CN101249963A - Method for preparing super-hydrophobic silica by one-step process - Google Patents
Method for preparing super-hydrophobic silica by one-step process Download PDFInfo
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- CN101249963A CN101249963A CNA2008100204639A CN200810020463A CN101249963A CN 101249963 A CN101249963 A CN 101249963A CN A2008100204639 A CNA2008100204639 A CN A2008100204639A CN 200810020463 A CN200810020463 A CN 200810020463A CN 101249963 A CN101249963 A CN 101249963A
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- Prior art keywords
- silica
- step process
- silicon dioxide
- hydrophobic silica
- preparing super
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical group CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000012074 organic phase Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- -1 polyoxy Polymers 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention discloses a process for preparing super hydrophobic silicon dioxide by the one-step method, the process of preparation is simple in technique, mild in reaction conditions and low in preparation cost. The prepared silicon dioxide has a water contact angle up to 155.1 degrees, which can effectively prevent secondary agglomeration on the surface of the silicon dioxide, thereby improving the interfacial compatibility of inorganic phase and organic phase and strengthening the combination force between the silicon dioxide and polymer. The method comprises steps of (A) dispersing, mixing the silicon dioxide solid powder and dissolvent at normal temperature and adding to a reactor after being uniformly dispersed, (B) reaction, heating the reactor to 60-100DEG C, adding in treating agent, continuing stirring to react for 20-40 minutes, then heating to 100-140 DEG C and flowing back for 3-6 hours to enable the surface of the silicon dioxide to be extra hydrophobic, (C) dispersing and drying, washing by using the dissolvent and filtering the super hydrophobic silicon dioxide, removing the dissolvent and residual reactant and vacuum-drying.
Description
Technical field
The present invention relates to a kind of preparation method of silicon-dioxide, more specifically to a kind of method of preparing super-hydrophobic silica by one-step process.
Background technology
Nano silicon is a kind of lightweight nano-porous materials, and it has, and specific surface area is big, the hole is rate height, dimensional effect and special light, electric rerum natura, with and at high temperature still have unusual characteristics such as high-strength, high-ductility, good stability.Therefore nano silicon has broad application prospects, and is obtaining application aspect coating, plastics and Rubber processing and support of the catalyst, the medical development at present.But there is hydroxyl in nano-silica surface, easily forms adsorption by hydrogen bond when meeting water molecules, makes its surperficial possess hydrophilic property, thereby causes its reunion, and difficult the dispersion, this has influenced the application of nano silicon in some field to a great extent.Therefore, by the surface-treated method, the hydroxyl value of elimination or minimizing silica sphere is the key of dealing with problems.
At present, to become hydrophobic report a lot of by hydrophilic to make silica sphere by heat treating process and chemic modified method.For example: among DE 2628975 and the DE 2729244, respectively silicone oil and dimethyldichlorosilane(DMCS) are added in the precipitated silica, carry out hydrophobization with wet method and dry method and handle, through 200 to 400 ℃ of high-temperature annealing step, prepared water drain silica at last; Among the JP194765,, make its surface reach hydrophobic state with disilazane compound treatment silicon dioxide gel; Among the CN 1161997, adopt the surface grafting method, polyoxy alkane is grafted to silica sphere, thereby makes it reach hydrophobic property.But by the method for surface modification, it is but very rare to make silica sphere reach the report of super-hydrophobic state.
Summary of the invention
The objective of the invention is to solve deficiency and the problem that above-mentioned prior art exists, a kind of method of preparing super-hydrophobic silica by one-step process is provided.
The present invention is achieved by the following technical solutions:
The method of preparing super-hydrophobic silica by one-step process provided by the invention mainly may further comprise the steps:
(A) disperse: under the normal temperature, will add reactor behind silica solid powder and solvent and the homodisperse;
(B) reaction: reactor is risen to 60～100 ℃, add treatment agent, after continuing stirring and reacting 20～40 minutes, make 100～140 ℃ of temperature liters and reflux to make silica sphere reach super-hydrophobic in 3～6 hours;
(C) separate, drying: with solvent wash and filter above-mentioned super-hydrophobic silica, remove solvent and remaining reactants and vacuum-drying.
Employed treatment agent among the present invention, its chemical molecular formula are R
4-mSi (OR)
m, wherein R is methyl, ethyl or many carbon alkyl group, m is 1,2 or 3, and the consumption of treatment agent is 0.5 to 5 times of silica weight.
In addition, employed SiO 2 powder is preferably the precipitator method or fumed silica among the present invention; Solvent is preferably toluene, dimethylbenzene, N, one or more in dinethylformamide, hexanaphthene, the methylene dichloride, and consumption is 10 to 50 times of silica weight; Described hybrid mode is ultrasonic wave or mechanical stirring; The method of removing solvent and residual reactant described in the step (C) is in 110 ℃ of vacuum drying ovens dry 11～13 hours.
The present invention compared with prior art has following beneficial effect:
Preparation method's technology of super-hydrophobic silica of the present invention is simple, the reaction conditions gentleness, and preparation cost is lower.Its water contact angle of silicon-dioxide with the inventive method preparation can reach 155.1 °, the secondary agglomeration phenomenon that can effectively stop silica sphere, improve interface compatibility inorganic and organic phase, strengthen it and polymer scale is made a concerted effort, thereby reach the effect of enhancing, toughening polymer based composites, can be widely used in many industrial circles such as silicon rubber, coating, plastics, medicine, papermaking.
Embodiment
Below by specific embodiment explanation the present invention, but the present invention not merely is defined in these embodiment, the present invention represents the hydrophobicity of silicon-dioxide with water contact angle, this numerical value is big more, shows that hydrophobicity is good more.
Embodiment 1
Take by weighing 3g precipitated silica (particle diameter 40-60nm, specific surface area 150m
2/ g), 30g toluene places the there-necked flask of 250ml, stir it is uniformly dispersed; Be warming up to 80 ℃, add 1.5g octadecyl Trimethoxy silane, react after 30 minutes, be warming up to 110 ℃ and make its backflow 4 hours, it is fully reacted; With toluene wash and filter the silica solid powder, place 110 ℃ vacuum drying oven at last, dry 12 hours.It the results are shown in Table 1 after testing
Embodiment 2
Take by weighing 3g precipitated silica (particle diameter 40-60nm, specific surface area 150m
2/ g), 150g toluene places the there-necked flask of 500ml, stir it is uniformly dispersed; Be warming up to 80 ℃, add 15g octadecyl Trimethoxy silane, react after 30 minutes, be warming up to 110 ℃ and make its backflow 4 hours, it is fully reacted; With toluene wash and filter the silica solid powder, place 110 ℃ vacuum drying oven at last, dry 12 hours.It the results are shown in Table 1 after testing
Embodiment 3
Take by weighing 3g fumed silica (particle diameter 20-40nm, specific surface area 380m
2/ g), 90g N, dinethylformamide place the there-necked flask of 250ml, stir it is uniformly dispersed; Be warming up to 90 ℃, add 3g hexadecyl triethoxyl silane, react after 30 minutes, be warming up to 120 ℃ and make its backflow 4 hours, it is fully reacted; Use N at last, the dinethylformamide washing is also filtered the silica solid powder, places 110 ℃ vacuum drying oven, dry 12 hours.It the results are shown in Table 1 after testing
Table 1: the variation table look-up of silicon-dioxide water contact angle before and after the reaction
| Project | Water contact angle |
| SiO 2 powder (before the reaction) embodiment 1 embodiment 2 embodiment 3 | 0° 151.4° 155.1° 153.6° |
Claims (7)
1, a kind of method of preparing super-hydrophobic silica by one-step process is characterized in that may further comprise the steps:
(A) disperse: under the normal temperature, will add reactor behind silica solid powder and solvent and the homodisperse;
(B) reaction: reactor is risen to 60～100 ℃, add treatment agent, after continuing stirring and reacting 20～40 minutes, make 100～140 ℃ of temperature liters and reflux to make silica sphere reach super-hydrophobic in 3～6 hours;
(C) separate, drying: with solvent wash and filter above-mentioned super-hydrophobic silica, remove solvent and remaining reactants and vacuum-drying.
2, the method for preparing super-hydrophobic silica by one-step process according to claim 1 is characterized in that its chemical molecular formula of treatment agent described in the step (B) is R
4-mSi (OR)
m, wherein R is a methyl, and ethyl or many carbon alkyl group, m are 1,2 or 3, and the consumption of treatment agent is 0.5 to 5 times of silica weight.
3, the method for preparing super-hydrophobic silica by one-step process according to claim 2 is characterized in that described treatment agent is octadecyl Trimethoxy silane or hexadecyl triethoxyl silane.
4, the method for preparing super-hydrophobic silica by one-step process according to claim 1 is characterized in that described silica solid powder is the precipitator method or fumed silica.
5, the method for preparing super-hydrophobic silica by one-step process according to claim 1, it is characterized in that described solvent is toluene, dimethylbenzene, N, in dinethylformamide, hexanaphthene, the methylene dichloride one or more, the middle solvent load of step (A) are 10 to 50 times of silica weight.
6, the method for preparing super-hydrophobic silica by one-step process according to claim 1 is characterized in that described hybrid mode is ultrasonic wave or mechanical stirring.
7, the method for preparing super-hydrophobic silica by one-step process according to claim 1, the method that it is characterized in that described in the step (C) removing solvent and residual reactant are in 110 ℃ of vacuum drying ovens dry 11～13 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810020463A CN100575255C (en) | 2008-03-07 | 2008-03-07 | A kind of method of preparing super-hydrophobic silica by one-step process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810020463A CN100575255C (en) | 2008-03-07 | 2008-03-07 | A kind of method of preparing super-hydrophobic silica by one-step process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101249963A true CN101249963A (en) | 2008-08-27 |
| CN100575255C CN100575255C (en) | 2009-12-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810020463A Expired - Fee Related CN100575255C (en) | 2008-03-07 | 2008-03-07 | A kind of method of preparing super-hydrophobic silica by one-step process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381713A (en) * | 2011-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | Hydrophobic silica gel for oil vapor recovery |
| CN102504787A (en) * | 2011-10-14 | 2012-06-20 | 中国石油天然气集团公司 | Novel hydrophobic modified nano-silicon material |
| CN101885469B (en) * | 2009-05-13 | 2013-07-31 | 财团法人工业技术研究院 | Phase transfer method of nano inorganic oxide |
| CN105176629A (en) * | 2015-10-29 | 2015-12-23 | 中国科学院新疆理化技术研究所 | Preparation method of modified nanometer-silicon dioxide lubricating oil additive |
| CN107128932A (en) * | 2017-05-04 | 2017-09-05 | 德清美联新材料科技有限公司 | A kind of preparation method for the VOC hydrophobic silicas adsorbed |
| CN109777260A (en) * | 2019-01-28 | 2019-05-21 | 中国科学院兰州化学物理研究所 | A method of traditional coating is changed into super hydrophobic coating |
-
2008
- 2008-03-07 CN CN200810020463A patent/CN100575255C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885469B (en) * | 2009-05-13 | 2013-07-31 | 财团法人工业技术研究院 | Phase transfer method of nano inorganic oxide |
| CN102381713A (en) * | 2011-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | Hydrophobic silica gel for oil vapor recovery |
| CN102381713B (en) * | 2011-08-30 | 2013-04-10 | 中国石油化工股份有限公司 | Hydrophobic silica gel for oil vapor recovery |
| CN102504787A (en) * | 2011-10-14 | 2012-06-20 | 中国石油天然气集团公司 | Novel hydrophobic modified nano-silicon material |
| CN105176629A (en) * | 2015-10-29 | 2015-12-23 | 中国科学院新疆理化技术研究所 | Preparation method of modified nanometer-silicon dioxide lubricating oil additive |
| CN105176629B (en) * | 2015-10-29 | 2018-03-20 | 中国科学院新疆理化技术研究所 | A kind of preparation method of modified manometer silicon dioxide lube oil additive |
| CN107128932A (en) * | 2017-05-04 | 2017-09-05 | 德清美联新材料科技有限公司 | A kind of preparation method for the VOC hydrophobic silicas adsorbed |
| CN109777260A (en) * | 2019-01-28 | 2019-05-21 | 中国科学院兰州化学物理研究所 | A method of traditional coating is changed into super hydrophobic coating |
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| Publication number | Publication date |
|---|---|
| CN100575255C (en) | 2009-12-30 |
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