CN1308401C - Method for preparing hydrophobic inorganic and organic composite corpuscle - Google Patents
Method for preparing hydrophobic inorganic and organic composite corpuscle Download PDFInfo
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- CN1308401C CN1308401C CNB2004100609548A CN200410060954A CN1308401C CN 1308401 C CN1308401 C CN 1308401C CN B2004100609548 A CNB2004100609548 A CN B2004100609548A CN 200410060954 A CN200410060954 A CN 200410060954A CN 1308401 C CN1308401 C CN 1308401C
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Abstract
The present invention provides a method for preparing inorganic and organic composite microparticles with excellent hydrophobic performance, namely an ammonia base type silane coupling agent is used for chemical modification on the surface of hydrophilicity silicon dioxide. Then, more than one compound is selected from carboxylic acid with a carbon number of more than 3 and a derivative thereof, an alkyl group enone dipolymer and a diisocyanate compound, or more than one kind of fluoride is selected from the fluorine compound of RfSO3F and RfCOOH under the condition of the existence of organic silicone oil or a fluorine containing surfactant to chemically react with processed silicon dioxide with the surface provided with amino groups. Consequently, the inorganic and organic composite microparticles with the excellent hydrophobic performance can be generated and can be used as filling material to be widely applied to the fields of high molecular material, such as paint, rubber, etc.
Description
Technical field
The present invention be relevant hydrophobicity inorganic/manufacture method of organic composite microparticle, this micropartical uses as filler can be widely used in industrial circles such as coating, rubber, papermaking.
Background technology
Used silica filler roughly has following three kinds in polymer industrial circles such as coating, rubber: the amorphous silica that the wet type precipitator method generate, the amorphous silica that amorphous silica that the wet type gel method generates and dry type vapor phase process generate.
Wet type precipitator method amorphousness wetting ability silicon-dioxide (hereinafter to be referred as wetting ability silicon-dioxide) is obtained by water glass and sulfuric acid neutralization reaction, and the amorphous silica that obtains with this method can extensively be used as the additive etc. of filler, rubber reinforcing filler, farm chemical carrier, paper industry filler and the defoamer of coating.
The silicon-dioxide that does not have the surface treated wet type precipitator method to generate is hydrophilic, generally be in the presence of interfacial agent, with the acid amides of higher fatty acid (erucic acid acyl by, oleic acid acyl press etc.), polyethylene or polypropylene synthesize paraffin wax, high fatty alcohol, be solid-state organic substance under the room temperature such as higher fatty acid and high-grade aliphatic ester, carry out surface-hydrophobicized processing.In addition, select the material more than a kind that wetting ability silicon-dioxide is carried out surface-hydrophobicized processing the mineral oils that can also under room temperature, be in a liquid state, plant oil and the organic silicone oil at least.As the synthetic paraffin wax of the described use polyethylene of the public Reported of the flat 7-166091 of ， Te Open the method that hydrophobization is handled is carried out on the surface of wetting ability silicon-dioxide.Can also use above-mentioned solid-state and liquid organic substance that hydrophobization is carried out on the surface of wetting ability silicon-dioxide simultaneously and handle according to the different purposes of macromolecular material in addition.
But the process for hydrophobicizing of above-described wetting ability silica sphere all depends on the hydrophilic of interfacial agent, and hydrophobic function is adsorbed on the silica sphere hydrophobic organic compound matter.Owing in the processing of macromolecular material, some reason in the use, these hydrophobic organic compound matter that are adsorbed on the silica sphere are easy to come off from silica sphere, hydrophobic silica presents wetting ability again, cause the immiscible or difficult dispersion of silicon-dioxide and organic polymer material, cause the physical and mechanical properties variation of material.
Among the public Reported of the flat 5-97423 of Zai Te Open, record and narrate the also usefulness of amino one type of silane coupling agent and organic silicone oil, at high temperature made the method for hydrophobic silica.But under this occasion, most organic silicone oil just is adsorbed on the silica sphere that contains amino one type of silane coupling agent, produces into hydrophobic effect thus.And on the surface of silicon-dioxide, the rare chemical reaction of the amino of silane coupling agent and organic silicone oil, the combination that is difficult for producing chemical bond.According to the difference of environment for use, these hydrophobic silicas and organic silicone oil are easy to generate separation phenomenon, cause the hydrophobic performance variation.
Among the public Reported of the clear 62-171913 of Zai Te Open, put down in writing the methods of hydrophobilization of use hexamethyldisiloxane siloxanes (simple HMD S) processing wetting ability silica sphere.Among the public Reported of the flat 8-259216 of Zai Te Open, the less silicon-dioxide of surperficial OH base is used in requirement before hydrophobization is handled, put down in writing HMDS and wetting ability silicon-dioxide when high temperature contacts, must use the manufacture method of the hydrophobic silica of alkaline gas such as ammonia or organic amine.But HDMS is difficult for the OH base complete reaction with the wetting ability silica sphere, so the hydrophobicity effect that generates is bad.
Summary of the invention
The objective of the invention is defective at prior art, make hydrophobicity organic composition and silica sphere generation chemical reaction produce chemical bonding thus, cause the hydrophobicity organic composition not come off, the manufacture method of the inorganic/organic composite microparticle with excellent hydrophobic performance is provided at silica sphere.
With amino one type of silane coupling agent the wetting ability silica sphere is carried out chemical treatment, then from carbonatoms more than 3 carboxylic acid and carboxylic acid derivative, alkyl ketene dimer, diisocyanate cpd select more than one compound with handle the rear surface and have amino silicon-dioxide and carry out chemical reaction, thus the hydrophobicity of Sheng Chenging inorganic/manufacture method of organic composite microparticle.
Above-mentioned hydrophobicity inorganic/hydrophobicity that generates thus after adding organic silicone oil in the manufacturing processed of organic composite microparticle is inorganic/manufacture method of organic composite microparticle.
Or above-mentioned hydrophobicity inorganic/hydrophobicity that generates thus after adding the fluorinated interfacial agent in the manufacturing processed of organic composite microparticle is inorganic/manufacture method of organic composite microparticle.
Or use fluorochemicals R
fSO
3F or R
fCOOH (R wherein
fBe the fluoro-containing group of carbonatoms more than 4) have amino silicon dioxde reaction with surface after treatment, generate hydrophobicity inorganic/manufacture method of organic composite microparticle.
It below is detailed description of the present invention.
There is no particular limitation to employed wetting ability silicon dioxide particles in the present invention.Add the dry type smog method of hydrothermal decomposition and the silicon-dioxide that generates though also can use, consider, the amorphousness wetting ability silicon-dioxide that should select for use the wet type precipitator method to make from economic aspect by chlorosilane.If consider from the save energy aspect, preferably use in wetting ability silicon-dioxide manufacturing processed, in the silicate alkaline aqueous solution, add in the mineral acid and the time, precipitation is separated out does not pass through exsiccant pulp-like silicon-dioxide.
Industrial amino one type of silane coupling agent kind, purity, rerum natura etc. are not had special requirement yet, and general molecular structural formula amino one type of silane coupling agent as follows all can use.
NH
2CH
2CH
2NHCH
2CH
2CH
2Si(OMe)
3，
NH
2CH
2CH
2NHCH
2CH
2CH
2SiMe(OMe)
2，
NH
2CH
2CH
2CH
2Si(OEt)
3，
NH
2CH
2CH
2CH
2SiEt(OEt)
2，
Among the present invention, the reaction of wetting ability silicon-dioxide and amino one type of silane coupling agent is at room temperature to carry out, and general prewiredly makes the amino one type of silane coupling agent aqueous solution that concentration is 0.5～2wt%, and then adds an amount of wetting ability silicon-dioxide.Amino one type of silane coupling agent has good water-soluble, can be made into the aqueous solution of quite stable.The reaction times of amino one type of silane coupling agent and wetting ability silicon-dioxide is 5～100 minutes, and optimum reacting time is 20～60 minutes.Contain amino silane coupling agent unimolecular layer if on the wetting ability silica sphere, formed one deck, we can say the composite microparticle that has obtained optimum performance so.The consumption of amino one type of silane coupling agent can be calculated by following formula:
The consumption of amino-organosilanes coupling agent (g)=silicon-dioxide (g) silicon-dioxide specific surface area (m
2/ g)/minimum of amino-organosilanes coupling agent coats area (m
2/ g)
In the formula: the minimum area that coats calculates according to Stuart-Briegleb molecule mole.
Among the present invention, because through the silicon-dioxide after the amino one type of silane coupling agent treatment, the amino on its surface is wanted and from carboxylic acid and the carboxylic acid derivative thereof of carbonatoms more than 3 again, alkyl ketene dimer, at least select the reaction of material more than a kind in the diisocyanate cpd, generate the hydrophobicity coating layer of long carbochain at silica sphere, so, the usage quantity of silane coupling agent when reaching same hydrophobicity effect, can be reduced greatly.
Among the present invention, the actual amount of amino one type of silane coupling agent is that the purposes according to the inorganic/organic composite microparticle that generates changes, and common consumption is 2～20wt% of wetting ability silicon-dioxide, and optimum amount is 4～10wt%.When amino one type of silane coupling agent consumption when the 2wt% of wetting ability silicon-dioxide is following, with the reactivity variation of silicon-dioxide, also very low with the reactivity of silicon-dioxide after the amino one type of silane coupling agent treatment and organic compound.When amino one type of silane coupling agent consumption when the 20wt% of wetting ability silicon-dioxide is above, resulting hydrophobicity is inorganic/raw materials cost of organic composite microparticle can be very high, moreover the easy aggegation of the composite microparticle that is generated, and gives the dry difficulty of disperseing to bring.
Among the present invention, the reaction of amino one type of silane coupling agent and wetting ability silicon-dioxide also can be used spray method except aqua-solution method.Spray method is earlier the wetting ability silicon-dioxide powdery to be dropped in decollator or the mixing machine, contains the aqueous solution of amino one type of silane coupling agent or the mixing solutions of water and organic solvent while stir to the silicon-dioxide powdery sprinkling.
Among the present invention, the surface that after amino one type of silane coupling agent treatment, generates have amino silicon-dioxide with from carboxylic acid and the carboxylic acid derivative thereof of carbon atom quantity more than 3, employed solvent when the material of selection more than a kind reacts in alkyl ketene dimer and the vulcabond, temperature of reaction, there is no particular limitation for reaction conditionss such as reaction times.According to the kind of organic compound, character and reaction type can be selected suitable reaction system, in the aqueous solution and organic solvent, or organic phase/water 2 phase systems.
The former several carboxylic acids more than 3 of carbon used in the present invention generally have capric acid, lauric acid, and stearic acid and oleic acid etc., carboxylic acid derivative has the acyl chlorides of carboxylic acid, acylbromide compound and anhydride compound.
Alkyl ketene dimer uses as cementing agent in paper industry, and technical grade alkyl ketene dimer wax generally contains anhydride compound and a spot of carboxylic acid, is a kind of mixture of alkyl ketene dimer.The alkyl ketene dimer wax that the present invention uses, its alkyl ketene dimer content is more than the 90wt%, and the content of anhydride compound is below 10wt%, and melting point is more than 50 ℃.
It is 4～20 aliphatic diisocyanate and aromatic diisocyanate that the diisocyanate compound that the present invention uses has carbonatoms, the preferably aliphatic diisocyanate of charcoal atomicity 6～14 or aromatic diisocyanate, be generally hexamethylene diisocyanate, 2,4-or 2, the 6-tolylene diisocyanate, naphthalene diisocyanate etc.When the carbonatoms less than 4 of diisocyanates, the composite microparticle hydrophobicity that obtains is bad, and carbonatoms surpasses 20 diisocyanates and is difficult to obtain as industrial raw material.
The fluorochemicals R that the present invention uses
fSO
3F or R
fR among the COOH
fBe fluoro-containing group, its carbonatoms is more than 4.When carbonatoms at 4 when following, fluorochemicals easy volatilization because its surface tension is low, also very low with the reactivity of amino on the silica sphere after the amino one type of silane coupling agent treatment, this class fluorochemicals is not suitable for doing hydrophobization reagent.
In the present invention, the amino on its surface of silicon-dioxide that after amino one type of silane coupling agent treatment, generates with from carbonatoms more than 3 carboxylic acid and carboxylic acid derivative, alkyl ketene dimer, diisocyanate cpd when selecting more than one material to carry out chemical reaction, equivalence ratio commonly used is 1: 1.The hydrophobicity of the inorganic/organic composite microparticle that generates when amino is excessive is bad, and organic compound when excessive the composite microparticle particle diameter become big being difficult for and disperse.
Powder technology developing direction from now on is the following ultramicron of micron order, and these micron particle and ultra micro rice corpuscles are difficult for keeping, the easy aggegation of powder from producing to this section period of using.Therefore of the present invention inorganic/organic composite microparticle added organic silicone oil or fluorinated interfacial agent during fabrication, what obtain is dispersed good composite microparticle.
Also there is no particular limitation to the kind of the organic silicone oil that uses in the present invention, but preferably select the non-reactive organic silicone oil of straight chain shape siloxane structure for use, such as non-reacted dimethyl silicone oil, methyl phenyl silicone oil, the alkyls modified silicon oil, polyethers modified silicon oil and fatty acid modified silicone oil, the kinetic viscosity of organic silicone oil are generally at 1～100,000 mm
2In/S the scope, and the optimum range of addition is 0.5～5wt% of silicon-dioxide.When being lower than 0.5wt%, prevent the aggegation weak effect, when being higher than 5wt%, prevent that the aggegation effect from not having significantly raising and having increased raw materials cost.
General fluorine-containing interfacial agent can make hydrophobicity inorganic/surface energy of organic composite microparticle reduces significantly, even also can demonstrate fabulous additive effect under extremely low concentration.The fluorine-containing interfacial agent that the present invention uses has with the R of perfluor charcoal chain as hydrophobic group
fThe X structure, general R
fCarbonatoms be more than 8, X is basic metal class (Li, Na, sulfonate groups K) or carboxylate groups.Can also use R in addition
fSO
3The interfacial agent that F and the reaction of non-fluorinated organic compound generate as following structure:
[C
8F
17SO
2NHC
3H
6N
+(CH
3)
3]I
-、
C
8F
17SO
2NH(C
2H
5)C
2H
4OPO(OH)
2、
C
8F
17SO
2N(C
2H
5)(C
2H
4O)
14H
The addition of fluorinated interfacial agent is preferably in 0.1～2wt% scope, and it prevents the aggegation DeGrain addition beyond this scope, and manufacturing cost is increased.
The measuring method of its hydrophobization degree of inorganic/organic composite microparticle that the present invention uses adopts the transmitance method to measure.Described in the public Reported of the flat 5-97423 of Te Open, that is: with 1g inorganic/organic composite microparticle and 100ml water pours fully vibrations in the flask into, stirs 5 minutes, leave standstill 1 minute after, stand-by from drag extraction small amount of liquid.Use ultraviolet and visible light light-splitting photometer to carry out transmission measurement to extracting liquid out then, the transmitance of pure water is decided to be 100, record the hydrophobization rate that the transmitance of extracting liquid out and pure water are defined as silicon-dioxide after relatively at the 550nm place.
Adopt hydrophobicity of the present invention inorganic/manufacture method of organic composite microparticle, the inorganic/organic composite microparticle with excellent hydrophobic performance can be provided, this micropartical can be widely used in coating, rubber and other polymer as packing material.
Embodiment
Below the present invention is illustrated in more detail.
Raw material
1. amino one type of silane coupling agent SH-6020
NH
2CH
2CH
2NHCH
2CH
2CH
2Si(OMe)
3
Toray Dow Corning Silicone produces
2. wetting ability silicon-dioxide ZEOSIL 200
J.M.Huber Corporation produces
3. dodecyl acid
Flower king (strain) produces
4. stearic acid
Rising sun Electricity chemical industry (strain) is produced
5. stearic acid emulsification (concentration of 20wt%)
Bai East (strain) produces
5. alkyl ketene dimer (AKD)
Suzhou heavenly steed chemical company produces
7.AKD emulsification (concentration of 20wt%)
Bai East (strain) produces
8.C
8F
17SO
2F
Sea, Wuhan Dehua worker company produces
9.2,4 and 2, the mixture of 6-tolylene diisocyanate
Asahi Chemical Industry's (strain) produces
10. two isocyanic acids 4, the 4-diphenyl ester
Asahi Chemical Industry's (strain) produces
11. Move viscosity 1000mm
2The dimethyl silicone oil of/s (SH200)
Toray Dow Corning Silicone produces
12. silicone oil emulsification thing (10wt% concentration)
Bai East (strain) produces
13、C
8F
17SO
3Na
Sea, Wuhan Dehua worker company produces
Embodiment 1:
The 100ml deionized water is poured in the stainless steel vessel of 500ml, after adding the dissolving of the amino one type of silane coupling agent of 1gSH-6020 dispersed with stirring, add 20g ZEOSIL 200 wetting ability silicon-dioxide in stirring lentamente, at room temperature stirring reaction is after 30 minutes then, and reaction ends.Agitator is equipped with in the slurry solids thing adding that filtration obtains, in 3 mouthfuls of glass flask of the 500ml of prolong.In addition, with the acid of 1.8g dodecyl, 0.5g kinetic viscosity 1000mm
2The dimethyl silicone oil SH-200 of/s and the toluene of 100ml add in the above-mentioned flask after pouring into and mixing in the beaker of 300ml.90～110 ℃ of following stirring reactions 2 hours, remove by component distillation and to anhydrate-toluene mixture, the hydrophobicity of embodiment 1 inorganic/organic composite microparticle 1.
Embodiment 2:
The slurry solids thing (through chemically treated silicon-dioxide) that uses embodiment 1 to obtain.With the 2.5g stearic acid, 0.5g kinetic viscosity 1000mm
2/ s dimethyl silicone oil SH-200 and 100ml toluene are poured in the 300mml beaker, be heated to 60 ℃ and make its dissolving in stirring.Then with the slurry solids thing, dissolved stearic acid toluene solution is poured in 3 mouthfuls of glass flask of the 500ml that agitator, prolong are housed, is warming up to 90 ℃.90～110 ℃ of following azeotropic 2 hours, the hydrophobicity that obtains embodiment 2 is inorganic/organic composite microparticle 2.
Embodiment 3:
Replacing the 2.5g stearic acid to join in the 100mml toluene 2.5g AKD, adopt the method for embodiment 2, the hydrophobicity that obtains embodiment 3 is inorganic/organic composite microparticle 3.
Embodiment 4:
The 100ml deionized water is poured in the stainless steel vessel of 500ml, after adding the dissolving of the amino one type of silane coupling agent of 2gSH-6020 dispersed with stirring, in stirring, add 20g ZEOSIL 200 wetting ability silicon-dioxide lentamente, stirring reaction after 30 minutes at room temperature then, reaction ends, slurry is poured into agitator is housed, in 3 mouthfuls of glass flask of the 500ml of prolong, then with 25g stearic acid emulsification (20wt% concentration), 10g silicone oil emulsification thing (10wt%), and the 50ml deionized water joins in the flask, stirs 1 hour.Filtration obtains the slurry solids thing, and then at 110 ℃ of following dry 6h, the hydrophobicity that obtains embodiment 4 is inorganic/organic composite microparticle 4.
Embodiment 5:
Adopting the method for embodiment 4, replace the 25g stearic acid to add the 30gAKD emulsification, the hydrophobicity that obtains embodiment 5 is inorganic/organic composite microparticle 5.
Embodiment 6:
The 100ml deionized water is poured in the stainless steel vessel of 500ml, after adding the dissolving of the amino one type of silane coupling agent SH-6020 of 0.4g (2wt% of silicon-dioxide) dispersed with stirring, in stirring, add 20g ZEOSIL 200 wetting ability silicon-dioxide lentamente, at room temperature stirring reaction is after 30 minutes then, and reaction ends.Then 5g stearic acid emulsification (20wt% concentration), 20g silicone oil emulsification thing (10wt%) and 50mml deionized water are joined in the flask, stirred 1 hour.Filter the slurry solids thing, then at 110 ℃ of following dry 6h, the hydrophobicity that obtains embodiment 6 is inorganic/organic composite microparticle 6.
Embodiment 7:
The 100ml deionized water is poured in the stainless steel vessel of 500ml, after adding the dissolving of the amino one type of silane coupling agent SH-6020 of 4g (20wt% of silicon-dioxide) dispersed with stirring, in stirring, add 20g ZEOSIL 200 wetting ability silicon-dioxide lentamente, at room temperature stirring reaction is after 20 minutes then, and reaction ends.Then with 50g stearic acid emulsification (20wt% concentration), 5g silicone oil emulsification thing (10wt%), and the 50mml deionized water joins in the above-mentioned stainless steel vessel, stirs 1 hour.Filter the slurry solids thing, then at 110 ℃ of following dry 6h, the hydrophobicity that obtains embodiment 7 is inorganic/organic composite microparticle 7.
Embodiment 8:
The 100ml deionized water is poured in the stainless steel vessel of 500ml, after adding the dissolving of the amino one type of silane coupling agent SH-6020 of 0.4g (2wt% of silicon-dioxide) dispersed with stirring, in stirring, add 20g ZEOSIL 200 wetting ability silicon-dioxide lentamente, stirring reaction after 20 minutes at room temperature then, add 0.15gNaOH then, stir reaction in 15 minutes and end, filter the slurry solids thing.In addition with 1.88g C
8F
17SO
3F and 100mml toluene are poured in the 300mml beaker, mix.Then with slurry solids thing and C
8F
17SO
3The F toluene solution adds to agitator is housed, and in 3 mouthfuls of glass flask of the 500ml of prolong, at room temperature reacts 2 hours, is warming up to 90 ℃ again.Then to remove in 2 hours and anhydrate and toluene at 90～110 ℃ of component distillations, the hydrophobicity that obtains embodiment 8 is inorganic/organic composite microparticle 8.
Embodiment 9:
The 100ml deionized water is poured in the stainless steel vessel of 500ml, after adding the dissolving of the amino one type of silane coupling agent SH-6020 of 2g (20wt% of silicon-dioxide) dispersed with stirring, in stirring, add 20g ZEOSIL 200 wetting ability silicon-dioxide lentamente, stirring reaction after 20 minutes at room temperature then, reaction ends, filter the slurry solids thing.Then the slurry solids thing is added to agitator is housed, in 3 mouthfuls of glass flask of the 500ml of prolong.In addition with 1.53g 2,4 and 2, the mixture of 6-tolylene diisocyanate, 0.2g C
8F
17SO
3Na and 100mml toluene are poured in the 300mml beaker, add in the flask after mixing.Reaction is 2 hours under 50 ℃ of stirrings.Being warmed up to 90 ℃ again, then removing in 2 hours and anhydrate and toluene at 90～110 ℃ of azeotropic, the hydrophobicity that obtains embodiment 9 is inorganic/organic composite microparticle 9.
Embodiment 10:
Adopt the method for embodiment 9, with 2.25g two isocyanic acids 4, it is above-mentioned 2,4 and 2 that 4-hexichol fat replaces, the mixture of 6-tolylene diisocyanate, and the hydrophobicity that obtains embodiment 10 is inorganic/organic composite microparticle 10.
Comparative example 1:
Adopt the described method of the public Reported of the flat 5-97423 of Te Open, use wetting ability silicon-dioxide ZEOSIL 200, obtain the hydrophobic silica 1 of comparative example 1.
Comparative example 2:
Adopt the described method of the public Reported of the flat 7-71411 of Te Open, use silicon-dioxide ZEOSIL 200, obtain the hydrophobic silica 2 of comparative example 2.
Adopt the transmitance method to measure embodiment 1～10 and comparative example 1,2, the hydrophobicity that obtains is inorganic/transmittance of organic particle, as shown in the table.
| Example | No. | Hydrophobization rate % (transmittance) |
| Embodiment | 1 | 96 |
| 2 | 94 | |
| 3 | 95 | |
| 4 | 97 | |
| 5 | 96 | |
| 6 | 90 | |
| 7 | 98 | |
| 8 | 94 | |
| 9 | 93 | |
| 10 | 92 | |
| Comparative example | 1 | 68 |
| 2 | 73 |
Claims (4)
1, hydrophobicity is inorganic/manufacture method of organic composite microparticle, it is characterized in that at first the wetting ability silica sphere being carried out chemical treatment with amino one type of silane coupling agent, then from carboxylic acid and the carboxylic acid derivative thereof of carbonatoms more than 3, alkyl ketene dimer, select more than one material to carry out chemical reaction in the diisocyanate cpd with the silicon-dioxide that the processing rear surface has amino, generate the hydrophobicity coating layer of long carbochain at silica sphere, remove impurity at last by heating up, wherein, the concentration of amino one type of silane coupling agent aqueous solution is 0.5～2wt%, consumption is 2～20wt% of wetting ability silicon-dioxide, the reaction times of amino one type of silane coupling agent and wetting ability silicon-dioxide is 5～100 minutes, the amino on its surface of silicon-dioxide that after amino one type of silane coupling agent treatment, generates with from carboxylic acid and the carboxylic acid derivative thereof of carbonatoms more than 3, alkyl ketene dimer, when selecting more than one material to carry out chemical reaction in the diisocyanate cpd, equivalence ratio is 1: 1, and the reaction times is 1～2 hour.
2, hydrophobicity inorganic/manufacture method of organic composite microparticle, it is characterized in that using fluorochemicals R
fSO
3F or R
fThe described surface after treatment of COOH and claim 1 has amino silicon dioxde reaction, wherein, and fluorochemicals R
fSO
3F or R
fR among the COOH
fBe fluoro-containing group, its carbonatoms is more than 4.
3, in accordance with the method for claim 1, it is characterized in that hydrophobicity inorganic/add organic silicone oil in the manufacturing processed of organic composite microparticle, the kinetic viscosity of organic silicone oil is at 1～100,000 mm
2In/S the scope, addition is 0.5～5wt% of silicon-dioxide.
4, in accordance with the method for claim 1, it is characterized in that hydrophobicity inorganic/add the fluorinated interfacial agent in the manufacturing processed of organic composite microparticle, addition is 0.1～2wt% of silicon-dioxide.
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| CN101906715B (en) * | 2010-08-03 | 2012-01-18 | 上海亚孚化学有限公司 | Fluorine-containing silane coupling agent and preparation method thereof |
| CN103589194B (en) * | 2012-08-16 | 2016-06-29 | 深圳市红叶杰科技有限公司 | A kind of gas-phase silica dewatering process method |
| CN102993782B (en) * | 2012-12-12 | 2014-04-16 | 江南大学 | Preparation method of polyurethane acrylate oligomer surface modified silica |
| CN104725142B (en) * | 2015-03-25 | 2017-12-19 | 合肥工业大学 | A kind of chitosan coated material of adjustable sustained release performance and preparation method thereof |
| CN104910649A (en) * | 2015-04-23 | 2015-09-16 | 信阳核工业恒达实业公司 | Quartz powder surface active composite modification method |
| CN105214626B (en) * | 2015-11-11 | 2018-01-23 | 刘沐琛 | A kind of slaughterhouse oiliness sewage treatment agent and preparation method based on modified hydrophobic oil suction solid fraction white carbon |
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| JPH0326272A (en) * | 1989-06-23 | 1991-02-04 | Shoko Kagaku Kenkyusho:Kk | Gradual releasing material |
| US5486420A (en) * | 1993-02-03 | 1996-01-23 | Mitsubishi Materials Corporation | Hydrophobic silica powder, manufacturing method thereof and developer for electrophotography |
| JPH06248116A (en) * | 1993-02-23 | 1994-09-06 | Bridgestone Corp | Rubber composition for tire |
| JPH1039534A (en) * | 1996-07-22 | 1998-02-13 | Tomoegawa Paper Co Ltd | Nonmagnetic one-component toner |
| US6420456B1 (en) * | 1997-05-22 | 2002-07-16 | Bayer Inc. | Process for hydrophobicizing particles, and their use as fillers in polymer masterbatches |
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