CN101108730A - Surface modified silicon dioxide - Google Patents

Surface modified silicon dioxide Download PDF

Info

Publication number
CN101108730A
CN101108730A CNA2006101426007A CN200610142600A CN101108730A CN 101108730 A CN101108730 A CN 101108730A CN A2006101426007 A CNA2006101426007 A CN A2006101426007A CN 200610142600 A CN200610142600 A CN 200610142600A CN 101108730 A CN101108730 A CN 101108730A
Authority
CN
China
Prior art keywords
silicon
dioxide
fluidized
bed
surface modification
Prior art date
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.)
Pending
Application number
CNA2006101426007A
Other languages
Chinese (zh)
Inventor
于尔根·迈尔
亨宁·卡贝
马里奥·肖尔茨
库尔特·施皮茨纳格尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of CN101108730A publication Critical patent/CN101108730A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a silicon dioxide with a modified surface, which is characterized in that the surface modification is processed by following surface modifier: D3-D9 type, especially D3, D4 and D5 types of epoxy polysiloxane, wherein D3-D9 especially D3, D4 and D5 are supposed to have 3-9 expecially 3, 4, and 5 epoxy polysiloxane with the type of -O-Si(CH3)2 units (such as octamethylcy-clotetrasiloxane = D4); and a mixture of the epoxy polysiloxane.

Description

The silicon-dioxide of surface modification
Technical field
The present invention relates to silicon-dioxide of surface modification and its production and use.
Background technology
Oxide compound, the hopcalite of the preparation of known pyrolysis method, or the mixed oxide of metal and/or metal oxide can by water repellent for example dimethyldichlorosilane(DMCS) handle (DE-B 11 63784).
Also known finely divided oxide compound can processed in having the bed of octamethylcyclotetrasiloxane (GB-A 887257).
Also known finely divided oxide compound can be endowed repellency by octamethylcyclotetrasiloxane in single jar of (one-pot) process (GB-A 932753, and US 2,803,617A).
The shortcoming that known method has is that octamethylcyclotetrasiloxane can not fully be bonded to oxide surface.
Summary of the invention
The present invention relates to the silicon-dioxide of surface modification, be characterised in that following surface-modifying agent is used for surface modification:
D3-D9 type, especially D3, D4 and D5 type cyclopolysiloxane, wherein, D3-D9, especially D3, D4 and D5 are understood that to have 3-9, particularly 3,4 and 5-O-Si (CH 3) 2The unitary cyclopolysiloxane of-type (for example, octamethylcyclotetrasiloxane=D4), and the mixture of described cyclopolysiloxane.
Especially, can use polysiloxane D4.
Silicon-dioxide according to surface modification of the present invention has following physical-chemical data:
BET surface-area m 2/ g:25-400
The median size nm:5-50 of primary particle
pH： 3-10
Carbon content weight %:0.1-10
Surface modification can followingly be carried out: if appropriate, at first use jet of water silicon-dioxide, and then spray silicon-dioxide with described surface-modifying agent.Described injection also can be carried out or carry out simultaneously with opposite order.Institute's water can with acid for example hcl acidifying be 7 to 1 to the pH value.Institute's water can with alkali for example ammoniacal liquor be adjusted to alkalescence to the pH value be 7 to 14.If use kinds of surface properties-correcting agent, they can be together, separately, apply successively or as mixture.
One or more surface-modifying agents can be dissolved in the appropriate solvent.After injection is finished, mixed again 5-30 minute.
After further mixing end, can comprise the curing time (maturing time).
Then, described mixture is by thermal treatment 0.1-6 hour under 20-600 ℃ in temperature.Described thermal treatment can for example be carried out under the nitrogen at rare gas element.
Described thermal treatment also can be carried out in a plurality of stages of differing temps.Applying of one or more surface-modifying agents can be by the nozzle of single-material, twin nipple or ultrasonic nozzle and carry out.
But surface modification can be carried out in heating mixer with jet apparatus and moisture eliminator continuously or off and on.Suitable device can be a ploughshare mixing tank (ploughsharemixer) for example, disk dryer, fluidized bed dryer or fluid bed dryer.
Used silicon-dioxide can all be pyrogenic silica.The silicon-dioxide of depickling and not depickling all can use.
Pyrogenic silica is known in Ullmann ' s Encyklopadie der technischenChemie[Ullmann ' s Encyclopaedia of Industrial Chemistry], 4 ThEdition, the 21st volume, 462 pages.Described silicon-dioxide preferably uses according to table 1, both can be with the form of depickling also can be with the form of depickling not.
Can be characterised in that according to silicon-dioxide of the present invention the dimetylsilyl that they have and the ratio of monomethyl silyl are 100: 0-50: 50, be preferably 100: 0-70: 30.
The ratio of dimetylsilyl and monomethyl silyl is determined by silicon-29 solid state NMR spectrum.
Temperature program(me) during giving the step of repellency is extremely important for the ratio of determining dimetylsilyl and monomethyl silyl.
Water-wetted surface is long-pending to be 200m to having under 350 ℃-450 ℃ of temperature 2In the processing of the pyrogenic silica of/g, can obtain to have the product of 100% dimetylsilyl on the surface of silicon-dioxide.The thickening effect of the water drain silica that obtains is 2500-3000mPa.s, measures with Araldite.If temperature is increased to 550 ℃-600 ℃, the part of monomethyl silyl increases to about 30%.Therefore the ratio of dimetylsilyl and monomethyl silyl is 70: 30.The thickening of the water drain silica that is obtained is 400-1000mPa.s.The amount of the carbon of chemical bonding increases to 1.6-1.9% from average 1.2%.The methyl alcohol wettability has increased 5-8% and has reached the value of average 45% (maximum value 51%).
Owing to can prepare ratio with definite dimetylsilyl and monomethyl silyl and the water drain silica that therefore has definite rheology (thickening behavior) and subchloride content, in the use of product, has following advantage, i.e. its allow to have low corrosive byproducts remaining low levels of (for example hydrochloric acid or ammoniacal liquor).
Its potential is used, ratio with dimetylsilyl and monomethyl silyl for example according to the present invention is 100: 0, promptly, water drain silica with 100% dimetylsilyl ratio and relative low methyl alcohol wettability and low chloride content, it is the stable especially sealed compound that is used for building industry, especially if desired high-clarity is for example in the connection of glass surface or in health field.
For having dimetylsilyl and monomethyl silyl ratio is 70: 30 according to of the present invention, the dimetylsilyl that promptly has 70% ratio of low thickening, the water drain silica of high methyl alcohol wettability and low chloride content, its potential use be used for component and joint optimum bonding/bridging from levelling (self-levelling) sealing material.Have low viscosity or thixotropic silicone materials, it guarantees accurately (for example, impress compound, dentistry is duplicated compound) of optimum impression accuracy and details.High transparent poly-methacrylic acid esters material; it uses pressing method (pressing methods) preparation so far usually; but owing to using silicon-dioxide according to the present invention to have lower viscosity now; and therefore by injection molding method (injection moulding process) preparation fully faster; for example be used for high transparent heel based on EPDM; in sealing based on the circuit of polysiloxane rubber, wherein low-down chloride content is for the life-span of electronic package extremely important (corrosion protection).
Can prepare by following processing pyrogenic silica according to silicon-dioxide of the present invention, described pyrogenic silica is in the presence of gas hydrolysis and/or oxidation or steam, obtains with the volatile compound of the silicon of steam form by thermolysis; By being present in the lip-deep free OH group of pyrogenic silica or free and be present in its lip-deep OH group, with be suitable for that water repellent with oh group reaction reacts the dimetylsilyl that has until described silicon-dioxide in fluidized-bed and the ratio of monomethyl silyl is 100: 0 to 50: 50, be preferably 100: 0 to 70: 30; Wherein, behind the described pyrogenic silica of preparation, to still mix as much as possible immediately for the water repellent of tart silicon-dioxide with gasification in advance, and do not exist under the oxygen, with a spot of water vapor and the optional rare gas element that exists in fluidized-bed, temperature is about 200 ℃ to about 800 ℃, and is preferably processed under the successive operation under about 400 ℃ to about 600 ℃; And described solid reaction product is randomly subsequently by depickling and drying, avoided suitably with contacting of oxygen being cooled to be lower than before about 200 ℃, be characterised in that not halogen-containing chain siloxanes, the mixture D 3-D9 of monocycle methyl/dimethyl cyclosiloxane, preferred octamethylcyclotetrasiloxane (D4) is as water repellent.
Polydimethylcyclosil.xane D3-D9 is that known empirical formula is [(CH 3) 2SiO] nCompound, wherein n can be 3-9.This naming method is at Ullmanns Encyklop  die dertechnischen Chemie[Ullmann ' s Encyclopaedia of Industrial Chemistry] (1982) the 21st the volume, the 515th page and W.Noll, Chemie und Technologie derSilicone[Chemistry and Technology of the Silicones] (1968), mention in the 237th page of VerlagChemie.
Preferably, the BET surface-area that has is 20-400m 2/ g is preferably 50-380m 2The pyrogenic silica of/g can be used as hydrophilic parent material.
In an embodiment of the invention, can be supplied in the fluidized-bed with transmission medium with octamethylcyclotetrasiloxane (D4) blended silicon-dioxide, and shift out continuously, preferably afterwards by known meadow (calming zone) from top.
And, can in the fluidized-bed of inside heating, handle.
Required heat can provide in known manner, partly with the form of rare gas element of steam and/or heat.
Described steam and/or rare gas element can be used simultaneously with the pneumatic transfer form that is used for reactant.
The method according to this invention shows in Fig. 1.
In the method according to the invention, the ratio of dimetylsilyl and monomethyl silyl and the pyrogenic silica that has been endowed repellency can be controlled by temperature program(me) during giving repellency.
In the preferred embodiment of the present invention, temperature can change in 500-600 ℃ of scope, can keep the residence time at 0.5 ± 0.2 hour.
The preferred water repellent octamethylcyclotetrasiloxane (D4) that uses can be supplied with the form of steam.
Any still adherent hydrochloric acid and excessive water repellent can be removed during the temperature 250-350 ℃ following residence time is 0.5 ± 0.2 hour in the adverse current fluidized-bed of downstream reserve.The compactedness of the depickling fluidized-bed of reserve can draw off valve by the adjusting product and realize.The fluidized-bed top of setting up by fluid pressure and the pressure difference of fluidized-bed bottom can draw off valve and remain on 20-40mm (water column) in the fluidized-bed exit by regulating product.
The method according to this invention, can by adverse current or more easily and the stream method carry out.Fluidized-bed can be set size so that the fluidized suspension liquid and the water repellent of silicon-dioxide move up continuously, and flows out from upper space continuously, preferably after passing through the meadow.
Advantageously, the ratio of dimetylsilyl/monomethyl silyl and therefore the thickening behavior of the product that obtains can change according to the mode of setting by the temperature that changes in the water repellent fluidized-bed.
At the top of fluidized-bed, with silica sphere non-chemically the excessive water repellent of bonding can be removed.
In the method according to the invention, giving repellency and depickling also can carry out in a device of uniting use.Described device can preferably be designed to following form, and giving of repellency can be so that also stream (interior chuck) and depickling can be carried out with adverse current (external jacket).
The method according to this invention can advantageously be carried out after the pyrolysis method oxides preparation process immediately.In continuation method according to the present invention,, can remove the acid or the alkali that in hydrosilylation reactions, are used as catalyzer usually from if giving on the pyrogenic silica of not depickling of repellency carried out.
Compare with DE-B 11 67 784 described methods, the method according to this invention has following advantage, promptly can not react in catalytic hydrosilylation to form for example hydrochloric acid of sour by product on required acid (for example hydrochloric acid)/alkali.
Process by coupled silicon dioxide preparation and immediately following thereafter Silanization reaction (giving repellency) step can obtain to have the product of seldom sour by product.
Because do not have for example hydrochloric acid formation of sour by product,, can suppress free silanol group and the not reaction of halogen-containing siloxanes according to Le Chatelier principle.Compare with known method according to DE-B 1,163 784, the faster speed of response of more optimizing also can be given repellency for the pyrogenic silica with big surface-area.
Advantage of having given the silicon-dioxide of repellency according to the present invention is the content with residual chloride thing of the low-down 100ppm of being no more than.
Table 1
AERO SILTT6 00 AERO SIL90 AERO SIL130 AERO SIL150 AERO SIL200 AERO SIL300 AERO SIL380 AERO SILO X50
The CAS registration number 112945-52-5 (old number: 7631-86-9)
Behavior with water Hydrophilic
Outward appearance Loose white powder
According to BET 1) surface-area m 2/g 200±50 90±15 130±25 150±15 200±25 300±30 380±30 50±15
The mean sizes mm of primary particle 40 20 16 14 12 7 7 40
Compacted density 2) conventional material g/l squeezed material g/l (additive " V ") About 60- About 80- About 50 about 120 About 50 about 120 About 50 about 120 About 50 about 120 About 50 about 120 About 130-
Leave the dry loss of loader 3) (following 2 hours at 105 ℃) % ＜2.5 ＜1.0 ＜1.5 ＜0.5 9) ＜1.5 ＜1.5 ＜2.0 ＜1.5
The calcination loss 4) 7) (following 2 hours at 1000 ℃) % ＜2.5 ＜1 ＜1 ＜1 ＜1 ＜2 ＜2.5 ＜1
The pH value 5) (at 4% concentration aqueous dispersions) 3.6-4.5 3.7-4.7 3.7-4.7 3.7-4.7 3.7-4.7 3.7-4.7 3.7-4.7 3.6-4.3
SiO 2 8)％ ＞99.8 ＞99.8 ＞99.8 ＞99.8 ＞99.8 ＞99.8 ＞99.8 ＞99.8
Al 2O 3 8)％ ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.08
Fe 2O 3 8)％ ＜0.003 ＜0.003 ＜0.003 ＜0.003 ＜0.003 ＜0.003 ＜0.003 ＜0.01
TiO 2 8)％ ＜0.03 ＜0.03 ＜0.03 ＜0.03 ＜0.03 ＜0.03 ＜0.03 ＜0.03
HCl 8) 10)％ ＜0.025 ＜0.025 ＜0.025 ＜0.025 ＜0.025 ＜0.025 ＜0.025 ＜0.025
Filter divides residual 6) (according to Mocker, 45 μ m) % ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 0.2
1) according to DIN 66131
2) according to DIN ISO 787/XI, JIS K 5101/18 (not sieved)
3) according to DIN ISO 787/II, ASTM D 280, JIS K 5101/21
4) according to DIN 55921, ASTM D 1208, JIS K 5101/23
5) according to DIN ISO 787/IX, ASTM D 1208, JIS K 5101/24
6) according to DIN ISO 787/XVIII, JIS K 5101/20
7) based on 2 hours material of drying under 105 ℃
8) based at 2 hours material of 1000 ℃ of following calcinations
9) extra package is with protection against the tide
10) the HCl content of loss when calcination
Embodiment
At first 1.5 kilograms of silicon-dioxide are incorporated in the mixing tank, behind thorough mixing, at first randomly the hydrochloric acid of water or dilution sprays, and uses D4 (octamethylcyclotetrasiloxane) to spray then.After injection is finished, continued remix 15 minutes.
After further mixing end, can comprise the curing time.Reacting by heating mixture then.
Following table 2 comprises the specifying information of embodiment preparation:
Used silicon-dioxide is pyrogenic silica AEROSIL  200.
Table 2
Title Silicon-dioxide D4 umber/100 part oxide compound H 2O umber/100 part oxide compound Curing time [h] Heating temperature [℃] Heat-up time [min]
Embodiment 1 Not depickling of AEROSIL  200 15.1 - 0 350 100
Embodiment 2 Not depickling of AEROSIL  200 15.1 - 24 350 100
Embodiment 3 Not depickling of AEROSIL  200 15.1 - 48 350 100
Embodiment 4 Not depickling of AEROSIL  200 15.1 - 144 350 100
Embodiment 5 Not depickling of AEROSIL  200 15.1 - 168 350 100
Embodiment 6 Not depickling of AEROSIL  200 12.1 - 72 350 100
Embodiment 7 AEROSIL200 12.1 7 * 0 350 90
*=replacement H 2O uses the hydrochloric acid of 11.44% concentration
Physics-chem characteristic according to the silicon-dioxide of surface modification of the present invention is as shown in table 3 below.
Table 3 silicon-dioxide physical-chemical data of the present invention
Title pH C content [%] Methyl alcohol wettability [%]
Embodiment 1 4.7 1.3 29
Embodiment 2 5.0 2.0 44
Embodiment 3 5.2 2.3 46
Embodiment 4 5.2 2.6 57
Embodiment 5 5.2 2.7 51
Embodiment 6 5.1 2.2 53
Embodiment 7 5.1 2.5 52
Embodiment 8
The preparation of water drain silica 1 (based on pyrogenic silica Aerosil 200) and water drain silica 2 (based on pyrogenic silica Aerosil 300) is carried out fully continuously according to DE-B 11 63 784.
Silicon-dioxide Aerosil 200 or Aerosil 300 in identical workshop-depickling in advance and intermediate store-do not mix in injector fully with octamethylcyclotetrasiloxane (D4) steam, and be conducted to cover with nitrogen and flow fluidized-bed.
By being 500-600 ℃ in temperature in fluidized-bed, the residence time is to use steam treatment during 0.5 hour, and octamethylcyclotetrasiloxane (D4) chemically is bonded to the Aerosil surface.By changing the temperature in the fluidized-bed, the ratio of dimetylsilyl/monomethyl silyl that can the control surface group.Still adherent hydrochloric acid and excessive octamethylcyclotetrasiloxane are to be removed (about 0.5 hour of the residence time) under 250-300 ℃ in temperature in the adverse current fluidized-bed of downstream reserve.The compactedness of the depickling fluidized-bed of reserve can draw off the valve realization by regulating product.Draw off valve by automatic adjusting product, can remain on 20-40mm (water column) in the fluidized-bed exit by the fluidized-bed top of fluid pressure foundation and the pressure difference of fluidized-bed bottom.Under the situation of two kinds of pyrogenic silicas, the ratio of dimetylsilyl and monomethyl silyl is 70: 30.
Embodiment 9
Described method is carried out according to embodiment 8, but has the intermediate feed bin between water repellent and depickling fluidized-bed.
Embodiment 10
Described method is carried out according to embodiment 8, and temperature is no more than 350 ℃, sprays other hydrochloric acid in addition during giving the step of repellency.The ratio of dimetylsilyl and monomethyl silyl is 100: 0.
The process parameter of embodiment 8-10 is as shown in table 4.The silica 1 of preparation and the physical-chemical data of silicon-dioxide 2 are as shown in table 5.
The pyrogenic silica that is used for parent material has following physics-chem characteristic:
Physics-chem characteristic A200 A300
Particular table area (m 2/g) 200±25 300±30
Dry loss (%) ＜1.5 ＜1.5
Calcination loss (%) ＜1 ＜2
SiO 2Content (%) ＞99.8 ＞99.8
Table 4
Embodiment 8 (silica 1)
Aerosil 200 106kg/h
D 4 177℃
D 4 14.5kg/h
D 4N2 Inj. 10m 3/h
N2 FB 9A 6m 3/h
Water 9A 5kg/h
FB 9A temperature top 540-570℃
FB 9B temperature top 300℃
T waste gas About 260 ℃
Embodiment 9 (silicon-dioxide 2)
Aerosil 300 106kg/h
D 4 170-175℃
D 4 15.5kg/h
D 4N2 Inj. 10m 3/h
N2 FB 9A 6m 3/h
Water 9A 7kg/h
FB 9A temperature top 550-580℃
FB 9B temperature top 350℃
T waste gas About 260 ℃
Embodiment 10 (silica 1)
Aerosil 200 1500kg/h
D 4 182g/h
The hydrochloric acid of about 11 weight % 35g/h-60g/h
Remove mineral water 65g/h-30g/h
The fluidized-bed temperature maximum value 350℃
Table 5
Character Silica 1 Silicon-dioxide 2
Behavior to water Hydrophobic Hydrophobic
Surface-area m according to BET 2/g 150±25 250±30
The mean sizes nm of primary particle 12 7
Dry loss ＜0.1 ＜0.3
Compacted density About 50 About 50
PH (4% concentration in the water) ＞4.0 ＞3.7
Carbon % 1.0-2.0 1.5-3.0
Dimethyl/monomethyl silicomethane % 50/50-100/0 50/50-100/0
SiO 2x％ ＜99.8 ＜99.8
Al 2O 3％ ＜0.05 ＜0.05
FeO 3％ ＜0.01 ＜0.01
TiO 2％ ＜0.03 ＜0.03
HCl％ ＜0.02 ＜0.025
Silica 1 and 2 methyl alcohol wettability are:
Silica 1 40% (high thickening) is to＞45% (low thickening)
Silicon-dioxide 235% (high thickening) is to＞40% (low thickening)
The method according to this invention can be carried out in device as shown in Figure 1.
As shown in Figure 1, water repellent gasifies in vaporizer 1, and mixes with the pyrolysis method oxide compound in pipeline 2.This mixture is conducted to fluidized-bed reactor 3 (fluidized-bed 1).In fluidized-bed reactor 3, the steam of preparation is from following supply in vaporizer 4.Temperature during giving repellency is controlled by temperature survey 5.Product after the processing is discharged at fluidized-bed reactor 3 tops, and is conducted to the top of counter-current reactor 6 (fluidized-bed 2).Supply with nitrogen upstream.Product after the processing is discharged in the bottom of counter-current reactor 6, and supplies to feed bin 7.

Claims (4)

1. the silicon-dioxide of surface modification is characterised in that and uses following surface-modifying agent to carry out surface modification:
D3-D9 type, especially D3, D4 and D5 type cyclopolysiloxane, wherein, D3-D9, especially D3, D4 and D5 are understood that to have 3-9, especially 3,4 and 5-O-Si (CH 3) 2The unitary cyclopolysiloxane of-type (for example, octamethylcyclotetrasiloxane=D4), and the mixture of described cyclopolysiloxane.
2. the silicon-dioxide of surface modification as claimed in claim 1 is characterised in that it has following physical-chemical data:
BET surface-area m 2/ g:25-400
The mean sizes nm:5-50 of primary particle
pH： 3-10
Carbon content weight %:0.1-10
3. the preparation method of the silicon-dioxide of surface modification as claimed in claim 1 or 2 is characterised in that randomly and earlier uses jet of water silicon-dioxide, and then sprays described silicon-dioxide with described surface-modifying agent.
4. the preparation method of the silicon-dioxide of surface modification as claimed in claim 1 or 2, be characterised in that by being present in the lip-deep free OH group of pyrogenic silica or free and be present in its lip-deep OH group, with be suitable for water repellent with oh group reaction and in fluidized-bed, react and handle pyrogenic silica, the dimetylsilyl that has until described silicon-dioxide and the ratio of monomethyl silyl are 100: 0 to 50: 50, are preferably 100: 0 to 70: 30; Wherein, described pyrogenic silica is in the presence of gas hydrolysis and/or oxidation or steam, and the volatile compound of the silicon by thermolysis steam form obtains; Wherein, behind the described pyrogenic silica of preparation, to still mix as much as possible immediately for the water repellent of tart silicon-dioxide with gasification in advance, and do not exist under the oxygen, with a spot of water vapor and the optional rare gas element that exists in fluidized-bed, temperature is about 200 ℃ to about 800 ℃, and is preferably processed under the successive operation under about 400 ℃ to about 600 ℃; And described solid reaction product is randomly subsequently by depickling and drying, avoided suitably with contacting of oxygen being cooled to be lower than before about 200 ℃, it is characterized in that not halogen-containing chain siloxanes, the mixture D 3-D9 of monocycle methyl/dimethyl-cyclosiloxane, preferred octamethylcyclotetrasiloxane (D4) is as described water repellent.
CNA2006101426007A 2006-07-18 2006-10-30 Surface modified silicon dioxide Pending CN101108730A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200610033136 DE102006033136A1 (en) 2006-07-18 2006-07-18 Surface modified silicic acid, modified using a surface modifying agent such as cyclic polysiloxane, useful e.g. as self-sealing materials
DE102006033136.2 2006-07-18

Publications (1)

Publication Number Publication Date
CN101108730A true CN101108730A (en) 2008-01-23

Family

ID=38859134

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2006101426007A Pending CN101108730A (en) 2006-07-18 2006-10-30 Surface modified silicon dioxide

Country Status (2)

Country Link
CN (1) CN101108730A (en)
DE (1) DE102006033136A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101920965B (en) * 2009-06-15 2012-04-25 宁波鑫谷硅胶有限公司 Novel white carbon black treatment kettle
CN103374194A (en) * 2012-04-16 2013-10-30 苏州萃智新技术开发有限公司 Gas phase nano silicon dioxide master batches for plastic modification and preparation method thereof
CN105228970A (en) * 2013-03-26 2016-01-06 喜利得股份公司 For the compositions of additives of amine hardener, its purposes and the amine hardener composition containing it
CN105585937A (en) * 2014-11-12 2016-05-18 三键精密化学有限公司 Epoxy resin composition
CN105860588A (en) * 2015-01-21 2016-08-17 中国石油天然气股份有限公司 Method for preparing modified white carbon black
CN106047158A (en) * 2016-07-13 2016-10-26 山东省地质科学研究院 Dinosaur fossil anti-weathering material and preparation method thereof
CN106854368A (en) * 2015-12-08 2017-06-16 信越化学工业株式会社 Inorganic particle silicone composites, the dispersion comprising compound and solid material and preparation method
CN107383658A (en) * 2017-08-03 2017-11-24 合肥泓定科技有限公司 Polystyrene flame-retardant thermal insulation material and preparation method thereof
CN114606222A (en) * 2022-03-31 2022-06-10 西南交通大学 Method for preparing biodiesel by enzyme-loaded microspheres and Pickering emulsion enzyme method

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101920965B (en) * 2009-06-15 2012-04-25 宁波鑫谷硅胶有限公司 Novel white carbon black treatment kettle
CN103374194A (en) * 2012-04-16 2013-10-30 苏州萃智新技术开发有限公司 Gas phase nano silicon dioxide master batches for plastic modification and preparation method thereof
CN105228970A (en) * 2013-03-26 2016-01-06 喜利得股份公司 For the compositions of additives of amine hardener, its purposes and the amine hardener composition containing it
CN105585937A (en) * 2014-11-12 2016-05-18 三键精密化学有限公司 Epoxy resin composition
CN105860588A (en) * 2015-01-21 2016-08-17 中国石油天然气股份有限公司 Method for preparing modified white carbon black
CN105860588B (en) * 2015-01-21 2018-09-04 中国石油天然气股份有限公司 A kind of preparation method of modified white carbon black
CN106854368A (en) * 2015-12-08 2017-06-16 信越化学工业株式会社 Inorganic particle silicone composites, the dispersion comprising compound and solid material and preparation method
CN106047158A (en) * 2016-07-13 2016-10-26 山东省地质科学研究院 Dinosaur fossil anti-weathering material and preparation method thereof
CN106047158B (en) * 2016-07-13 2018-06-26 山东省地质科学研究院 A kind of dinosaur fossil efflorescence prevention material and preparation method thereof
CN107383658A (en) * 2017-08-03 2017-11-24 合肥泓定科技有限公司 Polystyrene flame-retardant thermal insulation material and preparation method thereof
CN114606222A (en) * 2022-03-31 2022-06-10 西南交通大学 Method for preparing biodiesel by enzyme-loaded microspheres and Pickering emulsion enzyme method

Also Published As

Publication number Publication date
DE102006033136A1 (en) 2008-01-31

Similar Documents

Publication Publication Date Title
CN101108730A (en) Surface modified silicon dioxide
US5686054A (en) Process for the silylation of inorganic oxides
EP2171002B1 (en) Surface-modified, pyrogenically prepared silicas
JP5484329B2 (en) Surface-modified silica produced by pyrolysis
EP1304361B2 (en) Method for Producing Silica with homogenous silylating agent coating
CN103819942A (en) Silanised silicas
CN101522820A (en) Surface-modified silicas
KR101259244B1 (en) Hydrophobicization of silicas under oxidizing conditions
WO2001014480A1 (en) Chemically modified silica fillers, process for producing, and silicone compositions containing same
US20100105818A1 (en) Silicas
CN1930224B (en) Silicone rubber
US6316050B1 (en) Method of producing hydrophobic pyrogenically produced oxides
CN101723388A (en) Silica granules prepared on basis of pyrolysis and preparation method and app {} lication thereof
US6696034B2 (en) Method for producing hydrophobic silica fine powder
EP2268575A2 (en) Silica and also epoxy resins
KR101329381B1 (en) Pyrogenic silicic acid manufactured in a small-scale production plant
CN100506921C (en) Method for preparing hydrophobic type nano silicon dioxide thruogh continuous surface treatment
US4022152A (en) Apparatus for making particulate materials, particularly oxides, hydrophobic
JP3563281B2 (en) Hydrophobized, thermally decomposed metal and / or metalloid oxides, oxide mixtures or mixed oxides and methods for surface treatment of such oxides
JP4235169B2 (en) Aqueous dispersion
US4007050A (en) Hydrophobic oxides of metals and for metalloids
US4030940A (en) Method of producing fine disperse alkylated silica compounds
WO2004060803A1 (en) Highly dispersible, fine, hydrophobic silica powder and process for producing the same
JP2000191317A (en) Production of fused spherical silica
KR101787686B1 (en) Process for surface modification of particulate solids

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20080123