CN102161845A - Surface-modified precipitated silica - Google Patents
Surface-modified precipitated silica Download PDFInfo
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- CN102161845A CN102161845A CN2011100295752A CN201110029575A CN102161845A CN 102161845 A CN102161845 A CN 102161845A CN 2011100295752 A CN2011100295752 A CN 2011100295752A CN 201110029575 A CN201110029575 A CN 201110029575A CN 102161845 A CN102161845 A CN 102161845A
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- dioxide
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/42—Gloss-reducing agents
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- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- 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
- C01P2006/19—Oil-absorption capacity, e.g. DBP values
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- 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
- C01P2006/80—Compositional purity
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
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Abstract
The invention relates to surface-modified precipitated silica, which is characterized in that the surface is modified via polymer processing, and is particularly suitable for use as a delustering agent.
Description
The application is that application number is dividing an application of 200410047791.X application, and application number is that the applying date of 200410047791.X application is on May 13rd, 2004.
Technical field
The present invention relates to a kind of precipitated silica of surface modification, its surface is especially suitable for use as matting agent after the polymer treatment modification, the invention still further relates to the preparation method of this precipitated silica.
Background technology
The surface modification of precipitated silica is known already, and is used for preparing silicon rubber, ink-jet applications or the lacquer (as matting agent) that improves function.
EP 0922671 has described a kind of preparation method of hydrophobic precipitated silicas, wherein, commonly used, drying precipitated silicon-dioxide and polyethylene wax emulsion is reacted, and carries out grinding subsequently in sifter mill or fluidized-bed adverse current pulverizer.
DE 2513608 has described a kind of method that makes thin silicon dioxide drainageization, is under the fluidized of 200 to 300 ℃ of temperature, handles exsiccant silicon-dioxide with organosilane.
EP 0341383 has introduced a kind of easy methods of hydrophobilization, is to add silicone oil emulsion in precipitated silica suspension.
DE 2435860 has described a kind of similar approach, is to react at the organohalosilane that randomly makes precipitated silica suspension and precondensation.After filtering out solid, it is annealed under 300 to 400 ℃ of temperature, then grinding.
Precipitated silica usually is used as delustring lacquer surface.In each observing angle, the enamelled coating of delustring all should have as far as possible little gloss like this.Therefore because the wetting ability precipitated silica in the lacquer very easily in sedimentation, is difficult to or can not stirs fully, so the precipitated silica that usually uses waxing is as matting agent.By in the silica sphere waxing, improved its settling property basically.If not sedimentation of matting agent or sinkability are very little, need not to spend bigger energy consumption so and just can stir again.
When using varnish, the matting agent that requirement adds can not influence the transparency of lacquer.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of silicon-dioxide of surface modification, can improve the performance of lacquer when it makes matting agent in varnish.A kind of method for preparing the silicon-dioxide of surface modification is provided simultaneously.
Surprisingly, silicon-dioxide of the present invention has improved the transparency of lacquer, and the settling character of this silicon-dioxide is good equally with the silicon-dioxide that scribbles polyethylene wax (PE-wax) at least.Therefore compare with the waxing matting agent that usually causes the varnish muddiness, silicon-dioxide of the present invention takes advantage.
Experiment finds, available some polymer-coated precipitated silica to be carrying out modification, so that the refractive index that has added precipitated silica of the present invention is that 14000 to 15000 lacquer has the outstanding transparency.To make its refractive index of matting agent be that 14000 to 15000 lacquer is compared with containing the conventional silicon-dioxide that is coated with PE-wax, the same lacquer that contains silica flatting agent of the present invention then shows the transparency of obvious improvement, even the settling property under liquid form is given prominence to too.Varnish through conventional matting agent delustring generally is muddy under liquid form, in contrast, even also be as clear as crystal under liquid form through the varnish of precipitated silica delustring of the present invention.
Therefore, the purpose of this invention is to provide the precipitated silica of surface through polymer modification, compare through the same lacquer of the contrast precipitated silica of polyethylene wax processing with containing 5 weight %, the precipitated silica of modification of the present invention makes its refractive index n
D20=1.4492 and the transmissivity that contains the lacquer of 5 weight % modification precipitated silicas improves at least 20%.
For this reason, the purpose of this invention is to provide a kind of method for preparing the precipitated silica of surface modification, comprising:
A) in slightly acidic under alkaline condition, precipitate alkali metal silicate solutions with souring agent,
B) add souring agent again the pH value is adjusted to 2 from 7, obtaining silica suspension,
C) filter out precipitated solid, and
D) for example carry out slow drying solid, or for example carry out the rapid drying solid, make the residual water-content of product less than 10% by spray-dryer, fast rotational (Spinflash) moisture eliminator by revolving drier or pan dryer,
It is characterized in that, in step
E) in, with the sedimentary silicon-dioxide of polymer treatment, wherein, to the consumption of polymkeric substance and the selection of kind it is compared through the same lacquer of the precipitated silica of polyethylene wax processing with containing 5 weight %, the precipitated silica of this modification can make its refractive index n
D20=1.4492 and the transmissivity of varnish that contains the precipitated silica of 5 weight % modifications improves at least 20%.
The silicon-dioxide of surface modification of the present invention is the precipitated silica through polymer-coated, compares through the same lacquer of the contrast precipitated silica of polyethylene wax processing with containing 5 weight %, and this precipitated silica makes its refractive index n
D20=1.4492 and the transmissivity of varnish that contains the precipitated silica of 5 weight % modifications improves at least 20%.Preferred transmission property improvement at least 25%, particularly 30%.The contrast silicon-dioxide of handling with polyethylene wax preferably adopts ACEMATT OK 412, is the commercially available prod of Degussa company, and its specification is described by product information 12/02, introduces the present invention especially with for referencial use at this.The precipitated silica that the contrast precipitated silica also can use undressed silicon-dioxide of the same race and apply with polyethylene wax.
According to product information 12/02,
OK412 has following PC data:
1) in the exsiccant material
2) in the material of calcination
In addition, with following physical-chemical data characterization silicon-dioxide of the present invention:
Size distribution d50:1-50 μ m, preferable range 1-40 μ m, 1-30 μ m, 2-20 μ m and 3-15 μ m
Oil-absorption(number) DBP:100-600g/100g, preferable range 150-500g/100g, 200-450g/100g and 250-400g/100g
C content: 1-20%, preferable range 1-10% and 2-8%
Sears index V
2:＜25ml/5g
The surface modification polymkeric substance can be the organopolysiloxane of organopolysiloxane or modification.The organopolysiloxane of modification particularly polyether-modified with acrylate modified-or polyacrylate modified organopolysiloxane.Can use poly-oxyalkylsiloxane in addition.
In a preferred embodiment of the invention, use the organopolysiloxane of following general structure:
Wherein
Y=-OH ,-OR or
Y=H
5C
2-O-(C
2H
4O)
m-, H
7C
3-O-(C
3H
6O)
m-or
R=alkyl, particularly methyl or ethyl,
R
2=alkyl,
R
3=alkyl
a＝0-100，b＝0-100，c＝0-100，d＝0-100，
M=0-100, and k=0-100.
In another preferred embodiment of the present invention, use the organopolysiloxane of following general structure:
Wherein
R
1=methyl or
And/or
And unit sum a=0 to 100, unit sum b=0 to 15, wherein, for substituent R
1, when a=0, the ratio of methyl and alkoxyl group is less than 50: 1 and b 〉=1, when b=0, and a 〉=5.More detailed data particularly can be referring to DE 3627782A1 about the preparation of polysiloxane.The content of this patent application is drawn this as a reference.
Alkyl is to have 1 to 100 carbon atom, and is preferred 1 to 25, the straight or branched alkyl of preferred especially 1 to 10 carbon atom and the cycloalkyl that has 1 to 15 carbon atom.Alkyl can contain one or more pairs of keys or triple bond, and each atom can be replaced by the heteroatoms such as O, N or S.
Step a) and b in the inventive method) in, preferably use density to be about 1.343kg/l, SiO
2Content is 27.3 weight % and Na
2O content is that the water glass (water glass) of 7.9 weight % is as alkali metal silicate aqueous solution.Acidizing reagent can use any mineral acid, the particularly vitriol oil (96% H
2SO
4Or CO
2).
In step a),
It is described for example to press DE 3144299, and various components are under agitation mixed.The content of DE 3144299 is drawn this as a reference.Optional to be filled with water or the container of water glass in add acidizing reagent or acidizing reagent adds with water glass.It should be noted that and keeping slightly acidic to the pH value of alkalescence, to precipitate.The pH value is especially between 6-12.Choose wantonly under constant pH value or constant index of basicity and precipitate.
In step b),
By adding acidizing reagent, particularly add here and be used for sedimentary acidizing reagent, regulate the pH value to acidity or neutral range (pH from 7 to 2).
In step c),
Make the silicon-dioxide that contains in the suspension, randomly left standstill 0 to 90 minute, be washed till neutrality after filtration and with deionized water after preferred 15 to 60 minutes.
In step d),
Solid is through for example carrying out rapid drying by spray-dryer, fast rotational moisture eliminator, or through for example carrying out slow drying by revolving drier or pan dryer, the residual water-content that makes product is less than 10%.
Can carry out surface modification (step e)) at any time.
The embodiment 1 of the inventive method) in, in step e), the polymkeric substance of 0.5-30 weight % surface modification is added in pH is adjusted in the silica suspension of 7-2 in the step b).Add and preferably during 1 to 30 minute, to finish, particularly 5 to 15 minutes, and preferred under the precipitation reaction temperature of step a), that is, particularly 50 to 90 ℃, carry out under preferred 50 to 65 ℃.Subsequently, as step c) and d) as described in, the silicon-dioxide of filtration and desiccated surface modification.
Embodiment 2 in the inventive method) in, will be according to step a) and b) sedimentary silicon-dioxide is through filtering as described in step c), randomly use deionized water wash, again water or sulfuric acid or water and vitriolic mixture suspend it once more then, subsequently in step e), the polymkeric substance of the surface modification of 0.5-30 weight % is added in the suspension, and gained suspension is sprayed in spray-dryer, thereby carries out surface modification in drying process.In addition, also can spray into silica suspension and siloxanes simultaneously.Spray-dired temperature is 200-500 ℃, and the residual water-content of product is less than 10%.The solids content of the silica suspension of spraying mostly is 25 weight % most.
Embodiment 3 in the inventive method) in, as preparation and dried silica as described in the step a)-d).In step e), the polymer phase of the surface modification of exsiccant precipitated silica and 0.5-30 weight % is mixed subsequently, and thorough mixing.Add polymkeric substance in 0 to 120 minute, in preferred 0 to 60 minute, finish in preferred especially 0 to 30 minute.20-150 ℃ was continued blend mixture 0-2 hour down.Mix preferably at 20-100 ℃, carry out under preferred 20-80 ℃ especially.Mixing time is preferably 0-1 hour, preferred 0-30 minute especially.
In preparation method of the present invention, the preferred polymkeric substance that adds like this, when making polymkeric substance and silicon dioxde reaction, polymkeric substance is adjusted to 0.5g: 100g to 30g: 100g with the ratio of silicon-dioxide, particularly 2g: 100g is to 20g: 100g, particularly 3g: 100g to 13g: 100g.
In the methods of the invention, can use the polymkeric substance of the organopolysiloxane of organopolysiloxane or modification as surface modification.The organopolysiloxane of modification refers in particular to polyether-modified with acrylate modified or polyacrylate modified organopolysiloxane.Can use poly-oxyalkylsiloxane in addition.
In the present invention's one preferred embodiment, use the organopolysiloxane of following general formula:
Wherein
Y=-OH ,-OR or
Y=H
5C
2-O-(C
2H
4O)
m-, H
7C
3-O-(C
3H
6O)
m-or
R=alkyl, particularly methyl or ethyl,
R
2=alkyl,
R
3=alkyl
a＝0-100，b＝0-100，c＝0-100，d＝0-100，
M=0-100, and k=0-100.
In another preferred embodiment of the present invention, use the organopolysiloxane of following general formula:
Wherein
R
1=methyl or
And/or
And unit sum a=0 to 100, unit sum b=0 to 15, wherein, for substituent R
1, when a=0, the ratio of methyl and alkoxyl group is less than 50: 1 and b 〉=1, when b=0, and a 〉=5.More detailed data particularly can be referring to DE 3627782A1 about the preparation of polysiloxane.The content of this patent application with draw this as a reference.
Choose wantonly in embodiment 1) and 2) in add emulsion adjuvant, for example LA-S 687 (TEGO GmbH company).This is particularly suitable for water-fast silicoorganic compound.
For reaching required size distribution, need be after the silicon-dioxide drying of surface modification, in step f), carry out grinding and carry out classification simultaneously.Can carry out grinding with commercially available crossing current grinding machine (for example Alpine company, Nethsch-Condux company).
For fear of oversize (Oberkorn) or point (Stippen), suitable method is behind the precipitated silica of desiccated surface modification, perhaps after the grinding of step f) or during the grinding, isolates diameter greater than 50 μ m, be preferably greater than 30 μ m, be preferably greater than the particle of 20 μ m especially.This can for example be undertaken by corresponding sieve or stage equipment according to the fineness requirement of matting agent, and screening plant also can be complete with masher.
The physical/chemical data of precipitated silica of the present invention can be measured with following method:
Measure the transmissivity of lacquer
Adopt the UV/Vis spectrophotometer Specord 200 of ANALYTIK JENA GmbH company, in the quartzy colorimetric pool of 1cm, under room temperature, measure transmissivity as reference substance with air.Wavelength width of a slit and step pitch are 2nm.
For this reason, provide a kind of SH-lacquer, its refractive index n
D20=1.4492, composed as follows:
30.2 weight % dimethylbenzene
15.1 weight % oxyethyl group propyl alcohol
15.1 weight % ethanol
39.6 weight %Plastopa BT, 60% (urea formaldehyde resins contains urethane
The base and by short chain alcohol etherificate, BASF
AG company, Ludwigshafen),
And add 2.5g matting agent (silicon-dioxide of surface modification) separately.Here, at room temperature stir in the SH-lacquer that matting agent was distributed in 10 minutes the 50g lacquer with 2000 rev/mins with the blade stirrer.Under the room temperature, in the PE of 180ml mixing beaker, disperse.The blade of stirrer diameter is 43mm.Subsequently, the dispersion liquid of new system is added in the quartzy colorimetric pool of 1cm, and record UV/Vis spectrum 190 and 1100nm between transmissivity.
Measure the modification Sears index of silicon-dioxide
With potassium hydroxide solution titration silicon-dioxide, make pH be titrated to 9, Sears index (the following Sears index V of mensuration modification from 6
2) as the index of free hydroxyl group.
Measuring method comes from following chemical reaction, and wherein " Si "-OH represents silanol groups:
Embodiment
Embodiment
At the general grinding machine M20 of IKA (550W; 2000 rev/mins) in grinding 10.00g moisture content be 5 ± 1% Powdered, spherical or particulate silica, milling time is 60 seconds.Dry or even humidification is regulated moisture content in 105 ℃ loft drier in case of necessity.The silicon-dioxide that the 2.50g that weighs under the room temperature handles so also joins in the 250ml titration bottle, and mixes mutually with the analytical pure level methyl alcohol of 60.0ml.After sample soaks fully, add the 40.0ml deionized water, disperse through 30 seconds with Ultra Turrax T 25 (stir shaft KW-18G, diameter 18mm), its revolution is 18000 rev/mins.Be flushed in the suspension attached to the sample particle on wall of container and the agitator with 100ml deionized water handle, and constant temperature is handled in 25 ℃ of waters bath with thermostatic control.
Adopt buffered soln (pH 7.00 and 9.00) at room temperature to calibrate pH meter (Knick company, model: the 766pH that has temperature sensor counts Calimatic) and pH electrode (combined electrode of Schott company, model N7680).The initial pH value of suspension when at first measuring 25 ℃ with pH meter, then according to the result, regulating the pH value with potassium hydroxide solution (0.1mol/l) or hydrochloric acid soln (0.1mol/l) is 6.00.Reaching pH is that 6.00 o'clock KOH or the ml consumption of HCl should be V mutually
1'.
Be metered into 20.0ml sodium chloride solution (the analytical pure level NaCl of 250.00g is added to 1 liter with deionized water) then.Continuing the KOH titration with 0.1mol/l afterwards, is 9.00 up to pH.The ml consumption of the KOH solution when reaching pH 9.00 should be V mutually
2'.
Subsequently, at first with volume V
1' or V
2' be normalized to the theoretical weight of 1g, and enlarge 5 times, the unit of obtaining is the V of ml/5g thus
1With Sears index V
2All carry out secondary measures at every turn.
The DBP absorption value
DBP absorption value (DBP index) is measuring of expression precipitated silica receptivity, measures as follows according to standard DIN 53601:
Embodiment
Powdered or its moisture content of globular is that the silicon-dioxide of 0-10% (drying is regulated moisture content in 105 ℃ loft drier in case of necessity) is added in the kneading chamber (article number 279061) of Brabender absorptiometer " E " with 12.50g.If particle, adopting sieve fraction is 3.15 to 1mm (stainless steel sift of Retsch company), (with the soft extruding particle of plastic spoon, making it is the sieve of 3.15mm by the aperture).During room temperature, mixing continuously under (rotating speed of kneader impeller is 125 rev/mins), adding phthalic acid dibutyl ester by " Dosimaten BrabenderT 90/50 " speed in mixture with 4ml/ minute.It is very little to mix the power that needs, and this can show by digital indicator.When measuring fast the end, the mixture retrogradation, this power by unexpected increasing shows.When display digit is 600 (swinging moment is 0.6Nm),, close kneader and DBP feed by electrically contacting.Carry synchronous motor and the digital machine coupling of DBP, can read the ml consumption of DBP like this.
Analytical results
The DBP absorption value is calculated according to the DBP consumption that records by following formula by g/100g.The density of DBP is generally 1.047g/ml in the time of 20 ℃.
DBP absorption value g/100g=DBP consumption ml*DBP density g/ml*100/12.5g
The DBP absorption value is defined as anhydrous, exsiccant silicon-dioxide.When using moist precipitated silica, this value is revised by following correction chart.
Modified value corresponding to water-content is added on the DBP value of measuring; For example, 5.8% water-content is meant on the DBP absorption value and adds 33g/100g.
The correction chart of phthalic acid dibutyl ester absorption value-anhydrous-
Measure the humidity of silicon-dioxide
According to this method, after under 105 ℃ dry 2 hours, measure the volatile part (being designated hereinafter simply as " humidity ") of silicon-dioxide according to ISO 787-2.The general overwhelming majority of dry loss stems from water humidity.
Embodiment
In the dry weighing bottle (diameter 8cm, high 3cm) of band ground lid, add Powdered, the spherical or particulate silica of 10g, weighing precision is 0.1mg (balance E).Uncap, dry sample is 2 hours in 105 ± 2 ℃ loft drier.Cover weighing bottle subsequently, during room temperature in there being silica gel to do to cool off in the exsiccator of siccative.Weight analysis determining weight A.
Measure humidity (%) by [(E (g)-A (g))] * 100%/E (g).
Carrying out secondary once more measures.
Measure the calcination loss:
Dry back 1000 ℃ following 2 hours, DIN 55921/3,4, ISO 3262
Measure d50
Measure a size-grade distribution by laser diffraction (Coulter counter)
Instrument:
Laser-diffractometer LS230, Coulter company
Utraschallfinger Bandelin, model HD 2200, have Horn DH 13G
Cooling bath 80ml
Eppendorf transfer pipet 5ml
Centrifuge glass tube, high 7cm, diameter 3cm
Petri dish, high 4cm, diameter 7cm
Vacuum jacketed flask, high 21cm, diameter 4cm
Digital thermometer, precision ± 0.1K
Chemical reagent:
Ethanol, analytical pure level, Merck company
Triton X-100, Merck company
Hexamethyl phosphoric acid sodium, Baker company
Sample is prepared:
Particle is added in the mortar, and the thick particulate mass of crushing need not be ground.
The 1g that weighs is added in the round wall vase of 30ml without aged silicon-dioxide (preparation back 10 days at most at interval), mixes mutually with 20ml dispersion soln (20g hexamethyl phosphoric acid sodium is added to 1000ml with softening water).Sample is put into cooling bath subsequently, and this cooling bath can stop the rapid heating of suspension, supersound process 1 minute (power 20W, pulse 80%).Each silicon-dioxide is prepared into three kinds of dispersion soln samples.
Before in fluid die, adding sample,, suspension is placed the Petri dish that has magnetic stirring apparatus for fear of issuable sedimentation.
Embodiment:
Before beginning to measure, should be with instrument and fluid die preheating 30 minutes and flushing mould (menu bar " control/flushing ") 10 minutes automatically at least.
In the control group of Coulter software, by Menu key " measurement " select File window " calculating optical model " and fixing refractive index (liquid refracting index actual value=1.332; Material refractive index actual value=1.46, set(ting)value=0.1).
In file window " was measured circulation ", regulating pump speed power was 26%, ultrasonic power 3%.Select " adding during the sample ", " before each the measurement " and " during the measurement " ultrasonic key.
In addition, the following keys in the select File window:
Hectograph is measured (lx every day)
Proofread and correct
Background is measured
Regulate and measure concentration
Enter sample information,
Enter metrical information
Beginning 2 times measures
Automatically flushing
Have the PIDS data
Proofread and correct when finishing, add sample.Dispersed silicon dioxide is about 45% up to photoabsorption, and instrument sends OK.
Measure with Fu Lang and expense model, wherein, use the standard software of the laser-diffractometer LS 230 of Coulter company.
The secondary that each adding sample carried out three times 60 seconds is measured.
Can calculate by volume size-grade distribution with software by the raw data curve.
Measure carbon content
Instrument:
Analytical balance
Porcelain boat ware with cover
Tweezers
The metering spoon
Reagent
Euro-analysis-control sample 077-2 (
Instrument company)
Oxygen
Embodiment
Measure control sample
At first measure control sample.For this reason, using the 0.14-0.18g sample of in roasting, refrigerative porcelain boat ware, weighing on the analytical balance.Weigh when bringing into operation, because a day gentle C-mat is a coupled.Must in 30 seconds, the porcelain boat ware be shifted onto the middle part of incendiary pencil.Burning is converted to pulse with observed value after finishing, by computer analysis results.Carry out 2 times or repeatedly measure.Readjust the factor of instrument in case of necessity.According to the following formula calculated factor:
Measure the silicon-dioxide sample
After finding out the factor, measure the silicon-dioxide sample.For this reason, the 0.04-0.05g silicon-dioxide of in the porcelain boat ware, weighing, and cover the porcelain boat ware with porcelain.Be similar to control sample then, measure the silicon-dioxide sample.Deviation＞0.005% o'clock is measured for the third time, takes multiple measurements in case of necessity, and calculating mean value.
Analytical results
Be calculated as follows carbon content:
The definition here: I=pulse
The F=factor
E=weighing (g)
Result's report
Result's %C remembers behind the radix point 2.
Note
According to
The operation instruction operation " C-mat 500 " of instrument company.
Description of drawings
Fig. 1 represents relatively to contain the SH-lacquer of ACEMATTOK412 and contains the opacity that makes the SH-lacquer of matting agent by embodiment 2.
Fig. 2 represents relatively to contain the SH-lacquer of ACEMATTOK412 and contains the opacity that makes the SH-lacquer of matting agent by embodiment 3.
Following examples further specify the present invention, are not that restriction is as the described protection domain of claims.
Embodiment 1-3
Be similar to DE 1767332 preparation silicon-dioxide.
In heatable 120 liters of settling vessels that have a whipping device, add 80 premium on currency, with 5.5 premium on currency glass (density=1.346kg/l, SiO
2Content 27.3%, Na
2O content 7.9%) regulate index of basicity to 20.This test portion is heated to 85 ℃.Under this temperature, precipitate fully.The sulfuric acid (adding speed 45ml/ minute) that adds water glass (adding speed 207ml/ minute) and 50% afterwards simultaneously is so that index of basicity is constant.Connect shear after 30 minutes, further violent stirring precipitates suspension during the precipitation, to such an extent as to precipitate size distribution d50=7 μ m when finishing.After 45 minutes, stop to add water glass and sulfuric acid 30 minutes.And then add water glass and sulfuric acid, and add with speed same as described above.After spending 45 minutes again, stopping the adding of water glass, is 3.5 but add sulfuric acid up to pH.Finish precipitation afterwards.
The described amount of according to the form below once joins organopolysiloxane emulsion (TEGO Foamex 1435, TEGOGmbH company) in the silica suspension subsequently, at elevated temperatures, stirs 30 minutes.Subsequently, it is described to be similar to DE1767332, to the silicon-dioxide of such coating filter, clean, dry, grinding and classification.
Table 1 with three kinds according to the method described above preparation, the silicon-dioxide of surface modification and undressed silicon-dioxide ACEMATT HK 400 (commodity that DEGUSSA company is disclosed, can freely obtain) contrast.The silicon-dioxide that relates among the embodiment 1-3 is handled with the organopolysiloxane of different amounts.
Embodiment 4
By measuring the transmissivity of lacquer, compared the matting agent of matting agent of the present invention and prior art.For this reason, prepare three kinds of lacquer mixtures, wherein, the 2.5g matting agent joined 50g at every turn and have in the SH-lacquer of following common composition:
30.2 weight % dimethylbenzene
15.1 weight % oxyethyl group propyl alcohol
15.1 weight % ethanol
39.6 weight %Plastopal BT, 60% (urea formaldehyde resins contains poly-ammonia
Ester and use short chain alcohol etherificate, BASF
AG company, Ludwigshafen).
Sample is prepared:
In order to measure, at room temperature with the blade stirrer with in 2000 rev/mins of SH-lacquers that in 10 minutes, the 2.5g matting agent are dispersed in the 50g lacquer.In the PE of 180ml mixing beaker, disperse under the room temperature.The blade diameter of stirrer is 43mm.
Measure:
Write down freshly prepd dispersion night 190 and 1100nm between the UV/Vis spectrum of transmission.Measurement is the UV/Vis spectrophotometer Specord 200 that adopts Analytik Jena GmbH company, under the room temperature, in the quartzy colorimetric pool of 1cm, carries out, and with the air reference substance.Wavelength width of a slit and step pitch are 2nm.
By above-mentioned steps, measure the transmission value of lacquer, contain matting agent that obtains by embodiment 2 or 3 or the matting agent ACEMATT OK 412 that applies with PE-wax in these lacquers.ACEMATT OK 412 is commodity that DEGUSSAAG company is disclosed, can freely obtain, corresponding to product information 12/02.In addition, measure the transmission value of the pure lacquer that does not contain matting agent.
The transmission value that obtains is as follows:
As above shown in the table, contain the matting agent of the present invention that obtains by embodiment 2 or 3 lacquer transmission value and pure, the transmission value of the lacquer of delustring is very not approaching.Therefore these lacquers are extremely as clear as crystal.
The transmission value that contains lacquer conventional, widely used matting agent ACEMATT OK 412 will differ from 35% at least, and this shows that lacquer is serious muddy.
Attached Fig. 1 and 2 of back has done contrast to the SH-lacquer that contains the matting agent that is obtained by embodiment 2 or 3 with the identical SH-lacquer that contains ACEMATT OK 412.Can know and find out that the lacquer that contains matting agent of the present invention is limpider basically.
Claims (5)
1. the method for preparing following lacquer: the lacquer that comprises the precipitated silica of surface modification, the precipitated silica of wherein said surface modification has polymkeric substance on its surface, and wherein compare with the described varnish of the contrast precipitated silica that contains useful 5 weight % polyethylene waxs processing, the precipitated silica of described surface modification makes its refractive index n
D20=1.4492 and the transmissivity that contains the varnish of the described silicon-dioxide of 5 weight % improves at least 20%,
Wherein surface modification, hydrophobic precipitated silica obtains and joined in the lacquer formulations by the method that may further comprise the steps,
A) in slightly acidic under alkaline condition, precipitate alkali metal silicate solutions with souring agent,
B) adding souring agent again, to regulate the pH value be from 7 to 2, obtaining silica suspension,
C) filter to isolate precipitated solid, and
D) drying precipitated silicon-dioxide, make product residual water-content less than 10% and
E) use polyether-modified organopolysiloxane or acrylate modified organopolysiloxane or polyacrylate modified organopolysiloxane or poly-oxyalkylsiloxane to handle silica suspension or precipitated silica with one of following method, to obtain the precipitated silica of described surface modification, compare with the described varnish of the contrast precipitated silica that contains useful 5 weight % polyethylene waxs processing, the precipitated silica of described surface modification makes its refractive index n
D20=1.4492 and the transmissivity that contains the varnish of the described silicon-dioxide of 5 weight % improves at least 20%,
E1) organopolysiloxane that 0.5-30 weight % is polyether-modified or acrylate modified organopolysiloxane or polyacrylate modified organopolysiloxane or poly-oxyalkylsiloxane are added in that pH is adjusted in the silica suspension of 7-2 in the step b), joining day is 1 to 30 minute, temperature is 50 to 90 ℃, subsequently, as step c) and d) as described in, the silicon-dioxide of filtration and desiccated surface modification
E2) will be according to step a) and b) precipitated silica that obtains separates through filtration as described in step c), randomly use the isolating precipitated silica of deionized water wash, again water or sulfuric acid or water and vitriolic mixture suspend silicon-dioxide once more, to obtain the suspension that solids content mostly is 25 weight % most, the polyether-modified organopolysiloxane of 0.5-30 weight % or acrylate modified organopolysiloxane or polyacrylate modified organopolysiloxane or poly-oxyalkylsiloxane are joined in the gained suspension, gained suspension spraying drying in spray-dryer, temperature is 200-500 ℃, make the residual water-content of product less than 10%, perhaps
E3) as preparation exsiccant precipitated silica as described in the step a)-d), the polyether-modified organopolysiloxane or acrylate modified organopolysiloxane or polyacrylate modified organopolysiloxane or the poly-oxyalkylsiloxane that in 0 to 120 minute, add 0.5-30 weight %, thorough mixing continued blend mixture 0-2 hour down at 20-150 ℃.
2. according to the method for claim 1, it is characterized in that organopolysiloxane has following formula:
Wherein
Y=-OH ,-OR or
Y=H
5C
2-O-(C
2H
4O)
m-, H
7C
3-O-(C
3H
6O)
m-or
R=alkyl, particularly methyl or ethyl,
R
2=alkyl,
R
3=alkyl,
a＝0-100，b＝0-100，c＝0-100，d＝0-100，
M=0-100, and k=0-100.
3. according to the method for claim 1, it is characterized in that this polymkeric substance is the organopolysiloxane with following general structure:
Wherein
R
1=methyl or
And/or
And unit sum a=0 to 100, unit sum b=0 to 15, wherein, for substituent R
1, when a=0, the ratio of methyl and alkoxyl group is less than 50: 1 and b 〉=1, when b=0, and a 〉=5.
4. according to the method for one of claim 1 to 3, also be included in after silicon-dioxide to surface modification carries out drying, in step f), it is ground.
5. according to the method for claim 1 to 4, it is characterized in that, after the precipitated silica to surface modification carries out drying, after perhaps in step f), grinding or during grinding, diameter is gone out greater than the particle separation of 50 μ m.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10321575.1 | 2003-05-14 | ||
| DE10321575 | 2003-05-14 | ||
| DE102004012090.0 | 2004-03-12 | ||
| DE102004012090A DE102004012090A1 (en) | 2003-05-14 | 2004-03-12 | Surface-modified precipitated silicas |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200410047791XA Division CN1608984A (en) | 2003-05-14 | 2004-05-13 | Surface modified precipitated silica |
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| Publication Number | Publication Date |
|---|---|
| CN102161845A true CN102161845A (en) | 2011-08-24 |
| CN102161845B CN102161845B (en) | 2013-11-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100295752A Expired - Fee Related CN102161845B (en) | 2003-05-14 | 2004-05-13 | Surface-modified precipitated silica |
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| Country | Link |
|---|---|
| CN (1) | CN102161845B (en) |
| DE (1) | DE102004012090A1 (en) |
| MY (1) | MY137950A (en) |
| TW (1) | TWI394714B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359747A (en) * | 2013-06-25 | 2013-10-23 | 安徽敬业纳米科技有限公司 | Method for in situ modification of nano silica in batches |
| CN107674489A (en) * | 2017-11-08 | 2018-02-09 | 北京航天赛德科技发展有限公司 | A kind of sludge proof improved silica and its preparation method and application |
| CN110104655A (en) * | 2019-05-15 | 2019-08-09 | 福建省馨和纳米硅业有限公司 | A kind of preparation process of high-performance silicon dioxide |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009045109A1 (en) | 2009-09-29 | 2011-03-31 | Evonik Degussa Gmbh | Surface-modified semi-gels |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3627782A1 (en) * | 1986-08-16 | 1988-02-18 | Goldschmidt Ag Th | NEW ALKOXYSILOXANES, THE PRODUCTION AND USE THEREOF AS A VENTILATING AGENT FOR curable resins or plastisol |
| DE3815670A1 (en) * | 1988-05-07 | 1990-01-25 | Degussa | FINE-PARTICULATED SOFT SEEDS WITH HIGH STRUCTURE, METHOD FOR ITS MANUFACTURE AND USE |
| DE10138492A1 (en) * | 2001-08-04 | 2003-02-13 | Degussa | Hydrophobic, non-tempered precipitated silica with a high degree of whiteness |
-
2004
- 2004-03-12 DE DE102004012090A patent/DE102004012090A1/en not_active Withdrawn
- 2004-05-07 TW TW093112935A patent/TWI394714B/en not_active IP Right Cessation
- 2004-05-13 MY MYPI20041781A patent/MY137950A/en unknown
- 2004-05-13 CN CN2011100295752A patent/CN102161845B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359747A (en) * | 2013-06-25 | 2013-10-23 | 安徽敬业纳米科技有限公司 | Method for in situ modification of nano silica in batches |
| CN107674489A (en) * | 2017-11-08 | 2018-02-09 | 北京航天赛德科技发展有限公司 | A kind of sludge proof improved silica and its preparation method and application |
| CN110104655A (en) * | 2019-05-15 | 2019-08-09 | 福建省馨和纳米硅业有限公司 | A kind of preparation process of high-performance silicon dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200505790A (en) | 2005-02-16 |
| TWI394714B (en) | 2013-05-01 |
| MY137950A (en) | 2009-04-30 |
| CN102161845B (en) | 2013-11-13 |
| DE102004012090A1 (en) | 2004-12-09 |
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