogeneous, stable, good dispersity.And in chitosan macromole, having active hydroxyl and amino, they have stronger chemical reaction ability, and the hydroxyl under the condition of alkalescence on C-6 is more active.The hydroxyl of chitosan self can be adsorbed onto the surface just forming nano silicon Si-OH, and himself abundant amino can promote accelerating of reaction.Second, disodium ethylene diamine tetraacetate and nanometer titanium dioxide pasc reaction make a certain amount of amino of its finishing, and disodium ethylene diamine tetraacetate inherently a kind of stablizer and Synergist S-421 95, when it makes ammoniacal liquor drip, Hydrolysis of Ethyl Silicate is stablized, and the nano silicon therefore produced is relatively homogeneous, stable.3rd, nanometer titanium dioxide outer silicon has silanol and silicon is amino, and the tindichloride added makes silanol and silicon amino have very high activity to epoxy group(ing), accelerates the process of reaction, makes the percentage of grafting of surface modification of silica greatly improve simultaneously.4th, nano silicon is by after glytidyl methacrylate modification, and its hydrophobicity of surface enhanced outside, makes it can be dispersed in redispersion liquid, and lasting stability, not easily reunites.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of modified manometer silicon dioxide prepared by the embodiment of the present invention 1.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of preparation method of modified manometer silicon dioxide, comprise the following steps: hexanaphthene, styroyl phenol polyoxyethylene polyoxypropylene ether, n-hexyl alcohol and Unigly GO 102S a) mix by step, obtain microemulsion system after stirring; Step b) in described microemulsion system, add deionized water, 1-2 mass parts chitosan and 2-6 mass parts tetraethoxy successively, stir, dropwise drip ammoniacal liquor, add disodium ethylene diamine tetraacetate, acetone is added after stirring, then add 1,2 propylene glycol and deionized water wash, and obtain nano silicon; Step c) nano silicon that 2-8 mass parts step b obtains is added in deionized water and alcohol mixed solution, the polyoxyethylene glycol of 5-8 mass parts is added after stirring, continue to stir, drip the methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane of 1-2 mass parts, after reaction, obtain mixing solutions; Steps d) add the tindichloride of 1-2 mass parts in the mixing solutions that obtains to step c, add the glytidyl methacrylate of 5-10 mass parts after stirring, after reaction, obtain modified manometer silicon dioxide.
Step a) in, described styroyl phenol polyoxyethylene polyoxypropylene ether is tensio-active agent, as emulsifying agent in body series.Described Unigly GO 102S is cosurfactant, is a kind of long chain fatty acid ester.
Preferably, described hexanaphthene is preferably 100-120 mass parts, is more preferably 105-115 mass parts; Described styroyl phenol polyoxyethylene polyoxypropylene ether is preferably 10-20 mass parts, is more preferably 12-16 mass parts; Described n-hexyl alcohol is preferably 20-30 mass parts, is more preferably 23-27 mass parts; Described Unigly GO 102S is preferably 10-15 mass parts, is more preferably 11-14 mass parts.Step churning time a) is preferably 10-15 minute, is more preferably 11-14 minute.
Step b) in, add deionized water in described microemulsion system after, preferably stir 10-20 minute, be more preferably 12-18 minute.In this step, the churning time added after 1-2 mass parts chitosan and 2-6 mass parts tetraethoxy is preferably 5-10 minute, is more preferably 6-8 minute; Add the churning time after disodium ethylene diamine tetraacetate and be preferably 1-2 hour.
According to the present invention, containing active hydroxyl and amino in described chitosan macromole, it has stronger chemical reaction ability, and the hydroxyl under the condition of alkalescence on C-6 is more active.The hydroxyl of chitosan self can be adsorbed onto the surface just forming nano silicon Si-OH, and himself abundant amino can promote accelerating of reaction.Therefore, in the process of silicon-dioxide nucleation, chitosan is assembled collection and form protective layer around it, makes the nano silicon of formation more even and good dispersity.
Disodium ethylene diamine tetraacetate is a kind of stablizer and Synergist S-421 95, and it can react with silica sphere concentration Si-OH with two carboxyls, thus in the process of nano silicon nucleation, modify a certain amount of amino group.And disodium ethylene diamine tetraacetate inherently a kind of stablizer and Synergist S-421 95, when it makes ammoniacal liquor drip, Hydrolysis of Ethyl Silicate is stablized, and the nano silicon therefore produced is relatively homogeneous, stable.
In the process of above-mentioned acetone breakdown of emulsion, have some nano silicons and reunite, in order to anti-phenomenon here, after breakdown of emulsion, can add 1,2 propylene glycol carry out supersound process.
Preferably, step b) in, described ammoniacal liquor is preferably 1-3 mass parts, is more preferably 2-3 mass parts; Disodium ethylene diamine tetraacetate is preferably 1-2 mass parts; Described acetone is preferably 50-80 mass parts, is more preferably 60-75 mass parts, is more preferably 60-70 mass parts; 1,2 propylene glycol are preferably 5-10 mass parts, are more preferably 6-9 mass parts.
Step c) in, described polyoxyethylene glycol makes whole system viscosity increase, and nano silicon good dispersity, stability is high.Described methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane is made silane coupling agent and can be modified nano-silica surface, and the unsaturated link(age) in above-mentioned silane coupling agent can carry out graft reaction with the ester group of glytidyl methacrylate.
Preferably, described step c is specially: be added in deionized water and alcohol mixed solution by the nano silicon that 2-8 mass parts step b obtains, stir 5-10 minute, add the polyoxyethylene glycol of 5-8 mass parts, continue stirring 10 minutes, drip the methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane of 1-2 mass parts, reaction 10-30 minute, obtains mixing solutions.Step c) in, described deionized water is preferably 100 mass parts, and ethanol is preferably 200 mass parts.
Steps d) in, described tindichloride is equivalent to a kind of promoting catalyst, makes silanol and silicon amino have very high activity to epoxy group(ing), adds the process of fast response, also allow the percentage of grafting of its surface modification greatly improve simultaneously.
Preferably, described steps d) be specially: the tindichloride adding 1-2 mass parts in the mixing solutions that step c obtains, stir 5-8 minute, add the glytidyl methacrylate of 5-10 mass parts, react and obtain modified manometer silicon dioxide after 30-40 minute.
Nano silicon is by after glytidyl methacrylate modification, and its hydrophobicity of surface enhanced outside, makes it can be dispersed in redispersion liquid, and lasting stability, not easily reunites.
Preferably, after obtaining modified manometer silicon dioxide, preferably to modified manometer silicon dioxide centrifuge washing repeatedly.
As can be seen from above scheme, first the present invention prepares nano silicon, by the improvement to classical microemulsion method, makes preparation process highly stable; Then modification is carried out to the nano silicon of preparation, obtain modified manometer silicon dioxide.
The present invention has following features:
1 the present invention adds chitosan makes nano silicon in nucleation process, homogeneous, stable, good dispersity.
2, the disodium ethylene diamine tetraacetate added and nanometer titanium dioxide pasc reaction thus make a certain amount of amino of its finishing.
3, nanometer titanium dioxide outer silicon has silanol and silicon amino, and tindichloride has very high activity to the epoxy group(ing) of these two kinds of groups to glytidyl methacrylate, methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane is made silane coupling agent and is also had undersaturated C=O and C=C key and can carry out graft reaction with glytidyl methacrylate.
4, nano silicon is by after glytidyl methacrylate modification, outside its hydrophobicity of surface enhanced, makes it can be dispersed in redispersion liquid, and lasting stability, not easily reunites.
In order to understand the present invention further, be described in detail to technical scheme provided by the invention below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Tetraethoxy (analytical pure) in embodiment is from Chemical Reagent Co., Ltd., Sinopharm Group;
Ethyl phenol polyoxyethylene polyoxypropylene ether in embodiment is No. 12, emulsifying agent, from chemical plant, Lvshun;
Unigly GO 102S in embodiment is cosurfactant, model
oLEIQUE CC 497 is from good method lion (Shanghai) trade Co., Ltd;
Chitosan in embodiment is from Chemical Reagent Co., Ltd., Sinopharm Group;
Methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane in embodiment makes silane coupling agent from leaf organosilicon of speeding;
Glytidyl methacrylate in embodiment is from the happy Industrial Co., Ltd. of Shanghai Jin Jin;
Tindichloride in embodiment is from Weihui City Ya Xing Chemical Co., Ltd.;
Polyoxyethylene glycol model in embodiment can be PEG200 or PEG400, from Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1
The invention provides a kind of preparation method of nano silicon, comprise the steps:
1. the styroyl phenol polyoxyethylene polyoxypropylene ether of the hexanaphthene of 120 mass parts, 20 mass parts, the n-hexyl alcohol of 20 mass parts, the Unigly GO 102S of 12 mass parts are mixed, stir 15 minutes, in microemulsion system.
2. add the deionized water of 5 mass parts, stir 10 minutes.
3. add the chitosan of 1 mass parts and the tetraethoxy of 56 mass parts, stir 10 minutes.
4. dropwise drip the ammoniacal liquor of 3 mass parts, the disodium ethylene diamine tetraacetate adding 1 mass parts at room temperature stirs 1-2 hour.
5. the acetone breakdown of emulsion adding 80 mass parts makes nanometer ball be precipitated out, and adds 1 of 5 mass parts, and 2 propylene glycol carry out supersound process.Then a certain amount of deionized water and ethanol centrifuge washing several is repeatedly added.
6. the above-mentioned nano silicon of 5 mass parts is joined in the deionized water of 100 mass parts and the alcohol mixed solution of 200 mass parts and go, fully stir 10 minutes, add the polyoxyethylene glycol of 8 mass parts, continue stirring 10 minutes.
7. under mechanical agitation, the methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane of 2 mass parts is dropwise joined in above-mentioned solution and goes, fully reaction 20 minutes.
8. the tindichloride of 1 mass parts is joined in above-mentioned solution and go, fully stir 8 minutes, then the glytidyl methacrylate of 6 mass parts is added in above-mentioned solution, stir 30 minutes.
9. by with the nano silicon centrifuge washing of methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane and glytidyl methacrylate modification repeatedly.
Fig. 1 is the transmission electron microscope picture of modified manometer silicon dioxide prepared by the present embodiment.
Embodiment 2
1. the styroyl phenol polyoxyethylene polyoxypropylene ether of the hexanaphthene of 100 mass parts, 12 mass parts, the n-hexyl alcohol of 25 mass parts, the Unigly GO 102S of 10 mass parts are mixed, stir 15 minutes, in microemulsion system.
2. add the deionized water of 3 mass parts, stir 18 minutes.
3. add the chitosan of 1 mass parts and the tetraethoxy of 6 mass parts, stir 6 minutes.
4. dropwise drip the ammoniacal liquor of 2 mass parts, the disodium ethylene diamine tetraacetate adding 1 mass parts at room temperature stirs 1 hour.
5. the acetone breakdown of emulsion adding 60 mass parts makes nanometer ball be precipitated out, and adds 1 of 10 mass parts, and 2 propylene glycol carry out supersound process.Then a certain amount of deionized water and ethanol centrifuge washing several is repeatedly added.
6. the above-mentioned nano silicon of 2-8 mass parts is joined in the deionized water of 100 mass parts and the alcohol mixed solution of 200 mass parts and go, fully stir 8 minutes, add the polyoxyethylene glycol of 6 mass parts, continue stirring 10 minutes.
7. under mechanical agitation, the methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane of 1 mass parts is dropwise joined in above-mentioned solution and goes, fully reaction 30 minutes.
8. the tindichloride of 1.5 mass parts is joined in above-mentioned solution and go, fully stir 8 minutes, then the glytidyl methacrylate of 6 mass parts is added in above-mentioned solution, stir 30 minutes.
9. by with the nano silicon centrifuge washing of methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane and glytidyl methacrylate modification repeatedly.
Embodiment 3
1. the styroyl phenol polyoxyethylene polyoxypropylene ether of the hexanaphthene of 100 mass parts, 10 mass parts, the n-hexyl alcohol of 20 mass parts, the Unigly GO 102S of 10 mass parts are mixed, stir 15 minutes, in microemulsion system.
2. add the deionized water of 4 mass parts, stir 20 minutes.
3. add the chitosan of 2 mass parts and the tetraethoxy of 6 mass parts, stir 8 minutes.
4. dropwise drip the ammoniacal liquor of 2 mass parts, the disodium ethylene diamine tetraacetate adding 1 mass parts at room temperature stirs 2 hours.
5. the acetone breakdown of emulsion adding 60 mass parts makes nanometer ball be precipitated out, and adds 1 of 5 mass parts, and 2 propylene glycol carry out supersound process.Then a certain amount of deionized water and ethanol centrifuge washing several is repeatedly added.
6. the above-mentioned nano silicon of 8 mass parts is joined in the deionized water of 100 mass parts and the alcohol mixed solution of 200 mass parts and go, fully stir 10 minutes, add the polyoxyethylene glycol of 5 mass parts, continue stirring 10 minutes.
7. under mechanical agitation, the methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane of 2 mass parts is dropwise joined in above-mentioned solution and goes, fully reaction 10-30 minute.
8. the tindichloride of 2 mass parts is joined in above-mentioned solution and go, fully stir 5 minutes, then the glytidyl methacrylate of 6 mass parts is added in above-mentioned solution, stir 35 minutes.
9. by with the nano silicon centrifuge washing of methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane and glytidyl methacrylate modification repeatedly.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a preparation method for modified manometer silicon dioxide, is characterized in that, comprises the following steps:
Hexanaphthene, styroyl phenol polyoxyethylene polyoxypropylene ether, n-hexyl alcohol and Unigly GO 102S a) mix by step, obtain microemulsion system after stirring;
Step b) in described microemulsion system, add deionized water, 1-2 mass parts chitosan and 2-6 mass parts tetraethoxy successively, stir, dropwise drip ammoniacal liquor, add disodium ethylene diamine tetraacetate, acetone is added after stirring, then add 1,2 propylene glycol and deionized water wash, and obtain nano silicon;
Step c) nano silicon that 2-8 mass parts step b obtains is added in deionized water and alcohol mixed solution, the polyoxyethylene glycol of 5-8 mass parts is added after stirring, continue to stir, drip the methacrylic acid oxidase hydroxypropyl methyl dimethoxysilane of 1-2 mass parts, after reaction, obtain mixing solutions;
Steps d) add the tindichloride of 1-2 mass parts in the mixing solutions that obtains to step c, add the glytidyl methacrylate of 5-10 mass parts after stirring, after reaction, obtain modified manometer silicon dioxide.
2. preparation method according to claim 1, is characterized in that, step a) in, described hexanaphthene is 100-120 mass parts, and described styroyl phenol polyoxyethylene polyoxypropylene ether is 10-20 mass parts.
3. preparation method according to claim 1, is characterized in that, step a) in, described n-hexyl alcohol is 20-30 mass parts.
4. preparation method according to claim 1, is characterized in that, step a) in, described Unigly GO 102S is 10-15 mass parts.
5. preparation method according to claim 1, is characterized in that, step churning time a) is 10-15 minute.
6. preparation method according to claim 1, is characterized in that, step b) in, described ammoniacal liquor is 1-3 mass parts.
7. the preparation method according to claim 1 ~ 6 any one, is characterized in that, step b) in, disodium ethylene diamine tetraacetate is 1-2 mass parts.
8. the preparation method according to claim 1 ~ 6 any one, is characterized in that, step b) in, described acetone is 50-80 mass parts.
9. the preparation method according to claim 1 ~ 6 any one, is characterized in that, step b) in, 1,2 propylene glycol are 5-10 mass parts.
10. the preparation method according to claim 1 ~ 6 any one, is characterized in that, step c) in, described deionized water is 100 mass parts, and ethanol is 200 mass parts.
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