CN1055712C - Hydrophobic silicon deoxide and production method thereof - Google Patents
Hydrophobic silicon deoxide and production method thereof Download PDFInfo
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- CN1055712C CN1055712C CN96104564A CN96104564A CN1055712C CN 1055712 C CN1055712 C CN 1055712C CN 96104564 A CN96104564 A CN 96104564A CN 96104564 A CN96104564 A CN 96104564A CN 1055712 C CN1055712 C CN 1055712C
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Abstract
The present invention provides hydrophobic silica and a preparing method thereof. Common hydrophobic silica (a surface area is from 100 to 400m <2>/g), silicon oil, a dispersing agent, a catalyst and a molecular weight regulator react under a proper condition to prepare solid powdery silica with the surface grafted with polysiloxane, and the hydrophobic contact angle of the silica can achieve 70 to 150. The silica has good hydrophobicity and a defoaming function and can be suitable for the whole process of textile dyeing.
Description
The present invention relates to hydrophobic silica and manufacture method thereof.
Silicon-dioxide (silica) purposes is very extensive, and at coating, printing ink, plastics, rubber and makeup all usually add silicon-dioxide to increase performance, as oil suction, delustring, reinforcement mechanicalness ... etc., and can reduce cost.Its surface property must meet the characteristic that is added thing, so that can homodisperse.The general industry grade silicon dioxide, because preparation technology's difference, can be divided into two kinds, a kind of is dry type, sintered type (fume type), and a kind of is wet type, sedimentation type (precipitated type), the surface-area difference of the two, the hydroxyl that its surface has (OH) also has difference, in general, the former is less, the latter is more, and wetting ability all is partial on the two surface, as is applied in the lipophilicity polymer, as coating, rubber ... etc., if silica sphere is anticipated into hydrophobicity, effect is preferably arranged.
General the simplest method is as Zhao Chengchen professor's works: mention in " in the interface science basis, dispersion principle and application " piece of writing, utilize the absorption of solid surface to tensio-active agent, change the polarity of solid surface.Be dissolved in the polar solvent as Zinc Stearate, add silicon-dioxide, remove and desolvate, then the zine ion part is towards silicon-dioxide, hard ester dialkylaminobenzoic acid part, then towards the outside, and form the particle surface hydrophobicity, or silicon-dioxide adds silicoorganic compound, the methoxy or ethoxy on the Siliciumatom, can (OH) react with the hydroxyl of silica sphere, and organic moiety (vinyl, epoxy group(ing), propenyl (acrylic base) ...) then outward, not only make silica sphere be hydrophobicity, have more reactivity, can with part interlinkages such as lipophilicity polymer, and increase its physical strength.
Above-mentioned silicon-dioxide, transfer hydrophobic mode to by wetting ability and comprise: silica sphere has been covered with the organic fatty alkyl; No. 1163784, Deutsches Reichs-Patent is utilized dimethyldichlorosilane(DMCS) (Dimethyl dichlorosilane), and directly height is pressed into; Japan clear 61-50882 number at No. 1163784, Deutsches Reichs-Patent, produces the shortcoming of by product and hydrogenchloride and the method improved in preparation process; And the silicon-dioxide that has the dimethyl polysiloxane oligomer processing of three Si-OH with end group.Above-mentioned the whole bag of tricks all makes silica sphere be hydrophobic property, but does not have good their defoaming function.
The object of the invention is to provide a kind of silicon-dioxide of surface grafting polysiloxane.Surface-area is 100～400m
2/ g, surperficial tool hydrophobicity and have their defoaming function concurrently, preparation technology is simple, at normal pressure, operation below 100 ℃, and do not produce byproduct (as hydrogenchloride).
The present invention provides a kind of hydrophobic silica pressed powder of surface grafting siloxanes.No matter dry type method for making sintered type silicon-dioxide or wet type method for making sedimentation type silicon-dioxide, silanol (Silanol) is all contained on its surface, and can with the polysiloxane end group of silanol group reaction, must possess alkoxyl group (alkoxy) or silanol group, reaction in the presence of the catalyst of Lewis acid (Lewis ac-id) or Lewis base (Lewis base) simultaneously.For the surface that makes silicon-dioxide fully contacts with polysiloxane molecule, must add dispersion agent, for making silica sphere grafted polysiloxane molecule amount suitable, can add molecular weight regulator.
The method of the manufacturing of hydrophobic silica has two kinds, method one is in Glass Containers, add (1) dispersion agent, as mineral oil (mineral oil), organic solvent (dimethylbenzene), prestox Fourth Ring siloxanes (Octamethyl tetracyclosiloxane) or silicone oil (silic-one oil) ...; (2) wetting ability silica solid powder (silica), its surface-area is 100～400m
2/ g, contact angle is less than 70 °; (3) silicone oil (silicone oil); (4) catalyst, as aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, ammonium carbonate solution or sulfuric acid ... wait soda acid; (5) molecular weight regulator, its purpose is to make the silicon compound molecular weight that grafts on the silicon dioxide granule suitable, use always, as tetramethyl disiloxane (Tetramethyl disiloxane), hexamethyldisiloxane (Hexamethyl disi-loxane) or pentamethyl-methoxy silane (Pentamethyl methoxysilane).Homogenize with the clarifixator mixing, 5 to 20 minutes, be warming up to 60 ℃～80 ℃ then, continue to stir and to homogenize, 30 minutes to 120 minutes, filter and wash the hydrophobic silica pressed powder of reaction gained with organic solvent (as dimethylbenzene) collection, in about 120 ℃ baking oven, dry about 6 hours.Other method is except replacing silicone oil with the silicon compound monomer, other reactants and method one are same, silicon compound monomer such as tetramethyl-dimethoxy silane (Tetrameth-yl dimethoxysilane) commonly used because itself have the dispersive function concurrently, can not add other dispersion agent.As for reaction method, except homogenizing, after intensification with the clarifixator mixing, simultaneously in (reflux) mode that refluxes, in order to reaction, about 10～30 minutes of return time is after reaction is finished, vacuumize, to remove remaining silicon compound, wash and filter with organic solvent (as dimethylbenzene) collection again and reacted the silica solid powder of finishing, place 120 ℃ baking oven, dry about 6 hours, promptly get polysiloxane grafted silica solid powder.Do compressing tablet contact angle determination, FTIR spectrophotometer with this hydrophobic silica pressed powder, and the froth breaking test, the results are shown in the following subordinate list.
For above-mentioned and other purposes of the present invention, feature and advantage can be become apparent, hereinafter enumerate a preferred embodiment, and cooperate appended form, be described in detail below: " embodiment 1 "
Get 80g dimethylbenzene, place the Glass Containers of 200ml, add 10g silicone oil (Dow Cor-ning, DC-350), 0.1g hexamethyldisiloxane (Hexamethyl disiloxane), 2 10wt% sodium hydroxide (Sodium hydroxide), 20g wetting ability silica solid powder (PPG, Label 20), the particle diameter of this wetting ability silica solid powder is 30nm, surface-area is 200m
2/ g.With clarifixator, mix to homogenize 10 minutes, reheat to 80 ℃ continues to mix homogenizing 30 minutes, filters, and washes with the dimethylbenzene collection again, and the polysiloxane-grafted silica solid powder that the gained reaction is finished places 120 ℃ of baking ovens, dry about 6 hours." embodiment two "
Get the tetramethyl-dimethoxy silane (Tetramethyl dimethoxy silane) of 80g, insert in the Glass Containers of 200ml, add 0.8g pentamethyl-methoxy silane (Pentameth-yl methoxysilane) again, and 2g 20wt% volatile salt, with 20g wetting ability silicon-dioxide (PPG, Label 20), homogenized 10 minutes with the clarifixator mixing, after the heating, continue to mix homogenizing, and after refluxing 20 minutes, vacuumize to remove the silicon compound monomer, and with the polysiloxane-grafted silica solid powder that the dimethylbenzene collection is washed and filtering reaction is finished, place 120 ℃ baking oven, dry about 6 hours.Froth breaking test froth breaking emulsion preparation: the particle (PPG that gets wetting ability silicon-dioxide respectively, Label 20), embodiment one, two each 1.5g of prepared silicon dioxide granule, add an amount of silicone oil, emulsifying agent and dispersion agent, homogenize with the clarifixator mixing, become the froth breaking emulsion of the about 20wt% of solid content.Experimental procedure: with the pore forming material (Tween 80 0.1%) for preparing, insert in 41 liter the Glass Containers, reserve the height that bubbles more than 8 centimeters, the Glass Containers of splendid attire Tween 80 aqueous solution is placed 25 ℃ of thermostatic baths, respectively connect recycle pump (pump) in each container, the start cycles pump is measured the 8 centimeters required times that bubble, splash into 10 froth breaking emulsions that prepared respectively in the different glass container, bubble is high behind time that the measurement froth breaking is required and the froth breaking.
Table one, 2 112 ° of 0 ° of one 145 ° of embodiment of embodiment of contact angle project contact angle Lsbel 20 (reaction before) of silicon-dioxide before and after the reaction relatively
Table two, silicon-dioxide FTIR absorption spectrum before and after the reaction relatively: wave number (cm
-1) functional group react before reaction back 1260 Si-C do not have and have 2961 Si to go up Organoalkyl not have and have 3500-OH to have or not
Table three, silicon-dioxide antifoam performance before and after the reaction relatively
Tween 80 adds the Tween 80 that disappears and adds after the froth breaking emulsion that the high foam time of bubble steeps 5 minutes 30 seconds 6.5cm (before the reaction) of high Label 20 8cm, 2 minutes 30 seconds 2.5cm of 2 minutes 30 seconds 1cm embodiment two 8cm of embodiment one 8cm before the project bubble emulsion
Though the present invention with preferred embodiment openly as above, is not in order to limit the present invention.Anyly be familiar with this skill person, without departing from the spirit and scope of the present invention, can do some changes and modification, so protection scope of the present invention is when with being as the criterion that accompanying claims were limited.
Claims (19)
1. the manufacture method of a hydrophobic silica comprises:
At normal temperatures, wetting ability silica solid powder, silicone oil, molecular weight regulator, dispersion agent and catalyst are mixed, wherein the weight ratio of wetting ability silica solid powder, silicone oil, molecular weight regulator is 2-3: 1: 0.005-0.02, the weight of dispersion agent is 2.7 times of above-mentioned three kinds of reactant gross weights, stirred 5-20 minute, wherein the contact angle of this wetting ability silica solid powder is 100 to 400 square metres of every grams less than 70 °, surface-area; This molecular weight regulator is a kind of in hexamethyldisiloxane, pentamethyl-methoxy silane, the tetramethyl disiloxane, and described dispersion agent is mineral oil, prestox Fourth Ring siloxanes or dimethylbenzene; Described catalyst is Lewis acid or Lewis base;
Be warming up to 60 ℃-80 ℃, continue to mix 30-120 minute, form hydrophobic silica with reaction;
Wash and filter above-mentioned hydrophobic silica with organic solvent extracting; And
Remove this organic solvent and remaining reactants.
2. by the described manufacture method of claim 1, wherein, described intensification is meant and is warming up to 80 ℃ that described mixing time is 30 minutes.
3. by the described manufacture method of claim 1, wherein, the weight ratio of described wetting ability silica solid powder, silicone oil and molecular weight regulator is 2-3: 1: 0.01.
4. by the described manufacture method of claim 1-3, wherein, described mixing is to carry out in clarifixator.
5. by the described manufacture method of claim 1-3, wherein, described organic solvent is a dimethylbenzene.
6, by the described manufacture method of claim 1-3, wherein, the step of described removal solvent and residual reactant drying in 120 ℃ of baking ovens was finished in 6 hours.
7, by the described manufacture method of claim 1-3, wherein, described Lewis acid or Lewis base are sodium hydroxide, potassium hydroxide, volatile salt or sulfuric acid.
8, by the described manufacture method of claim 1-3, wherein, described catalyst consumption is 0.1 to 1 weight percent.
9, a kind of hydrophobic silica, its hydrophobic contact angle that uses the described manufacture method of claim 1-3 and make is 70 to 150 degree.
10, a kind of manufacture method of hydrophobic silica comprises:
At normal temperatures, with weight ratio is 1: wetting ability silica solid powder, the silicon compound monomer of 2-5: 0.01-0.1 are mixed with molecular weight regulator, catalyst, stirred 5-20 minute, wherein the contact angle of this wetting ability silica solid powder is 100 to 400 square metres of every grams less than 70 °, surface-area; This molecular weight regulator is a kind of in hexamethyldisiloxane, pentamethyl-methoxy silane, the tetramethyl disiloxane; This silicon compound monomer has the alkoxy-functional base; Described catalyst is Lewis acid or Lewis base;
Be warming up to the boiling point of reactant, continue to mix, and refluxed 10 to 30 minutes, form hydrophobic silica with reaction;
Wash and filter above-mentioned hydrophobic silica with organic solvent extracting;
Remove this organic solvent and remaining reactants.
11, by the described manufacture method of claim 10, wherein, the weight ratio of described wetting ability silica solid powder, silicon compound monomer and molecular weight regulator is 1: 4: 0.04.
12, by the described manufacture method of claim 10, wherein, described return time is 20 minutes.
13, by the described manufacture method of claim 10-12, wherein, described silicon compound monomer is the tetramethyl-dimethoxy silane.
14, by the described manufacture method of claim 10-12, wherein, described mixing is to carry out in clarifixator.
15, by the described manufacture method of claim 10-12, wherein, described organic solvent is a dimethylbenzene.
16, by the described manufacture method of claim 10-12, wherein, the step of described removal solvent and residual reactant drying in 120 ℃ of baking ovens was finished in 6 hours.
17, by the described manufacture method of claim 10-12, wherein, described catalyst consumption is 0.1 to 1 weight percent.
18, by the described manufacture method of claim 10-12, wherein, acid of described Louis or Lewis base are sodium hydroxide, potassium hydroxide, volatile salt or sulfuric acid.
19, the prepared hydrophobic silica of a kind of described manufacture method of use claim 10-12, its hydrophobic contact angle are 70 to 150 degree.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96104564A CN1055712C (en) | 1996-04-10 | 1996-04-10 | Hydrophobic silicon deoxide and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96104564A CN1055712C (en) | 1996-04-10 | 1996-04-10 | Hydrophobic silicon deoxide and production method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1161997A CN1161997A (en) | 1997-10-15 |
| CN1055712C true CN1055712C (en) | 2000-08-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN96104564A Expired - Lifetime CN1055712C (en) | 1996-04-10 | 1996-04-10 | Hydrophobic silicon deoxide and production method thereof |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303663B1 (en) * | 1999-03-26 | 2001-10-16 | Cognis Corporation | Process for making defoaming compositions |
| DE102004029074A1 (en) * | 2004-06-16 | 2005-12-29 | Degussa Ag | Paint formulation for improving the surface properties |
| GB0516272D0 (en) * | 2005-08-09 | 2005-09-14 | Univ Sunderland | Hydrophobic silica nanoparticles |
| CN100463851C (en) * | 2005-10-26 | 2009-02-25 | 太原理工大学 | Method for preparing super fine hydrophobic silicon dioxide |
| CN100575256C (en) * | 2008-03-07 | 2009-12-30 | 南京工业大学 | A kind of preparation method of super-hydrophobic silica |
| 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 |
| CN106380945A (en) * | 2016-10-27 | 2017-02-08 | 重庆大学 | Anti-pollution-flashover superhydrophobic paint, and preparation method and application thereof |
| PL3877332T3 (en) * | 2020-01-14 | 2022-07-11 | Evonik Operations Gmbh | Fumed silica with modified surface activity |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4191587A (en) * | 1977-12-07 | 1980-03-04 | Wacker-Chemie Gmbh | Preparation of hydrophobic silicon dioxide |
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1996
- 1996-04-10 CN CN96104564A patent/CN1055712C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4191587A (en) * | 1977-12-07 | 1980-03-04 | Wacker-Chemie Gmbh | Preparation of hydrophobic silicon dioxide |
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| CN1161997A (en) | 1997-10-15 |
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