CN108264651B - Process for the preparation of substantially spherical reaction complexes of sulfur-containing silanes with carbon black and products obtained by said process - Google Patents
Process for the preparation of substantially spherical reaction complexes of sulfur-containing silanes with carbon black and products obtained by said process Download PDFInfo
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Abstract
The invention provides a method for preparing a substantially spherical reaction compound of sulfur-containing silane and carbon black, which uses the sulfur-containing silane and the carbon black for rubber as raw materials, adopts a conical single-spiral reaction mixer to mix firstly to form spherical premixed particles, then forms reaction compound in vacuum, and obtains the spherical particle reaction compound with a certain particle size through vibration sieve classification. The invention has the advantages of simple production equipment, full contact reaction of sulfur-containing silane and carbon black, proper particle size, good use dispersibility and good use effect, is suitable for preparing the carbon black granules for the tire rubber at present and is suitable for large-scale industrial production.
Description
Technical Field
The present invention relates generally to silane coupling agents, and more particularly, to a method for preparing substantially spherical reactive composites of sulfur-containing silanes and carbon black, and the composites prepared by the method.
Background
The carbon black is an aggregate with a specific structure formed by aggregating a plurality of carbon black primary particles with a nearly nanometer scale, the primary particles formed by the aggregate have stronger hardness, and the aggregate has rich specific surface and more reactive groups such as active hydroxyl groups. In the existing rubber industry, carbon black is commonly used as a reinforcing material for rubber, and can be used for improving the tensile strength, the tear strength and the wear resistance of tire rubber. In the tire rubber, if the carbon black is directly mixed with the rubber compound, the compatibility is poor due to the large difference in properties such as surface polarity between the carbon black and the rubber compound. In order to improve the compatibility of carbon black and rubber compounds, a common method in the industry is to add a sulfur-containing silane coupling agent, react with hydroxyl on the surface of the carbon black for condensation crosslinking by virtue of alkoxy of the sulfur-containing silane, and break bonds of polysulfide groups in the sulfur-containing silane and simultaneously react with sulfur bonds in rubber for crosslinking, so that the sulfur-containing silane firmly combines carbon black particles and rubber structural units together under the action of a molecular bridge, thereby greatly improving the reinforcing effect of the carbon black in tread rubber.
Silane coupling agents used in the rubber industry to advantage are sulfur-containing silanes or sulfur-containing organosilicon compounds, which generally have the following general formula:
Z‐Alk‐Sn‐Alk‐Z，
wherein Alk is an alkyl group, n represents the number of sulfur atoms connected in the middle, and the terminal groups Z on both sides have the formula Si (R)1R2R3) (ii) a Wherein R is1、R2And R3And each is an alkoxy group having the same or different carbon number, and the Si atom is further bonded to a carbon atom in the alkyl Alk group. An exemplary sulfur-containing silane is bis- [3- (trialkoxysilyl) -propyl]-tetrasulfide or bis- [3- (trialkoxysilyl) -propyl]-a disulfide.
In the rubber industry, tire compounds are generally mixed with carbon black by means of high-temperature mixing in an internal mixer, wherein for the convenience of handling and use, carbon black and sulfur-containing silane are often mixed in a certain proportion, for example, in a mass ratio of 1:1, to form a premix, and the premix is then fed into the internal mixer for mixing with rubber during the mixing of the compounds. For example, the national Standard GB/T30309-20163 of the people's republic of China is established for silane coupling agents which are mixtures of bis- [ propyltriethoxysilyl ] -tetrasulfide (or bis- [3- (triethoxysilyl) -propyl ] -disulfide) and carbon black.
One of the biggest problems in the early days of operating conditions with sulfur-containing silanes and carbon black is the potential safety hazard caused by dust. To overcome the dust safety problem, it is common to prepare a sulfur-containing silane and carbon black premix, and in the conventional technical route for preparing a sulfur-containing silane and carbon black premix, a screw extrusion granulator is basically used to produce a mixture of the silane coupling agent and carbon black. The production process comprises the following steps: firstly, mixing carbon black and sulfur-containing silane according to a mass ratio of 1:1, then adding a small amount of adhesive or polymer to be uniformly mixed, then adding the mixture into a screw extrusion granulator, and carrying out rotary extrusion and granulation through a screw to obtain a mixture product. Due to the essential principle of screw extrusion granulation, the carbon black and the sulfur-containing silane which are melted and mixed uniformly pass through a die head of an extruder under the pressure of forward conveying of the extruder, extruded material strips are cut by a cutter of a rotating granulator which is arranged at a certain distance away from the die head, and the cut granules are naturally cooled to obtain the product. Although depending on the die design of the extruder, the resulting product is generally cylindrical, typically 3-4 mm in diameter and 8-10 mm in length, or a product of a close particle size specification. In addition, if the die is designed to have an oval interface, the resulting strands may also be oval in cross-section in nature, but the mixture of sulfur-containing silane and carbon black obtained by extrusion granulation in a screw extruder is a cylindrical product having a cross-sectional shape such as a circle or an oval. As substantially described in the utility model CN 2623689Y.
The mixture of sulfur-containing silane and carbon black produced by the method overcomes the defect of dust generation in the mixing process of the sulfur-containing silane, the carbon black and the rubber compound at the earliest stage when in use, but has the following obvious defects. Firstly, the granules of the mixture produced by the method are large, which is determined by the nature of extrusion granulation, so that the mixture is not easy to disperse when mixed with rubber compounds in an internal mixer, thereby prolonging the mixing time; secondly, in order to maintain the stability of the appearance structure of the product, a small amount of adhesive or special polymer is usually added into the formula, and the additive has potential adverse effects on the components and the structure of the rubber mixing product; and thirdly, in the screw extrusion process, due to the fact that the temperature of the mixed materials is high and the speed is high, the self hydrolytic crosslinking of the sulfur-containing silane is easily caused, and meanwhile, the condensation reaction amount of the sulfur-containing silane and carbon black is reduced, so that the coupling effect of the sulfur-containing silane and the carbon black is reduced. Finally, in the process of screw extrusion granulation, the pressure born by the carbon black material is also larger, which is easy to destroy the particle structure of the carbon black aggregate and also reduces the reinforcing effect of the carbon black.
Therefore, there is a continuing need in the market for further improving the composition and morphology of silane coupling agents comprised of carbon black solids and sulfur-containing silane liquids so that the resulting coupling agent product is further advantageous for compounding with rubber.
Disclosure of Invention
The object of the present invention is to overcome all the above-mentioned disadvantages of the prior art. The present invention is directed to a method of preparing a substantially spherical reaction complex of a sulfur-containing silane and carbon black, and to a substantially spherical reaction complex of a sulfur-containing silane and carbon black prepared by the method.
The present inventors have surprisingly found that the process can be carried out simply by controlling the order of addition, the rotational speed during addition, the addition time, the system temperature, etc. by means of a conical single-screw reaction mixer with a temperature control device to give a substantially spherical reaction premix, which is then reacted by stirring at elevated temperature, the low-boiling substances such as alcohol formed by the reaction are removed by applying vacuum, and then a substantially spherical reaction complex of sulfur-containing silane and carbon black having a diameter of about 0.8 to 2.5mm is obtained by sieving and separating.
Specifically, the present invention provides a method of producing a reactive composite of a sulfur-containing silane liquid and carbon black, said method comprising the steps of:
(A) feeding carbon black solids and a sulfur-containing silane liquid in portions in two stages in a conical single-screw reaction mixer with a temperature-controlled jacket, wherein in the first stage 60 to 90% by weight, preferably 70 to 80% by weight, based on the total weight of the carbon black, of carbon black is initially introduced at a first stirring speed, and thereafter the entire sulfur-containing silane is added at a constant rate while stirring the carbon black while maintaining the first stirring speed, to obtain a reaction premix, optionally further stirring at the first stirring speed, for example for 5 to 10 minutes, at the end of the introduction of the sulfur-containing silane liquid, wherein during the introduction of the sulfur-containing silane liquid and optionally during the further stirring, the first stirring speed and the rate of introduction of the sulfur-containing silane are controlled such that the temperature of the premix is maintained between 35 and 45 ℃; then stopping stirring, starting the cooling liquid in the jacket, and standing the mixed material, for example, for 1 to 3 hours, preferably for 2 to 3 hours, so that the inside of the carbon black particles can fully absorb the liquid sulfur-containing silane and can fully contact with the hydroxyl on the surface of the carbon black; and then restarting stirring, adding the rest amount of carbon black at a second stirring rotating speed, and continuing to stir the premix at the second stirring rotating speed after all the carbon black is added, wherein the second stirring rotating speed ensures that the temperature of the materials during the stirring does not exceed 30 ℃ until a substantially spherical reaction premixed crude product is formed, and the rotating speed ratio of the first stirring rotating speed to the second stirring rotating speed is 3: 1 to 5: 1;
(B) continuously controlling the stirring speed of the reaction mixer at a second stirring speed, vacuumizing the reaction mixer by a vacuum device, controlling the vacuum degree to be more than-0.096 MPa, then heating the materials in the mixer, preferably introducing steam and the like through a jacket to ensure that the temperature of the materials reaches 80-98 ℃, preferably 86-94 ℃, and stirring and reacting under the vacuum condition, for example, reacting for 15-30 hours, preferably for 16-22 hours, and preferably recovering low-boiling-point alcohol generated by the reaction by a low-temperature condensing device during the reaction; then cooling the material by introducing cooling liquid through a jacket, and stopping vacuum, stirring and cooling after the temperature of the material is reduced to below 35 ℃, thereby obtaining a reaction compound crude product with a spherical appearance;
(C) and classifying the crude compound through a vibrating screen to obtain the finished product of the compound of the sulfur-containing silane liquid and the carbon black solid in a basically spherical shape.
In the above-mentioned step (A), it is important to control the temperature of the mixed materials in the first stage to be in the range of 35 to 45 ℃ because the temperature rise is caused by the exothermic heat of reaction and frictional heat generation upon stirring the carbon black solid and the sulfur-containing silane liquid; controlling the temperature at this time within the above range is very important for obtaining the desired spherical or nearly spherical particles of the present invention, and if the temperature exceeds the upper limit temperature, it will cause the surface of the carbon black to become wet and further agglomerate during the subsequent stirring process, thereby failing to obtain a premix of a suitable size; if the temperature is lower than the lower limit temperature, the liquid sulfur-containing silane is liable to be unevenly absorbed and dispersed during the dropwise addition. Also, the temperature of the premix is important to the degree of softness and hardness of the carbon black.
Without wishing to be bound by theory, because the increase in temperature is caused by the reaction and friction between the carbon black and the liquid sulfur-containing silane caused by agitation, the control of the temperature of the reaction premix described above is primarily controlled by the first agitation speed and the agitation time and feed rate. The specific stirring speed and the time of addition of the sulfur-containing silane can vary greatly due to the difference in the physical dimensions of the conical single-screw mixer, but the temperature of the premix can be controlled within the above-described range by controlling the stirring speed and the rate of addition of the sulfur-containing silane. In practice, the temperature of the premix can be controlled by controlling the time of addition of the sulfur-containing silane at a substantially fixed first stirring speed.
In step (A) described above, it is also important to control the temperature of the premix in the second stage to not exceed 30℃, since the carbon black added in the second stage will coat the surface of the premix formed in the first stage and gradually form firm spheres of the substantially spherical crude premix at a relatively low temperature. When the temperature exceeds the upper limit, the shape of the resulting particles is too soft to be easily fixed.
More importantly, the system temperature in the first stage and the second stage is controlled by the stirring rotation speed, and the first rotation speed of the first stage is set to be higher than the second rotation speed of the second stage, specifically, the rotation speed ratio of the first stirring rotation speed to the second stirring rotation speed is 3: 1 to 5: 1, i.e., the stirring speed in the first stage is several times the stirring speed in the second stage. Within this range of rotation rates, it will be particularly helpful to form a stable, spherical reaction premix of the sulfur-containing silane liquid and the carbon black solid having a particular particle size range.
In the step (B) described above, it is important that the pre-mixture formed first is further reacted under vacuum heating, because the pre-mixture formed first can ensure that the carbon black is fully contacted with the sulfur-containing silane in the previous period, and can also fully ensure that the sulfur-containing silane molecules are contacted with the hydroxyl groups on the surface of the carbon black or partially condensed, and simultaneously, the self-reaction polymerization of the sulfur-containing silane during the reaction period is avoided to influence the use effect; heating the material under the condition that the vacuum degree of the system reaches more than-0.096 MPa is also important, because reaction crosslinking can generate alcohol with low boiling point, and the alcohol can be taken away in a gaseous state immediately under the condition of higher vacuum, so that the alcohol can be prevented from being gathered on the surface of the carbon black, and the phenomenon that the carbon black is agglomerated in the stirring process due to partial humidity of the surface of the carbon black is avoided, so that the appearance size of the product is damaged; the reaction temperature in the step (B) is 80-98 ℃, preferably 86-94 ℃ and the reaction time is 15-30 hours, preferably 16-22 hours, which are also important, the lower reaction temperature can cause insufficient hydroxyl reaction on the surface of the carbon black, which affects the later use effect, and the higher reaction temperature can cause partial self-reaction polymerization crosslinking of the sulfur-containing silane, thereby reducing the use effect of the product.
Further, according to the present invention, the specific rotation speed of the conical single-screw reaction mixer employed in the first stage and the second stage may be determined depending on the specific volume of the mixer, provided that the first rotation speed allows the temperature of the mixed materials to be controlled within the above-mentioned range, and the particle diameter thereof to be also controlled within the range of 0.8 to 2.5mm or less of the target particle diameter.
Taking a 1000 liter conical single screw reaction mixer as an example, the first rotational speed of the first stage may be, for example, 6-10 rpm, while the second rotational speed of the second stage may be, for example, 2-3 rpm. If the volume of the conical single-screw reaction mixer is changed, the corresponding stirring speed can also be adjusted as desired by the person skilled in the art.
In the above-mentioned step (A), after the end of the first-stage stirring, it is necessary to leave the premix for 1 to 3 hours, preferably 2 to 3 hours, with the jacket cooling liquid turned on. During the said standing process, it happens that the liquid sulfur-containing silane is sufficiently absorbed in the carbon black solid and comes into contact with the hydroxyl groups inside the carbon black. By the standing treatment, the reaction premix particles of the sulfur-containing silane and the carbon black for further reaction at a later stage can be more advantageously formed. During this phase, the temperature of the reaction premix will steadily decrease and the resulting mixed material particles will gradually solidify.
In the above-mentioned step (A), the cooling liquid, preferably cooling water, in the jacket may optionally be turned on in the stirring reaction in the first stage; preferably, in said step (A), the reaction is stirred in the first stage without opening the cooling liquid in the jacket.
In the above-mentioned step (A), the cooling liquid in the jacket may optionally be turned on in the stirring reaction in the second stage; preferably, in said step (A), the second stage, the reaction is stirred without opening the cooling liquid in the jacket.
In addition, the present inventors have also found that the substantially spherical reaction complex of sulfur-containing silane and carbon black referred to in the present invention can be obtained better by using a conical single-screw reaction mixer. If a conical double-helix stirring reactor is adopted, due to the structural characteristics of the double-helix stirring reactor, the temperature of reaction mixture materials can rise too fast in the mixing process, and the temperature of the system is already over 45 ℃ when liquid sulfur-containing silane materials are not fed completely, so that excessive caking mixed materials are generated, and a required product is not easily obtained or a premix product with a low proportion and a required granularity is obtained.
The process according to the invention, wherein examples of the sulfur-containing silane are bis- [3- (triethoxysilyl) -propyl ] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl ] -disulfide, bis- [3- (trimethoxysilyl) -propyl ] -tetrasulfide, bis- [3- (trimethoxysilyl) -propyl ] -disulfide and the like. Preferred sulfur-containing silanes in the present invention are bis- [3- (triethoxysilyl) -propyl ] -tetrasulfide or bis- [3- (triethoxysilyl) -propyl ] -disulfide.
The process according to the invention, in which the carbon black concerned is a carbon black for rubber, preferably a carbon black according to one or more combinations of carbon blacks numbered N330, N339, N351, N220 or N335 in GB 3778-2011.
The method of the invention comprises the step (C) of passing the crude mixture obtained in the step (B) through an upper sieve with 8-10 meshes and a lower sieve with 18-20 meshes, wherein the sieves meet the Chinese national standard, such as the specifications defined in GB/T10061-2008.
The process according to the present invention, wherein in said step (C), the oversized and undersized particles that did not pass through the upper screen and that leaked through the lower screen may be reintroduced into the conical single-screw reaction mixer, again undergoing the entire process.
The process according to the invention, wherein the weight ratio of carbon black to total charge of sulfur-containing silane is from about 1:1, the reaction complex thus obtained is able to meet the customer requirements.
The invention also provides a reaction composite of the sulfur-containing silane liquid obtained according to the method of the invention and carbon black.
According to the invention, wherein the reaction complex is substantially spherical in appearance.
According to the present invention, the particle diameter of the reaction composite of the sulfur-containing silane liquid and carbon black, in which the appearance is substantially spherical, is 0.8 to 2.5mm, preferably 1.0 to 2.0 mm.
The method of the invention brings beneficial technical effects that:
1. the reaction compounds of sulfur-containing silanes with carbon black of the present invention, obtained by chemical reaction, having the stated particle size range, are completely free from the risk of dust formation in use, compared with the earliest mixtures of sulfur-containing silanes with carbon black.
2. Compared with the method for preparing the compound of the sulfur-containing silane and the carbon black by a screw extrusion method commonly adopted in the market, the method can obtain spherical or near-spherical particles with small particles and moderate size, and is more favorable for mixing with rubber particles in the mixing process, so that the time of the mixing process is shortened, and the mixing effect is improved.
3. The invention has high efficiency, good effect and simple method, especially the main equipment of the invention is very simple, which is very favorable for saving the investment cost of industrial production.
4. The production process of the invention has relatively low temperature, less adverse effect on the physical structure of the carbon black, and better use effect in rubber because other components such as a binder are not added in the process in practice.
5. The spherical particles obtained by the invention are reaction compounds formed by pre-reacting and combining the sulfur-containing silane and the hydroxyl on the surface of the carbon black, and the re-reaction crosslinking of the sulfur-containing silane and the hydroxyl is greatly reduced in the rubber mixing process, so that the use convenience can be improved, and the coupling effect can be fully ensured.
Drawings
FIG. 1 is a schematic diagram of a conical single-screw reaction mixer for carrying out the process of the present invention.
FIG. 2 is a photograph showing a composite of carbon black and sulfur-containing silane produced according to the method of the present invention.
Detailed Description
The technical contents of the present invention will be specifically described below with reference to examples. The examples are intended only to specifically illustrate the experimental procedures of the present invention and should not be construed as limiting the scope of the invention.
The raw material sulfur-containing silane and carbon black to be used in the present invention may be commercially available sulfur-containing silane and carbon black for rubber, respectively, for example, industrial-grade sulfur-containing silane and carbon black, respectively.
The conical single-screw reaction mixer used in the present invention may be a commercially available conical single-screw reaction mixer.
Examples
Example 1
Starting stirring of a conical single-spiral reaction mixer with the volume of 1000L, putting 300kg of carbon black N330 into the conical single-spiral reaction mixer, adjusting the stirring speed to 8 revolutions per minute, and stirring for 10 minutes; then uniformly dropwise adding 400kg of bis- [3- (triethoxysilyl) -propyl ] -disulfide silane coupling agent, continuing stirring for 5min after finishing dropwise adding in 23-25 min, stopping stirring again, opening the kettle, cooling and standing for 2.5h, wherein the material temperature is 43 ℃; the stirring was then started and 100kg of carbon black N330 were added, the stirring speed being controlled at 2 revolutions/min and the mixture being mixed for 10 minutes, forming about 800kg of crude reaction premix.
Continuously controlling the stirring speed of the mixer to be 2 r/min, vacuumizing the mixer to be more than-0.096 MPa, introducing steam into the jacket to heat the jacket, keeping stirring and reacting for 16 hours under the vacuum condition when the temperature of the materials reaches 86-90 ℃, and recovering extracted ethanol through a low-temperature condensing device; the temperature was then reduced until the temperature of the material dropped to 35 ℃ and then the vacuum, stirring and temperature reduction were stopped, whereby 720kg of a crude reaction complex having a substantially spherical appearance was obtained.
And (3) putting the crude compound into a vibrating screen with an upper layer of 8 meshes and a lower layer of 20 meshes, and starting the vibrating filtering screen to obtain 660kg of a reaction compound particle product with a spherical middle layer and a particle size of 0.8-2.5 mm.
Example 2
Starting stirring of a conical single-screw reaction mixer with the volume of 1000L, putting 300kg of carbon black N330 into the conical single-screw reaction mixer, and adjusting the stirring speed to 6 revolutions per minute for stirring for 8 minutes; then uniformly dropwise adding 400kg of bis- [3- (triethoxysilyl) -propyl ] -tetrasulfide compound silane coupling agent, continuing stirring for 5min after finishing dropwise adding in 23-25 min, stopping stirring, and opening to cool at the material temperature of 36 ℃, and standing for 2.5 h; the stirring was turned on and 100kg of carbon black N330 was added, and the mixture was stirred and mixed at a rate of 2 revolutions/min for 10 minutes to form about 800kg of the reaction premix.
Continuously controlling the stirring speed of the mixer to be 2 r/min, vacuumizing the mixer to be more than-0.096 MPa, introducing steam into the jacket to heat the jacket, keeping stirring and reacting for 20 hours under the vacuum condition when the temperature of the materials reaches 90-94 ℃, and recovering extracted ethanol through a low-temperature condensing device; then, the temperature was decreased until the temperature of the material was decreased to 35 ℃ and then the vacuum, stirring and temperature decrease were stopped, thereby obtaining 698kg of a crude reaction complex having a substantially spherical appearance.
And putting the crude compound into a vibrating screen with an upper layer of 8 meshes and a lower layer of 20 meshes, and starting the vibrating filtering screen to obtain 602kg of a reaction compound particle product with a spherical middle layer and a particle size of about 0.8-2.5 mm.
Collecting the reaction compound with the oversize upper layer and the undersize lower layer, putting the obtained oversize and undersize particles into a mixer, and repeating the steps to obtain the reaction compound particle product.
Example 3
Starting stirring of a conical single-screw reaction mixer with the volume of 1000L, putting 300kg of carbon black N330 into the conical single-screw reaction mixer, and adjusting the stirring speed to 8 revolutions per minute for stirring for 10 minutes; then uniformly dropwise adding 400kg of bis- [3- (triethoxysilyl) -propyl ] -tetrasulfide compound silane coupling agent, continuing stirring for 5min after finishing dropwise adding in 23-25 min, stopping stirring, and opening to cool at the material temperature of 43 ℃, and standing for 2.5 h; 100kg of carbon black N330 was added thereto, and the mixture was stirred and mixed at a rate of 2 revolutions/min for 10 minutes to form 800kg of a crude mixture.
Continuously controlling the stirring speed of the mixer to be 2 r/min, vacuumizing the mixer to be more than-0.096 MPa, introducing steam into the jacket to heat the jacket, keeping stirring and reacting for 20 hours under the vacuum condition when the temperature of the materials reaches 90-94 ℃, and recovering extracted ethanol through a low-temperature condensing device; then, the temperature was decreased until the temperature of the material dropped below 35 ℃ and then the vacuum, stirring and temperature decrease were stopped, whereby 690kg of a crude reaction complex having a substantially spherical appearance was obtained.
And (3) putting the crude compound into a vibrating screen with an upper layer of 10 meshes and a lower layer of 18 meshes, and starting the vibrating screen to obtain 635kg of a mixture particle product with a spherical middle layer and a particle size of 1.0-2.0 mm.
Collecting the oversize and undersize mixed reaction compound at the upper layer, putting the obtained oversize and undersize mixed particles into a mixer, and repeating the steps to obtain the reaction compound particle product.
Comparative examples
Starting stirring of a conical double-helix reaction mixer with the volume of 1000L, putting 300kg of carbon black N330 into the conical double-helix reaction mixer, and adjusting the stirring speed to 8 revolutions per minute for stirring for 10 minutes; then uniformly dropwise adding 400kg of bis- [3- (triethoxysilyl) -propyl ] -disulfide silane coupling agent, continuing stirring for 5min after finishing dropwise adding in 23-25 min, stopping stirring again, opening and cooling the materials at the temperature of 62 ℃, and standing for 3 h; 100kg of carbon black N330 was added thereto, and the mixture was stirred and mixed at a rate of 2 rpm for 10 minutes to form 800kg of a crude reaction premix.
Continuously controlling the stirring speed of the mixer to be 2 r/min, vacuumizing the mixer to be more than-0.096 MPa, introducing steam into the jacket to heat the jacket, keeping stirring and reacting for 16 hours under the vacuum condition when the temperature of the materials reaches 86-90 ℃, and recovering extracted ethanol through a low-temperature condensing device; then, the temperature was decreased until the temperature of the material was decreased to 35 ℃ and then the vacuum, stirring and temperature decrease were stopped, whereby 745kg of a crude reaction complex having an irregular appearance and containing a large amount of agglomerated particles was obtained.
And (3) putting the mixture into a vibrating screen with an upper layer of 8 meshes and a lower layer of 20 meshes, and starting the vibrating filtering screen to obtain 220kg of the composite granular material product with the grain diameter of the middle layer of 0.8-2.5 mm.
Claims (16)
1. A method of producing a reactive composite of a sulfur-containing silane liquid and carbon black, said method comprising the steps of:
(A) feeding carbon black solid and sulfur-containing silane liquid in two stages in a conical single-screw reaction mixer with a temperature-control jacket, wherein in the first stage, 60-90 wt% of carbon black based on the total weight of the carbon black is added at a first stirring speed, and then all the sulfur-containing silane is added at a constant speed under the condition of keeping the first stirring speed to stir the carbon black to obtain a reaction premix, and optionally further stirring is carried out at the first stirring speed for 5-10 minutes at the end of feeding the sulfur-containing silane liquid, wherein during the feeding of the sulfur-containing silane liquid and during the optional further stirring, the first stirring speed and the speed of adding the sulfur-containing silane are controlled to keep the temperature of the premix between 35 and 45 ℃; then stopping stirring, starting the cooling liquid in the jacket, and standing the premix; and then restarting stirring, adding the rest amount of carbon black at a second stirring rotating speed, and continuing stirring at the second stirring rotating speed after all the carbon black is added, wherein the second stirring rotating speed is ensured that the material temperature during the stirring period does not exceed 30 ℃ until a substantially spherical reaction premix crude product is formed, wherein the rotating speed ratio of the first stirring rotating speed to the second stirring rotating speed is 3: 1 to 5: 1;
(B) vacuumizing the reaction mixer at a second stirring speed, heating the materials in the reaction mixer until the temperature of the materials reaches 80-98 ℃, and continuously stirring for reaction under the condition of maintaining the temperature and the vacuum; cooling the material by cooling liquid in the jacket until the temperature of the material is reduced to below 35 ℃, and stopping vacuumizing and stirring to obtain a spherical reaction compound crude product;
(C) grading the crude compound product through a vibrating screen to obtain a finished reaction compound product of a basically spherical sulfur-containing silane liquid and carbon black solid; and is
Wherein the sulfur-containing silane is selected from the group consisting of bis- [3- (triethoxysilyl) -propyl ] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl ] -disulfide, bis- [3- (trimethoxy-silicon) -propyl ] -tetrasulfide and bis- [3- (trimethoxy-silicon) -propyl ] -disulfide.
2. The method as set forth in claim 1,
wherein in step (A) 70-80 wt.% carbon black, based on the total weight of carbon black, is initially added at a first stirring rotational speed; and/or
Wherein the premix is allowed to stand for 1 to 3 hours in step (A); and/or
Wherein in step (B) the contents of the reaction mixer are heated to a temperature in the range of from 86 to 94 ℃; and/or
Wherein the reaction is continuously stirred in step (B) for 15 to 30 hours while maintaining the temperature and vacuum.
3. The process of claim 2, wherein the reaction in step (B) is continued with stirring for 16-22 hours while maintaining the temperature and vacuum.
4. The method according to claim 1 or 2, wherein the carbon black is carbon black for rubber.
5. A process according to claim 4 wherein the carbon black for rubber is one or a combination of carbon blacks GB3778-2011 numbered N330, N339, N351, N220 or N335.
6. The method according to claim 1 or 2, wherein the particle size of the obtained final reaction composite product of the spherical sulfur-containing silane liquid and the carbon black solid is 0.8 to 2.5 mm.
7. The method as claimed in claim 6, wherein the particle size of the obtained final product of the reaction composite of the spherical sulfur-containing silane liquid and the carbon black solid is 1.0-2.0 mm.
8. The process as claimed in claim 1 or 2, wherein the weight ratio of carbon black to total charge of sulfur-containing silane is from 1: 1.
9. the method according to claim 1 or 2, wherein in the step (C), the crude reaction compound obtained in the step (B) is passed through a vibrating screen having an upper screen of 8 to 10 mesh and a lower screen of 18 to 20 mesh, and the final reaction compound is passed between the upper screen and the lower screen.
10. The process of claim 8, wherein in step (B), the crude reaction complex which has not passed through the upper screen and which has leaked through the lower screen is re-introduced into the conical single-screw reaction mixer and subjected to the process of claim 1 again.
11. The method according to claim 1 or 2, wherein the degree of vacuum in the evacuation is controlled to be-0.08 MPa or more, and the degree of vacuum is a relative degree of vacuum.
12. The method according to claim 11, wherein the degree of vacuum in the evacuation is controlled to be-0.09 MPa or more.
13. The method according to claim 12, wherein the degree of vacuum in the evacuation is controlled to be-0.096 MPa or more.
14. A reaction composite of a sulfur-containing silane and carbon black obtained according to the process of any one of claims 1 to 13.
15. The reactive composite of claim 14, wherein the reactive composite is substantially spherical in appearance, and wherein the final reactive composite of the sulfur-containing silane liquid and carbon black having a substantially spherical in appearance has a particle size of 0.8 to 2.5 mm.
16. The reaction composite of claim 15, wherein the final reaction composite of the sulfur-containing silane liquid and carbon black has a particle size of 1.0 to 2.0 mm.
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| CN101798473A (en) * | 2010-02-10 | 2010-08-11 | 广州吉必盛科技实业有限公司 | Silane-modified white carbon black-carbon black composite filling and preparation method thereof |
| CN201632224U (en) * | 2010-03-10 | 2010-11-17 | 双龙集团有限公司 | Conic single-screw mixer |
| CN103497357A (en) * | 2013-10-10 | 2014-01-08 | 张义纲 | Modified carbon black and preparation method thereof |
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| IT1320840B1 (en) * | 2000-11-17 | 2003-12-10 | Bridgestone Firestone Tech | VULCANIZABLE RUBBER MIXTURE CONTAINING SILICA AND AIMED AT THE PRODUCTION OF TIRES BANDS FOR TIRES. |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101798473A (en) * | 2010-02-10 | 2010-08-11 | 广州吉必盛科技实业有限公司 | Silane-modified white carbon black-carbon black composite filling and preparation method thereof |
| CN201632224U (en) * | 2010-03-10 | 2010-11-17 | 双龙集团有限公司 | Conic single-screw mixer |
| CN103497357A (en) * | 2013-10-10 | 2014-01-08 | 张义纲 | Modified carbon black and preparation method thereof |
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