CN105153992B - It is a kind of using polysiloxane-modified filler and preparation method and application - Google Patents
It is a kind of using polysiloxane-modified filler and preparation method and application Download PDFInfo
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- CN105153992B CN105153992B CN201510531598.1A CN201510531598A CN105153992B CN 105153992 B CN105153992 B CN 105153992B CN 201510531598 A CN201510531598 A CN 201510531598A CN 105153992 B CN105153992 B CN 105153992B
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Abstract
The invention discloses a kind of using polysiloxane-modified filler and preparation method and application.Using the preparation method of polysiloxane-modified filler, include the following steps：Filler is added to by powder feeding device in modifying machine, while polysiloxanes is added to by liquid charging device in the modifying machine, mixes the filler and the polysiloxanes, react to get to described using polysiloxane-modified filler.Or dedicated unit is prepared using polysiloxane-modified filler and is made using the device continuous several times modification of more set series connection.Using polysiloxane-modified applying filler in preparing organic silicon rubber adhesive sealant or the reinforcement as rubber or resin or functional filler.For the present invention by controlling the inlet amount of raw material, the modified effect for making filler is more preferable；It is repeatedly modified by the device of series connection, makes preparation process simply controllable.
Description
Technical field
It is more particularly to a kind of to be changed using polysiloxanes the present invention relates to a kind of filler of modification and preparation method and application
Filler of property and preparation method and application.
Background technology
Organic silicon rubber has the excellent properties such as good high temperature resistant, low temperature resistant, ageing-resistant, thus navigates in electronics, aviation
The high-tech sectors such as it obtain extensive use, but the organic silicon rubber as adhering and sealing materials'use need addition reinforcement fill out
Material could obtain the mechanical property for meeting the requirement of its performance, so that its excellent characteristic is embodied.In silicon rubber
In the most widely used reinforced filling be white carbon, precipitated silica is divided into according to the difference of preparation method and vapor phase method is white
Carbon black, although the preparation process of the two is entirely different, all there are substantial amounts of hydroxyls on surface so that white carbon surface exhibits
Go out strongly hydrophilic, a certain amount of white carbon makes the viscosity of silicon rubber increase rapidly, cause silicon rubber after being mixed with silicon rubber
Processing performance declines or even is not achieved the reinforcing effect of silicon rubber.This just needs dialogue carbon blacksurface to be modified processing, reduces
The hydroxyl quantity on white carbon surface, makes white carbon surface become hydrophobicity from hydrophily, and silicon rubber is made to obtain good reinforcement effect
There is good processing performance, so as to meet the requirement of the performance of silicon rubber adhering and sealing material while fruit.
The surface modification treatment of white carbon is exactly to pass through certain process white carbon using certain modifying agent
Surface hydroxyl react with modifying agent, eliminate or reduce its surface-active hydroxyl, with achieve the purpose that change surface nature.
The process for modifying surface of white carbon can be divided into two classes：One kind is that white carbon is pre-processed using modifying agent, these modifying agent
Liquid or certain including small-molecular-weights such as organophalosilane, siloxanes, silane coupling agent, silazane, titanate esters, stearic acid
The oligosiloxane of molecular weight.The selection of these modifying agent and its corresponding realization are based on for the study on the modification of white carbon
The work of technique expansion optimization, different modifying agent and its corresponding modified technique respectively have its advantage and disadvantage.Using organic halogenation silicon
Substantial amounts of corrosivity can be generated in the technical process of alkane [JP clear 57-30803, EP251176, USP4554147] processing white carbon
Extremely strong hydrogen chloride gas, it is necessary to increase additional acid removal process, and modified technique need at a high temperature of 300~600 DEG C into
Row, energy consumption is high, it is high that the high temperature corrosion of equipment is required.Using siloxanes [Shenyang University of Technology's Master's thesis, 2006], silane
Coupling agent [CN101514263A, CN102220036A], silazane [organosilicon material, 2010 (24)：37-39], titanate esters [should
With chemical industry, 2007 (36)：703-704], oligosiloxane [USP3532664] when modifying agent, though will not in modifying process
The hydrogen chloride gas of severe corrosive is generated, but is needed using high temperature, the pretreating process of long-time heating or a large amount of auxiliary agents of addition
(such as methanol, ethanol water, toluene, dimethylbenzene) is white so as to cause as far as possible with the contact probability on white carbon surface to improve modifying agent
Carbon blacksurface processing is uniform, this results in long processing period, energy consumption high, and the dosage of modifying agent is much larger than theoretical amount, and usually
Also to increase to remove the technical process such as adjuvant used necessary subsequent wash, drying, crushing, with the last handling process
Substantial amounts of adjuvant used waste is generated, thus such processing method is of high cost.Another kind of processing method is by these modifying agent
As a component of silicon rubber adhering and sealing material prescription, used during the kneading, mixed refining process in silicon rubber, such place
Reason method eliminates heat-treatment process, while the dosage of modifying agent is less, but the degree for the treatment of of such method and uniformity have
Limit, is only suitable for the application field relatively low to the performance requirement of silicon rubber adhering and sealing material.Therefore, it is necessary to develop a kind of letter
Just white carbon surface treatment method, treatment process process is easy, efficient, and consume energy low and high treating effect.
In numerous method of modifying of white carbon, core key technology is how to realize uniform point of modifying agent and white carbon
Cloth, this just needs corresponding equipment to realize, at present mostly using high temperature resistant, the reaction kettle kind equipment of resistance to certain pressure
[CN202107542U, organosilicon material, 2010 (24)：37-39], fixed bed, vibrated fluidized bed [Shenyang University of Technology master discuss
Text, 2006], baking oven is [using chemical industry, 2007 (36)：703-704], tube type resistance furnace [chemical industry be in progress, 2005 (24)：1265-
1268], ultrasound or high speed shear disperse [CN102220036A] etc., and the realization of these modified technique methods is required to high temperature
Condition or even substantial amounts of solvent or auxiliary agent is needed to aid in realizing, and be intermittent modified technique, therefore high, the processing effect that consumes energy
Rate is low.How to realize efficient, easy continuous process becomes the difficulty of field of material preparation to handle white carbon or powder stuffing
Point.
In numerous modifying agent of white carbon, as the certain molecular weight generated during the extraordinary silicone product of preparation
Polysiloxanes by-product be a kind of potential, the good white carbon surface modifier of modified effect, but because it is easily by white carbon
Dispersiveness is uneven so that the technique is difficult to realize caused by absorption.The present invention is based on dedicated reforming apparatus, realizes
Polysiloxanes prepares the white carbon of high-quality to the excellent surface modified effect of white carbon, while can be by organosilicon industry
In a large amount of polysiloxanes by-products be utilized, realize the maximization of benefit.
The content of the invention
The object of the present invention is to provide a kind of using polysiloxane-modified filler and preparation method and application, also provide
A kind of dedicated unit being modified using polysiloxane-modified surface, the present invention is easy, dialogue carbon blacksurface efficiently, inexpensive
Processing is modified, so as to provide excellent reinforced filling to prepare high performance organic silicon rubber adhering and sealing material.
It is provided by the invention a kind of using polysiloxane-modified filler preparation method, filler is passed through into powder feeding device
Be added in modifying machine, while polysiloxanes be added to by liquid charging device in the modifying machine, make the filler and
Polysiloxanes mixing, react to get to described using polysiloxane-modified filler；
The filler is white carbon, zinc oxide, aluminium oxide, iron oxide, magnesium hydroxide, aluminium hydroxide, calcium carbonate, sulfuric acid
Barium, kaolin, bentonite, montmorillonite, diatomite, flyash, talcum, vermiculite, glass microsphere, wollastonite, silica flour, mica or
Titanium dioxide.
Another preparation method using polysiloxane-modified filler provided by the invention, includes the following steps：
1) filler is added to by powder feeding device I in modifying machine I, while polysiloxanes is filled by liquid addition
It puts I to be added in the modifying machine I, mixes the filler and the polysiloxanes, reaction, the filler pre-processed；
2) filler of above-mentioned pretreatment by collecting device I is collected, is added to through metering pump III in modifying machine II, simultaneously
The polysiloxanes is added to by liquid charging device II in the modifying machine II, makes the filler of the pretreatment and described
Polysiloxanes mix, react to get to described using polysiloxane-modified filler；
The filler is white carbon, zinc oxide, aluminium oxide, iron oxide, magnesium hydroxide, aluminium hydroxide, calcium carbonate, sulfuric acid
Barium, kaolin, bentonite, montmorillonite, diatomite, flyash, talcum, vermiculite, glass microsphere, wollastonite, silica flour, mica or
Titanium dioxide.
In above-mentioned second method, further included after step 2) and receive the filler of step 2) processing by collecting device II
Collection, is added to through metering pump IV in modifying machine III, while the polysiloxanes is added to by liquid charging device III described
In modifying machine III, make the filler of the processing and polysiloxanes mixing, the step of reaction；
Filler through above-mentioned 3 modifications can also continue to collect by collecting device III, is added to and changes through metering pump V
In property machine IV, while the polysiloxanes is added to by liquid charging device IV in the modifying machine IV, makes the processing
Filler and the polysiloxanes mixing, reaction, obtain the filler of 4 modifications；The filler of 4 modifications can be according to
It is secondary carry out 5,6 ... secondary modification, concretely collecting device III, collecting device IV ... collect, through metering pump VI, meter
Amount pump VII ... be added to modifying machine V, modifying machine VI ... in, make the processing filler and the polysiloxanes mixing,
Reaction.
In the present invention, modified number is 1~6 time, preferably 1~4 time, most preferably 3~4 times.
In above-mentioned two methods, the structural formula of the polysiloxanes is formula I,
In formula I, R1For hydrogen, methyl, ethyl, vinyl, hydroxyl, carboxyl, amino, ketoxime base, methoxy or ethoxy；R2
For hydrogen, methyl, ethyl, propyl, vinyl, phenyl, hydroxyl, methoxyl group, ethyoxyl, trifluoro propyl, cyano or epoxy group；R3For
Hydrogen, methyl, ethyl, propyl, vinyl, phenyl, hydroxyl, methoxyl group, ethyoxyl, trifluoro propyl, cyano or epoxy group；R4For
Hydrogen, methyl, ethyl, propyl, vinyl, phenyl, hydroxyl, methoxyl group, ethyoxyl, trifluoro propyl, cyano or epoxy group；R5For
Hydrogen, methyl, ethyl, propyl, vinyl, phenyl, hydroxyl, methoxyl group, ethyoxyl, trifluoro propyl, cyano or epoxy group；
X and y can be 0~20 positive integer, and be asynchronously 0, concretely 4~8,3~6,2~4 or 2~8；
The molecular weight of the polysiloxanes can be 100~10000, concretely 200,400,800,900 or 200~900；
The white carbon is precipitated silica or fume colloidal silica；
The quality of the filler and the polysiloxanes can be 100：1~20, concretely 100:5、100:10、100:20
Or 100:5~20；
In step 1), modifying agent polysiloxanes can be replaced with to the catalyst needed for modified-reaction, it will by step 1)
Catalyst is uniformly supported on the surface of white carbon；
The catalyst of the reaction is tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutylammonium hydroxide, the tetrabutyl
Phosphonium hydroxide, butyl tin dilaurate, stannous octoate, ethanolamine or triethylamine；The matter of the catalyst and the polysiloxanes
Amount is than that can be 0.01~1：100；
The frequency of the frequency converter of the powder feeding device can be 1~50Hz, concretely 40Hz, 50Hz or 40~
50Hz；
The charging rate of the filler can be 1~1000kg/h, concretely 35kg/h, 40kg/h, 60kg/h, 80kg/h
Or 35~80kg/h；
The frequency of the frequency converter of the liquid charging device be 1~50Hz, concretely 20Hz, 30Hz, 26Hz, 50Hz or
20~50Hz；
The charging rate of the polysiloxanes be 10g/h~10kg/h, concretely 3kg/h, 4kg/h, 3.5kg/h,
8kg/h, 16kg/h or 3~16kg/h；
The time of the reaction is 5s~5min, concretely 40s, 1min or 40s~1min.
In the present invention, the structural formula of the polysiloxanes is concretely such as IV compound represented of following formula II, formula III or formula.
The present invention also provides above method preparation using polysiloxane-modified filler.
The present invention also provides it is above-mentioned using polysiloxane-modified filler prepare organic silicon rubber adhesive sealant or
As the application in the reinforced filling of rubber or resin；The rubber is natural rubber, butyl rubber, ethylene propylene diene rubber, fourth
Nitrile rubber or fluorubber etc.；The resin is epoxy resin, phenolic resin, polyurethane or silicones.
Invention further provides a kind of organic silicon rubber adhesive sealant, it is by organic silicon rubber basis glue and above-mentioned
It is obtained using polysiloxane-modified filler through mediating, being kneaded.
In above-mentioned adhesive sealant, organic silicon rubber basis glue is contracting and type silicon rubber or addition-type silicon rubber；
Organic silicon rubber basis glue can be 100 with the mass ratio for using polysiloxane-modified filler：10~
300, concretely 100：25、100：50 or 100：25~50.
Invention further provides the dedicated units using polysiloxane-modified preparation, it includes powder charging dress
It puts, liquid charging device, modifying machine and collection device；
The powder feeding device includes powder stuffing material pot I and connected metering pump I；
The liquid charging device includes modifying agent material pot II and the metering pump II being attached thereto, and the metering pump I
It is connected with the metering pump II, the metering pump II is connected with the modifying machine；
The collecting device includes the material pot III that is connected with discharge port therewith of collector, the feed inlet of the collector and
The modifying machine is connected, and the collector is also associated with wind turbine and compressor.
In above-mentioned device, drying device and packaging facilities are also sequentially connected after the collection device；
The drying device includes the feeder, fluid desicator, heat exchanger, carrier gas drying machine and the by-product that are sequentially connected
Object storage tank, the heat exchanger and the carrier gas drying machine are also connected with carrier gas reservoir；
The feeder is connected with the material pot III, and the fluid desicator is also connected with material pot IV；
The packaging facilities includes compressing-packing machine and the packaging bag machine being attached thereto；
The compressing-packing machine is connected with the material pot IV.
In above-mentioned device, liquid charging device I, modifying machine I and collection device I are also connected with after the collection device；
Liquid charging device I includes metering pump IV and connected modifying agent material pot V；
The collection device I includes the material pot VI that collector I is connected with discharge port therewith；
Metering pump III, modifying machine I and collector I are sequentially connected after the material pot III；
The metering pump III is also connected with metering pump IV；
The collector I is also associated with wind turbine I and compressor I.
In the present invention, the metering pump I, the metering pump III are screw metering pump；
The metering pump II is plunger type metering pump；
The modifying machine is driven by motor.
The present invention has the following advantages：
Using feed arrangement when the present invention adds in raw material, and polysiloxanes is low-molecular weight polymer, is avoided that device
Wind turbine blows away a part of raw material, avoids the waste of raw material.The present invention is made filler modified by controlling the addition speed of raw material
Degree is controlled, and modified effect is more preferable.The present invention is simple to the method for modifying on the fillers such as white carbon surface, and no high temperature is pre-
Processing, without using substantial amounts of auxiliary agent, washing necessary to auxiliary agent need not be removed, it is dry, the postprocessing working procedures such as crush；Use phase
The processing procedure for the processing unit answered is easy, preparation efficiency is high, at low cost, the large-scale hard charcoal suitable for industrial processes
A variety of powder stuffing surface modification treatments such as black.The present invention is to be generated in organosilicon industry in silicone product preparation process
A large amount of low molecular weight polysiloxane by-products provide a kind of application approach of new high added value, enrich the powders such as white carbon
The modification process of filler.The present invention prepares the white carbon reinforced filling of high added value, is further able to prepare high performance
Organic silicon rubber adhering and sealing material, its preparation method are more easy, efficient, controllable.
Description of the drawings
Fig. 1 is device flow chart in the embodiment of the present invention 1.
It is marked in figure as follows：
1 powder stuffing material pot I, 2,10 and 18 modifying agent material pots II, 3 metering pumps II, 4,11 and 17 screw metering pumps
I, 5,12 and 19 modifying machines, 6,15 and 22 collectors, 7,14 and 21 wind turbines, 8,13 and 20 compressors, 9,16 and 23 material pots III,
24 feeders, 25 fluid desicators, 26 heat exchangers, 27 carrier gas reservoirs, 28 carrier gas drying machines, 29 accessory substance storage tanks, 30 materials
Tank IV, 31 compressing-packing machines, 32 packaging bag machines, 33 and 34 metering pumps III.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1, the dedicated unit using polysiloxane-modified filler
The dedicated unit of polysiloxane-modified filler is used for the present invention as shown in Figure 1, it includes powder feeding device, liquid
Body feeding device, modifying machine and collection device further include drying device to dry modified filler, in order to pack modified filler also
Add packaging facilities.Powder feeding device includes powder stuffing material pot I 1 and connected by motor-driven screw rod
Metering pump I 4, liquid charging device include modifying agent material pot II 2 and the metering pump II 3 (plunger type) being attached thereto, and screw rod
Metering pump I 4 is connected with metering pump II 3, and metering pump II 3 is connected with modifying machine 5.Collection device includes collector and therewith discharge port
Connected material pot, modifying machine 5 are connected with collector 6, and collector 6 is connected with material pot III 9, and wind is also associated on collector 6
Machine 7 and compressor 8.Material pot III 9 is connected with screw metering pump I 11, in order to carry out second of modified, modifying agent to powder stuffing
Material pot II 10 is connected by metering pump III 33 with screw metering pump I 11, adds in modifying agent.Screw metering pump I 11 is with being modified
Machine 12 is connected, and modifying machine 12 is connected with collector 15, is also associated with wind turbine 14 and compressor 13 on collector 15, collector 15 and
Material pot III 16 is connected.Material pot III 16 is connected with screw metering pump I 17, modified in order to carry out third time to powder stuffing, is changed
Property agent material pot II 18 be connected by metering pump III 34 with screw metering pump I 17, add in modifying agent.Screw metering pump I 17 with
Modifying machine 19 is connected, and modifying machine 19 is connected with collector 22, and wind turbine 21 and compressor 20, collector are also associated on collector 22
22 are connected with material pot III 23.In order to which modified powder stuffing is dried, material pot III 23 and feeding in drying device
Machine 24 is connected, and drying device includes the feeder 24, fluid desicator 25, heat exchanger 26, the carrier gas drying machine 27 that are sequentially connected
With accessory substance storage tank 29, heat exchanger 26 and carrier gas drying machine 28 are also connected with carrier gas reservoir 27, and modified is powder-modified
Material pot IV is entered by fluid desicator 25 after the completion of agent drying, enters back into compressing-packing machine 31 in packaging facilities and therewith phase
Packaging bag machine 32 even, packaging are completed.
The method that the above-mentioned device of the present invention is modified powder stuffing surface, includes the following steps：
Processing procedure 1)：White carbon A in material pot I 1 flows to modifying machine 5, while modifying agent object through screw metering pump I 4
Modifying agent a in batch can II 2, which is flowed to through metering pump II 3 after screw metering pump I 4 is mixed with white carbon, flows through modifying machine 5, in motor
Under drive in the processing chamber of modifying machine 5 high-speed rotation, and constantly with processing cavity wall on dense blades collide so that hard charcoal
Black A is uniformly mixed with modifying agent a in continuous random collision process and so that modifying agent a can be adsorbed on the table of white carbon A
On face, if chemical reaction can occur for the activity of the modifying agent a used so as to change the surface functional group of white carbon A when sufficiently high,
If the absorption that physics can occur when not high enough for the activity of the modifying agent a used can also change the surface characteristic of white carbon A, make its work
It sexually revises, the catalysis needed for modified-reaction is replaced with so as to the needs for meeting further surface modification treatment or by modifying agent a
Agent so that catalyst and white carbon A are uniformly supported on the table of white carbon in modifying machine processing chamber during high velocity impact
On face, so as to promote the chemical reaction course of modifying agent and white carbon surface hydroxyl in subsequent processes, reaction institute is reduced
The temperature needed improves modification effect.Enter through this processing procedure acquisition white carbon B under the traction of wind turbine 7 in collector 6
And be blocked and collect under the action of the filter cloth bag on collector top, it will not enter in ambient external environment, so as to fulfill close
Closed operation is collected into material pot III 9 under the airflow functions that can be provided in compressor 8 of white carbon B that filter cloth bag adsorbs, real
The one-time surface for having showed white carbon is modified；
Processing procedure 2)：White carbon B in material pot III 9 flows to modifying machine 12, while modifying agent through screw metering pump I 11
Modifying agent b in material pot II 10 flows to modifying machine 12 through metering pump III 33, in the processing chamber of modifying machine 12 under motor drive
Interior high-speed rotation, and constantly collided with the dense blades in processing cavity wall so that white carbon B and modifying agent b is in continuous nothing
It is uniformly mixed in regular collision process and modifying agent b can be adsorbed on the surface of white carbon B, if the modifying agent b used
Chemical reaction can occur for activity so as to change the surface functional group of white carbon B when sufficiently high, if the activity of the modifying agent b used is not
The absorption of physics can occur when enough high can also change the surface characteristic of white carbon B, make its activity change, so as to meet further table
The needs of face modification enter in collector 15 and are being received under the traction of wind turbine 14 through this processing procedure acquisition white carbon C
It is blocked and collects under the action of the filter cloth bag on storage top, will not enter in ambient external environment, so as to fulfill closed-loop operation,
Material pot III 16 is collected under the airflow function that can be provided by the white carbon C that filter cloth bag adsorbs in compressor 13, is realized
Second of modification of white carbon；
Processing procedure 3)：White carbon C in material pot III 16 flows to modifying machine 19 through screw rod screw metering pump I 17, simultaneously
Modifying agent c in modifying agent material pot II 18 flows to modifying machine 19 through metering pump III 34, in modifying machine 19 under motor drive
High-speed rotation in processing chamber, and constantly collided with the dense blades in processing cavity wall so that white carbon C and modifying agent c is not
It is uniformly mixed in disconnected random collision process and modifying agent c can be adsorbed on the surface of white carbon C, if the modification used
Chemical reaction can occur for the activity of agent c so as to change the surface functional group of white carbon C when sufficiently high, if the modifying agent c used
The absorption that physics can occur when not high enough for activity can also change the surface characteristic of white carbon C, make its activity change, so as to meet into
The needs of one step surface modification treatment enter under the traction of wind turbine 21 in collector 22 through this processing procedure acquisition white carbon D
And be blocked and collect under the action of the filter cloth bag on collector top, it will not enter in ambient external environment, so as to fulfill close
Closed operation is collected into material pot III 23 under the airflow functions that can be provided in compressor 20 of white carbon D that filter cloth bag adsorbs,
Realize the third time modification of white carbon；
According to the modification effect requirements on white carbon surface, above-mentioned processing procedure can be increased or decreased, that is,
The number of this processing procedure is comprehensively considered according to modified effect and the cost factors such as the artificial, raw material consumed and water, electricity and gas
To determine；
Processing procedure 4)：The white carbon D collected in material pot III 23 is after feeder 24 enters fluid desicator 25, by carrying
Processing or chemical reaction post processing is dried in carrier gas under the heating of the heating system of fluid desicator 25 in gas storage tank 27
And the issuable by-product of discharge, carrier gas carry out the heat exchange of cold carrier gas and hot carrier gas in heat exchanger 26, save heat
The carrier gas efficiency of heating surface is improved while energy, is dried by the hot carrier gas of fluid desicator 25 after heat exchanger 26 into carrier gas
Machine removes and carrier gas reservoir 27 is returned to after the small molecule by-product of carrying, and the by-product of small molecule it is condensed after can be recycled to pair
It is collected in product reservoir 29, prevents from discharging small molecule by-product to air, in order to avoid environmental pollution is caused, and white carbon D is passing through
Generation white carbon E enters material pot IV 30 after dry or subsequent heating reaction；
Processing procedure 5)：White carbon in material pot IV 30 by compressing-packing machine 31 through can be measured after the assay was approved
After be put into packaging bag 32 and packed.
Embodiment 2, precipitated silica modification and the preparation of condensed type silicon rubber adhesive sealant
Using device in the embodiment of the present invention 1, precipitated silica surface is modified and only carries out processing procedure in embodiment 1
1), precipitated silica (Z-142) enters modification through powder feeding device in the case where frequency converter is 50Hz with the rate of 40kg/h
Machine exists with the hydrogen containing siloxane (value of x and y are 4~8, average molecular weight 800) shown in up-to-date style II through liquid charging device
Frequency converter is under 30Hz, enters modifying machine with the rate of 4kg/h, and it is 100 to control the inventory of white carbon and hydrogen containing siloxane:
10, under room temperature (25 DEG C), the two is reacted in modifying machine, and reaction time 40s is collected by collecting device after processing, adopted
With the white carbon of polysiloxane-modified 1 time.
Using the condensed type silicon rubber of 5000cps and the white carbon of above-mentioned processing, the two is according to 100：25 proportioning kneading,
After mixing, condensed type silicon rubber adhesive sealant is obtained.The viscosity of condensed type silicon rubber adhesive sealant of the present invention is 140,000
Cps, no contact metamorphism；And the precipitated silica without above-mentioned processing in comparative example adds in condensed type silicon under same formula
In rubber, viscosity is 220,000 cps, and there are contact metamorphisms.
Embodiment 3, precipitated silica modification and the preparation of condensed type silicon rubber adhesive sealant
Using device in the embodiment of the present invention 1, the precipitated silica that the embodiment of the present invention 2 is obtained carries out embodiment 1
Middle processing procedure 2) or process repeats 2) repeatedly processing.The precipitated silica that the embodiment of the present invention 2 is obtained passes through again
Powder feeding device is 50Hz in frequency converter, enters modifying machine in screw metering pump with the rate of 35kg/h, shown in up-to-date style II
Hydrogen containing siloxane (value of x and y be 4~8, average molecular weight 800) through liquid charging device in the case where frequency converter is 26Hz,
Entered with the rate of 3.5kg/h in modifying machine, it is 100 to control the ratio of white carbon and hydrogen containing siloxane:10, the two is modified
It reacts after (25 DEG C) mixing of machine room temperature, after reacting 40s, is collected after processing by collecting device, obtain hydrogen containing siloxane processing 2
Secondary white carbon；The white carbon of 2 processing of gained is again introduced into modifying machine at the same rate, uses same hydrogeneous poly- silicon
Oxygen alkane is again introduced into modifying machine at the same rate, and it is 100 to control the ratio of white carbon and hydrogen containing siloxane:10, through room temperature
After hybrid reaction 40s, collect and obtain the white carbon that the hydrogen containing siloxane handles 3 times；And so on, repeatedly obtained respectively after processing
To hydrogen containing siloxane processing 4 times, the white carbon of 5 times.With each processing, the modification degree on white carbon surface is progressively complete
Entirely, it can obtain the precipitated silica of different modification degrees.
Using the condensed type silicon rubber and above-mentioned 2 times, 3 times, 4 times, 5 times treated white carbon of 5000cps according to 100：
25 proportioning mediates, be kneaded after, the viscosity that obtains condensed type silicon rubber adhesive sealant be respectively 7.5 ten thousand cps, 6.2 ten thousand cps,
4.9 ten thousand cps and 3.1 ten thousand cps, without contact metamorphism；The condensed type silicon rubber adhesive sealant of gained is handed over through 5 parts of polysilazanes
After joining agent curing, tensile strength is respectively 2.23MPa, 2.34MPa, 2.45MPa and 2.25MPa, and elongation at break is respectively
230%th, 250%, 267% and 240%.And the white carbon without above-mentioned processing in comparative example adds in condensation under same formula
In type silicon rubber, viscosity is 220,000 cps, and there are contact metamorphisms.
Embodiment 4, fume colloidal silica modification and the preparation of condensed type silicon rubber adhesive sealant
Using device in the embodiment of the present invention 1, fume colloidal silica surface, which is modified, only carries out processing procedure in embodiment 1
1), fume colloidal silica (150P) is through powder feeding device in the case where frequency converter is 40Hz, and screw metering pump is with the rate of 35kg/h
Into modifying machine, with hydrogen containing siloxane (x and y values are respectively 4~8, average molecular weight 800) warp of structure shown in up-to-date style II
Liquid charging device under 26Hz, to enter modifying machine with the rate of 3.5kg/h, controls fume colloidal silica and hydrogeneous in frequency converter
The ingredient proportion of polysiloxanes is 100：10, the modified machine of the two mixes under room temperature (25 DEG C), after reacting 1min, is set by collection
Standby collect obtains the fume colloidal silica that the hydrogen containing siloxane is modified 1 time.
Using the condensed type silicon rubber of 5000cps and the white carbon of above-mentioned processing according to 100：25 proportioning is mediated, is kneaded
Afterwards, the viscosity of condensed type silicon rubber adhesive sealant is obtained as 250,000 cps, and there are contact metamorphisms for rubber compound, it is impossible to flow；And not
White carbon through above-mentioned processing can not be added under same formula in the condensed type silicon rubber.
Embodiment 5, fume colloidal silica modification and the preparation of condensed type silicon rubber adhesive sealant
Using device in the embodiment of the present invention 1, fume colloidal silica surface, which is modified, carries out processing procedure 2 in embodiment 1) or
To the device process repeats 2 of consecutive) repeatedly.Embodiment 4 is handled to the fume colloidal silica of 1 time to feed through powder again
Device is 50Hz in frequency converter, enters modifying machine with the rate of 35kg/h, with hydrogen containing siloxane (x the and y values shown in up-to-date style II
Respectively 4~8, average molecular weight 800) through liquid charging device in the case where frequency converter is 26Hz, entered with the rate of 3.5kg/h
Modifying machine, it is 100 to control the ratio of white carbon and hydrogen containing siloxane:10, it is anti-after (25 DEG C) mixing of the modified machine room temperature of the two
Should, it after reacting 40s, is collected after processing by powder collecting device, obtains the white carbon that the hydrogen containing siloxane handles 2 times；By institute
The white carbons for obtaining 2 processing are again introduced into modifying machine at the same rate, using same hydrogen containing siloxane with same speed
Rate is again introduced into modifying machine, and it is 100 to control the ratio of white carbon and hydrogen containing siloxane:10, through room temperature (25 DEG C) hybrid reaction
After 40s, collect and obtain the white carbon that the hydrogen containing siloxane handles 3 times；And so on, it is hydrogeneous repeatedly this to be respectively obtained after processing
Polysiloxanes handles 4 times, the white carbon of 5 times.With each processing, the modification degree on white carbon surface is progressively complete, can obtain
To the fume colloidal silica of different modification degrees.
Using the condensed type silicon rubber and above-mentioned 2 times, 3 times, 4 times, 5 times treated white carbon of 5000cps according to 100：
25 proportioning is mediated, after mixing, obtains the viscosity of condensed type silicon rubber adhesive sealant to be respectively 180,000 cps, 110,000 cps, 9
Ten thousand cps and 80,000 cps, with the increase of number of processes, the contact metamorphism of rubber compound mitigates, the prepared mixing after handling four times
Glue can be very good to flow；And the white carbon without above-mentioned processing can not be added to the condensed type silicon under same formula
In rubber.The silicon rubber adhesive sealant of the fume colloidal silica through above-mentioned processing 3 times and 5 times in this formula passes through in the present invention
After 5 parts of polysilazane crosslinking agents cure, tensile strength is respectively 2.6MPa and 2.8MPa, and elongation at break is respectively 250% He
300%.
Embodiment 6, precipitated silica modification and the preparation of condensed type silicon rubber adhesive sealant
Using device in the embodiment of the present invention 1, precipitated silica surface, which is modified, carries out processing procedure 1 in embodiment 1)-
2) or process 3 is continued with) i.e. reprocessing is 2) repeatedly.Precipitated silica (Z-142) is through powder feeding device in frequency converter
Under 50Hz, to enter modifying machine with the rate of 40kg/h, while during winning new material company system with Jiangxi silicon for containing hydrogen silicone oil
(trade mark 706, main component are hydrogen containing siloxane shown in formula II to the bottom material of generation, and 2~4, molecular weight exists for the value of wherein x and y
300) through liquid charging device in frequency converter under 50Hz, to enter modifying machine with the rate of 8kg/h, control white carbon and hydrogeneous poly-
The inventory of siloxanes is 100:20, under room temperature (25 DEG C), the modified machine mixing of the two, reaction time 1min, after processing
It is collected by powder collecting device, obtains being modified the white carbon of 1 time using the hydrogen containing siloxane.
It is again 50Hz in frequency converter through powder feeding device by the above-mentioned modification white carbon of 1 time, with the rate of 35kg/h
Into modifying machine, with the hydrogen containing siloxane shown in up-to-date style 2 through liquid charging device in the case where frequency converter is 42Hz, with 7kg/h's
Rate enters modifying machine, and it is 100 to control the ratio of white carbon and hydrogen containing siloxane:20, after the modified machine mixed at room temperature of the two
Reaction after reacting 1min, is collected after processing by powder collecting device, obtains the white carbon that the hydrogen containing siloxane handles 2 times；It will
The white carbon of 2 processing of gained is again introduced into modifying machine at the same rate, using same hydrogen containing siloxane with same
Rate is again introduced into modifying machine, and it is 100 to control the ratio of white carbon and hydrogen containing siloxane:20, react 1min through mixed at room temperature
Afterwards, collect and obtain the white carbon that the hydrogen containing siloxane handles 3 times；And so on, it is hydrogeneous poly- that this is repeatedly respectively obtained after processing
Siloxane treated 4 times, 5 times, the white carbon of 6 times.It is to be added to 4 modified filler collections when 5 times or 6 times modified
In the powder feeding device of unmodified filler, then carry out multiple modification.With each processing, the modification on white carbon surface
Degree is progressively complete, can obtain the precipitated silica of different modification degrees.
It is obtained for 2 times, 3 times, 4 times, 5 times and 6 times through processing procedure with above-mentioned respectively using the condensed type silicon rubber of 5000cps
White carbon is according to 100：25 proportioning is mediated, is kneaded, and the viscosity for obtaining condensed type silicon rubber adhesive sealant is respectively 200,000
Cps, 150,000 cps, 9.8 ten thousand cps, 7.6 ten thousand cps, 4.8 ten thousand cps, with white carbon processing pass increase, under viscosity is apparent
Drop, can reach preferable treatment effect.25 parts of additions of precipitated silica that the present invention is obtained through 6 processing procedures
The condensed type silicon rubber of 5000cps prepares corresponding silicon rubber adhesive sealant, and the silicon rubber adhesive sealant of gained is through 5 parts
After polysilazane crosslinking agent cures, tensile strength 2.4MPa, elongation at break 210%.The processing method effectively utilizes
The bottom material by-product generated in containing hydrogen silicone oil preparation process, while enrich the surface treatment means of white carbon, realize money
The comprehensive utilization in source.
Embodiment 7, nano-calcium carbonate surface treatment and silicon rubber adhesive sealant
Using device in the embodiment of the present invention 1, nano-calcium carbonate through powder feeding device in the case where frequency converter is 50Hz, with
The rate of 80kg/h enters modifying machine, and (value of wherein x and y are put down 3~6 for hydrogeneous epoxy based polysiloxane shown in up-to-date style III
Average molecular weight enters modifying machine, control is white 900) through liquid charging device in the case where frequency converter is 50Hz with the rate of 16kg/h
The inventory of carbon black and hydrogen containing siloxane is 100:20, under room temperature (25 DEG C), the mixing of the two modified machine, the reaction time is
1min is collected after processing by powder collecting device, obtains the nano-calcium carbonate using polysiloxane-modified 1 time of the hydrogeneous epoxy group
Calcium.
Using the condensed type silicon rubber of 4000cps and the calcium carbonate of above-mentioned processing, the two is according to 100：50 proportioning kneading,
After mixing, condensed type silicon rubber adhesive sealant is obtained.The viscosity of condensed type silicon rubber adhesive sealant of the present invention is 150,000
Cps, after 5 parts of polysilazane crosslinking agent room temperature curings, tensile strength 2.4MPa, elongation at break 120%.
Embodiment 8, magnesium hydroxide surface treatment and flame retardant type silicon rubber adhesive sealant
Magnesium hydroxide, in the case where frequency converter is 50Hz, enters modifying machine, simultaneously through powder feeding device with the rate of 60kg/h
(2~4,400) average molecular weight is filling the value of wherein x and y hydrogeneous vinyl polysiloxane shown in formula IV through liquid addition
It puts in the case where frequency converter is 20Hz, modifying machine is entered with the rate of 3kg/h, the inventory for controlling white carbon and hydrogen containing siloxane is
100:5, under room temperature (25 DEG C), the modified machine mixing of the two, reaction time 1min is received after processing by powder collecting device
Collection obtains being modified the magnesium hydroxide of 1 time using the hydrogeneous vinyl polysiloxane.
Using the silicon rubber of 50000cps and the magnesium hydroxide of above-mentioned processing, the two is according to 100：50 proportioning mediates, is mixed
After refining, flame retardant type silicon rubber adhesive sealant is obtained.Through 5 parts of 160 DEG C of 2.5- dimethyl -2.5- two (tert-butyl hydroperoxide) hexanes
After curing, limit oxygen index 35, tensile strength 6.0MPa, elongation at break 480%.
Comparative example,
Using the condensed type silicon rubber and precipitated silica of 5000cps, the two is according to 100：25 mass ratio through mediate,
After mixing, condensed type silicon rubber adhesive sealant is obtained.The viscosity of condensed type silicon rubber adhesive sealant is 220,000 cps, is existed
Contact metamorphism.
Claims (8)
1. a kind of preparation method using polysiloxane-modified filler includes the following steps：
Filler is added to by powder feeding device in modifying machine, while polysiloxanes is added to by liquid charging device
In the modifying machine, the filler and the polysiloxanes are mixed, reacts and is filled out to get to described using polysiloxane-modified
Material；
The filler is white carbon, zinc oxide, aluminium oxide, iron oxide, magnesium hydroxide, aluminium hydroxide, calcium carbonate, barium sulfate, height
Ridge soil, bentonite, montmorillonite, diatomite, flyash, talcum, vermiculite, glass microsphere, wollastonite, silica flour, mica or titanium white
Powder；
The structural formula of the polysiloxanes is formula II, formula III or formula IV；
In formula II, formula III or formula IV, x and y are 0~20 positive integer, and are asynchronously 0；
The molecular weight of the polysiloxanes is 100~10000；
The white carbon is precipitated silica or fume colloidal silica；
The quality of the filler and the polysiloxanes is 100：1~20；
The frequency of the frequency converter of the powder feeding device is 1~50Hz；
The charging rate of the filler is 1~1000kg/h；
The frequency of the frequency converter of the liquid charging device is 1~50Hz；
The charging rate of the polysiloxanes is 10g/h~10kg/h；
The time of the reaction is 5s~5min.
2. method described in claim 1 prepare using polysiloxane-modified filler.
3. a kind of preparation method using polysiloxane-modified filler includes the following steps：
1) filler is added to by powder feeding device I in modifying machine I, while polysiloxanes is passed through into liquid charging device I
It is added in the modifying machine I, mixes the filler and the polysiloxanes, reaction, the filler pre-processed；
2) filler of above-mentioned pretreatment by collecting device I is collected, is added to through metering pump III in modifying machine II, while by institute
It states polysiloxanes to be added in the modifying machine II by liquid charging device II, makes the filler of the pretreatment and the poly- silicon
Oxygen alkane mix, react to get to described using polysiloxane-modified filler；
It is further included after step 2) and collects the filler of step 2) processing by collecting device II, modification is added to through metering pump IV
In machine III, while the polysiloxanes is added to by liquid charging device III in the modifying machine III, makes the processing
The step of filler and polysiloxanes mixing, reaction；
The filler is white carbon, zinc oxide, aluminium oxide, iron oxide, magnesium hydroxide, aluminium hydroxide, calcium carbonate, barium sulfate, height
Ridge soil, bentonite, montmorillonite, diatomite, flyash, talcum, vermiculite, glass microsphere, wollastonite, silica flour, mica or titanium white
Powder；
The structural formula of the polysiloxanes is formula II, formula III or formula IV；
In formula II, formula III or formula IV, x and y are 0~20 positive integer, and are asynchronously 0；
The molecular weight of the polysiloxanes is 100~10000；
The white carbon is precipitated silica or fume colloidal silica；
The quality of the filler and the polysiloxanes is 100：1~20；
The frequency of the frequency converter of the powder feeding device is 1~50Hz；
The charging rate of the filler is 1~1000kg/h；
The frequency of the frequency converter of the liquid charging device is 1~50Hz；
The charging rate of the polysiloxanes is 10g/h~10kg/h；
The time of the reaction is 5s~5min.
4. preparation method according to claim 3, it is characterised in that：Polysiloxane-modified dose can be replaced in step 1)
Promote the catalyst of surface modification reaction, by the processing procedure of step 1), catalyst can be uniformly supported on to white carbon table
On face, the homogeneity of catalytic reaction is realized；
The catalyst of the reaction is tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutylammonium hydroxide, tetrabutyl hydrogen-oxygen
Change phosphorus, butyl tin dilaurate, stannous octoate, ethanolamine or triethylamine；
The mass ratio of the catalyst and the polysiloxanes is 0.01~1：100.
5. method described in claim 3 or 4 prepare using polysiloxane-modified filler.
6. claim 2 or 5 is described to prepare organic silicon rubber adhesive sealant or conduct using polysiloxane-modified filler
Application in the reinforced filling of rubber or resin.
7. a kind of organic silicon rubber adhesive sealant, it is characterised in that：It is by organic silicon rubber basis glue and claim 2 or 5
It is described to be obtained using polysiloxane-modified filler through mediating, being kneaded.
8. adhesive sealant according to claim 7, it is characterised in that：Organic silicon rubber basis glue is contracting and type silicon
Rubber or addition-type silicon rubber；
Organic silicon rubber basis glue uses the mass ratio of polysiloxane-modified filler as 100 with described：10~300.
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| EP3425009A1 (en) * | 2017-07-05 | 2019-01-09 | Venator Germany GmbH | Surface modified barium sulfate particles and their use |
| CN107553767A (en) * | 2017-10-10 | 2018-01-09 | 广东普赛达密封粘胶有限公司 | A kind of serialization moisture curable polyurethane composition production line and its production method |
| CN108659580B (en) * | 2018-04-03 | 2019-11-08 | 中国科学院化学研究所 | A kind of apparatus and method of the organic silicon byproduct processing filler with silica structure |
| WO2020168542A1 (en) * | 2019-02-22 | 2020-08-27 | 湖州五爻硅基材料研究院有限公司 | Method for preparing spherical or angular powder filler, spherical or angular powder filler obtained thereby and application thereof |
| CN113717662A (en) * | 2021-09-24 | 2021-11-30 | 深圳市美之电实业有限公司 | Waterproof adhesive and preparation method thereof |
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| CN103146232A (en) * | 2013-03-18 | 2013-06-12 | 潍坊埃尔派粉体技术设备有限公司 | Intensive powder surface modification device and production technology thereof |
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| CN101479342A (en) * | 2006-06-26 | 2009-07-08 | 陶氏康宁公司 | Preparation of silicone rubber elastomers |
| CN103146232A (en) * | 2013-03-18 | 2013-06-12 | 潍坊埃尔派粉体技术设备有限公司 | Intensive powder surface modification device and production technology thereof |
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