CN111592694B - Natural rubber masterbatch filled with carbon black and preparation method and application thereof - Google Patents
Natural rubber masterbatch filled with carbon black and preparation method and application thereof Download PDFInfo
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- CN111592694B CN111592694B CN202010407028.2A CN202010407028A CN111592694B CN 111592694 B CN111592694 B CN 111592694B CN 202010407028 A CN202010407028 A CN 202010407028A CN 111592694 B CN111592694 B CN 111592694B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F1/00—Springs
- F16F1/36—Springs made of rubber or other material having high internal friction, e.g. thermoplastic elastomers
- F16F1/3605—Springs made of rubber or other material having high internal friction, e.g. thermoplastic elastomers characterised by their material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2407/00—Characterised by the use of natural rubber
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Abstract
The invention belongs to the technical field of preparation of carbon black natural rubber master batch, and particularly discloses carbon black-filled natural rubber master batch as well as a preparation method and application thereof. The invention firstly mixes and flocculates the carbon black slurry and latex to obtain the aggregate, and then dehydrates and dries the aggregate. Because the centrifugal dehydration and extrusion dehydration expansion drying integrated post-treatment technology is adopted, compared with the conventional air-blast drying, the drying time is greatly shortened, the shearing force applied in the extrusion dehydration process is stronger, the probability of secondary aggregation of the carbon black in a wet flocculation product is favorably reduced, the interaction between the carbon black and a rubber matrix is favorably realized, and higher bound rubber content is obtained, thereby being favorable for obtaining a carbon black-filled masterbatch product with good carbon black dispersion and rubber/carbon black interaction. And secondly, because no surfactant is added, the defects of reduced surface activity of the carbon black, reduced content of the bound rubber, poor mechanical property of vulcanized rubber and the like caused by the addition of the surfactant are overcome.
Description
Technical Field
The invention belongs to the technical field of preparation of natural rubber master batch, and particularly relates to carbon black-filled natural rubber master batch as well as a preparation method and application thereof.
Background
The technology for preparing a rubber/carbon black composite (also called as masterbatch) by a wet method is a technical method for preparing rubber masterbatch containing carbon black based on a latex/carbon black slurry mixing technology, compared with the high viscosity of rubber dry rubber, the viscosity of the latex is extremely low, carbon black is mixed with low-viscosity latex, and then flocculation and drying are carried out to prepare the carbon black masterbatch containing carbon black, so that the carbon black/carbon black composite is beneficial to reducing the energy consumption for dispersing the carbon black in the rubber and improving the dispersion of the carbon black in the rubber, and therefore the carbon black/carbon black composite is valued by the industry in recent years.
At present, the disclosed technical route for preparing natural rubber master batch containing carbon black by a wet method is roughly as follows:
(1) preparation of carbon black slurry: dispersing carbon black in water by certain shearing force in the presence of surfactant (also called dispersant, emulsifier, etc.) to obtain relatively stable carbon black slurry;
(2) mixing and flocculation of the carbon black slurry with the latex: mixing the carbon black slurry and latex under a certain stirring condition, adding a flocculating agent (acid, monovalent or multivalent water-soluble salt and a mixture of the acid and the salt) after stirring for a certain time to obtain a mixture containing carbon black/wet rubber, and then washing, dehydrating and drying to obtain the natural rubber master batch containing the carbon black.
For example, patent 02152077.1 proposes a method for preparing carbon black-filled powdered rubber: dispersing carbon black in water in the presence of an emulsifier (a nonionic surfactant or an anionic surfactant) to prepare carbon black slurry, mixing the carbon black slurry with latex, heating, flocculating and drying to prepare carbon black filled powder rubber with the particle size of 0.2-1.0 mm; in the method, a certain amount of surfactant is added as a carbon black dispersing agent, so that the stretching stress and strength of the rubber possibly caused by the surfactant remained in the rubber are reduced, and the washed surfactant can also cause the cost of wastewater treatment. Patent publication 201410337186.X provides a preparation method of carbon black-extended styrene-butadiene rubber master batch suitable for non-contact pollution without adding a surfactant, wherein in the preparation stage of carbon black slurry, the surfactant for improving carbon black dispersion is not added, and uniform and stable carbon black slurry is obtained only through strong mechanical shearing and mechanical stirring action; however, this patent does not teach a method for the aftertreatment of the flocculated product produced, i.e.the carbon black-containing/wet rubber mixture. Patent publication 201210266789.6 proposes a wet-refining method for preparing natural rubber-carbon black compound, in which various water-soluble alcohols or ethers are added in the preparation stage of carbon black dispersion, which increases the cost of waste water treatment and causes environmental pollution.
In addition, in the carbon black-containing/wet rubber mixture obtained by the flocculation treatment, since the rubber phase contains much moisture and is not crosslinked, the carbon black therein tends to be aggregated thermodynamically.
Disclosure of Invention
In order to overcome the shortcomings and drawbacks of the prior art, the present invention provides a method for preparing a carbon black-filled natural rubber masterbatch.
The invention also aims to provide the carbon black-filled natural rubber master batch prepared by the method.
The invention further aims to provide application of the carbon black-filled natural rubber master batch in tread rubber of heavy duty radial tires, tread rubber of engineering machinery tires and rubber air springs.
The purpose of the invention is realized by the following scheme:
a preparation method of carbon black-filled natural rubber master batch comprises the following steps:
(1) preparing materials: the ingredients are proportioned according to the following components in parts by weight
Natural latex: 100 parts (based on dry glue); carbon black: 40-100 parts; water: 1500-3000 parts; operating oil: 0-30 parts of a solvent; coagulant: 1-3 parts;
(2) preparation of carbon black slurry: adding carbon black and water into a colloid mill, keeping the concentration of the carbon black at 2.5-9.0wt%, and grinding to obtain carbon black slurry;
(3) mixing and flocculation of the carbon black slurry with the latex: adding the carbon black slurry into natural latex under the conditions of normal temperature and high-speed stirring to obtain a latex/carbon black mixed system; then preserving heat for reaction, and adding a coagulant aqueous solution after the reaction is finished; the system generates the condensation and coprecipitation phenomenon, and the aggregates are separated out in a granular shape;
(4) dewatering and drying treatment of the condensate: dehydrating the aggregate; putting the product obtained by dehydration into an extrusion dehydration expansion drying all-in-one machine, wherein the temperature of a machine head is 160-180 ℃, the pressure of the machine head is not less than 10MPa, and performing further extrusion dehydration and expansion drying under high shear to obtain a dried product with the water content of about 5-10%; and then further drying the dried product in a fourdrinier dryer by hot air at the temperature of 80-100 ℃ until the moisture content is below 1 percent to obtain the carbon black-filled natural rubber master batch.
The natural latex in the step (1) is field latex which is not subjected to concentration treatment or natural latex which is subjected to concentration treatment; the carbon black is ultrahigh wear-resistant carbon black (SAF), medium super wear-resistant carbon black (ISAF), high wear-resistant carbon black (HAF) or semi-reinforcing carbon black (SRF); the operating oil is common operating oil or filling oil in the rubber industry, and is specifically alkane oil or aromatic oil; the coagulant is one or a mixture of calcium chloride, sulfuric acid and acetic acid;
and (3) grinding for 30-90 min in the step (2). The size of the carbon black dispersion in the carbon black slurry obtained in the step (2) is 300nm or less.
The concentration of the natural latex in the step (3) is 5-20 wt%;
and (4) the high-speed stirring speed in the step (3) is 3000-6000 rpm.
And (4) keeping the temperature of the heat preservation reaction in the step (3) at 70-90 ℃ for 10-15 min.
The concentration of the coagulant aqueous solution in the step (3) is 5-20% wt, preferably 10% wt.
And (3) when the formula in the step (1) contains the operation oil, adding the operation oil after the aggregate is separated out in the step (3), and continuously stirring for 10-15 min.
A natural rubber masterbatch filled with carbon black is prepared according to the method.
The carbon black-filled natural rubber master batch has good application in occasions requiring excellent dispersion of carbon black in natural rubber and good combination between the carbon black and the rubber, such as tread rubber of a truck radial tire, tread rubber of an engineering mechanical tire, a rubber air spring and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the carbon black-filled natural rubber masterbatch prepared by the method adopts an integrated post-treatment technology of centrifugal dehydration and extrusion dehydration expansion drying, compared with the conventional air-blast drying, the drying time is greatly shortened, the shearing force applied in the extrusion dehydration process is stronger, the method is not only beneficial to reducing the probability of the carbon black in the wet flocculation product, but also beneficial to the interaction between the carbon black and the rubber matrix, and obtaining higher bound rubber content, thereby being beneficial to obtaining the carbon black-filled masterbatch product with good carbon black dispersion and rubber/carbon black interaction.
(2) The carbon black-filled natural rubber master batch prepared by the method of the invention obtains the carbon black slurry with the carbon black dispersed in the water in a metastable state by improving the preparation process, and the preparation method is simple and has good repeatability. It is not necessary to add a surfactant for improving the dispersibility of the carbon black in water.
(3) The method for preparing the natural rubber masterbatch filled with the carbon black overcomes the defects of reduced surface activity of the carbon black, reduced content of the combined rubber, poor mechanical property of vulcanized rubber and the like caused by adding the surfactant because the surfactant is not added, and avoids the defect of increased wastewater treatment cost caused by the emulsifier.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Examples 1 to 6
(I) preparing materials
The materials are mixed according to the mixture ratio in the table 1.
TABLE 1 amounts of reagents and Process conditions for the examples
(II) preparation of carbon Black suspension
According to the formulation and control conditions listed in Table 1, a carbon black slurry was prepared by a colloid mill circulation milling method by adding metered amounts of water and carbon black to a reaction vessel. The colloid mill is connected with the carbon black slurry storage tank in series, and the carbon black slurry which is ground and dispersed by the colloid mill is pumped back to the carbon black slurry storage tank again. Adding carbon black into a carbon black storage tank, adding water to adjust the concentration of the carbon black to 2.5-9.0wt%, starting a colloid mill, and circularly dispersing carbon black slurry in the carbon black slurry storage tank for 30-90 minutes at a high speed by the colloid mill to obtain carbon black slurry with good dispersion of the carbon black in the water; the carbon black dispersion level of the carbon black slurry is rapidly detected by sampling or is measured on line, and when the average particle diameter of the carbon black dispersion is below 300 nanometers, the dispersion is stopped, so that the uniformly and stably dispersed carbon black slurry is prepared.
(III) mixing and flocculation of carbon Black slurry and latex
Adding the carbon black slurry into natural latex with the concentration of 5-20 wt% under the conditions of normal temperature and high-speed stirring to obtain a latex/carbon black mixed system; then heating the reaction kettle to 70-90 ℃, keeping the temperature for 10-15 minutes, adding a measured coagulant aqueous solution with the mass concentration of 10%, and precipitating the coagulants in a granular form when the system is coagulated and coprecipitated; if the formula contains the operation oil, adding the operation oil under stirring; continuously stirring for 10-15 minutes and discharging.
(IV) dehydration and drying treatment of the condensate
The dehydration and drying treatment of the condensate is divided into three process stages:
(1) a centrifugal dehydration section: transferring the condensate to a horizontal spiral centrifuge through a feed opening of a reaction kettle for dehydration treatment to obtain a loose and continuous blocky product with the water content of about 50%;
(2) extrusion dehydration expansion drying section: putting the preliminary dehydration product into an extrusion dehydration expansion drying all-in-one machine (the temperature of a machine head is 160-180 ℃, the pressure of the machine head is not less than 10MPa), and performing further extrusion dehydration and expansion drying under high shear, wherein the water content of the dried product is about 5-10%;
(3) a fourdrinier drying section: and further drying the extruded and dehydrated product in a fourdrinier dryer by hot air at the temperature of 80-100 ℃ until the moisture content is below 1 percent, wherein the required time is about 30-60 minutes, and obtaining the carbon black-filled natural rubber masterbatch (CNR).
The carbon black-filled styrene butadiene rubber master batch is in an irregular long strip shape with rough surface and 2-5 mm diameter, and the physical and mechanical properties are shown in Table 2:
TABLE 2 physical and mechanical Properties of carbon Black-filled Natural rubber masterbatch
Note:
1. the vulcanization formula of the carbon black-filled natural rubber comprises the following components: 100 parts of raw rubber (without carbon black), 3 parts of stearic acid, 5 parts of zinc oxide and 0.6 part of accelerator DM; vulcanization conditions are as follows: 30min at 145 ℃.
2. The reference example formulation was: 100 parts of natural rubber (SCR 5), 50 parts of carbon black (N234), 3 parts of stearic acid, 5 parts of zinc oxide and 0.6 part of an accelerator DM; vulcanization conditions are as follows: 30min at 145 ℃.
As can be seen from Table 2, the carbon black-filled natural rubber masterbatch of the present invention has excellent physical and mechanical properties.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of carbon black-filled natural rubber master batch is characterized by comprising the following steps:
(1) preparing materials: the ingredients are proportioned according to the following components in parts by weight
Natural latex: 100 parts by weight of dry glue; carbon black: 40-100 parts; water: 1500-3000 parts; operating oil: 0-30 parts of a solvent; coagulant: 1-3 parts;
(2) preparation of carbon black slurry: adding carbon black and water into a colloid mill, keeping the concentration of the carbon black at 2.5-9.0wt%, and grinding to obtain carbon black slurry;
(3) mixing and flocculation of the carbon black slurry with the latex: adding the carbon black slurry into natural latex under the conditions of normal temperature and high-speed stirring to obtain a latex/carbon black mixed system; then preserving heat for reaction, and adding a coagulant aqueous solution after the reaction is finished; the system generates the condensation and coprecipitation phenomenon, and the aggregates are separated out in a granular shape;
(4) dewatering and drying treatment of the condensate: dehydrating the aggregate; putting the product obtained by dehydration into an extrusion dehydration expansion drying all-in-one machine, wherein the temperature of a machine head is 160-180 ℃, the pressure of the machine head is not less than 10MPa, and performing further extrusion dehydration and expansion drying under high shear to obtain a dried product with the water content of 5-10%; then further drying the dried product in a fourdrinier dryer by hot air at the temperature of 80-100 ℃ until the moisture content is below 1 percent to obtain the carbon black-filled natural rubber master batch;
the natural latex in the step (1) is field latex which is not subjected to concentration treatment or natural latex which is subjected to concentration treatment; the concentration of the natural latex in the step (3) is 5-20 wt%; the concentration of the coagulant aqueous solution is 5-20% wt.
2. The method of claim 1, wherein:
the carbon black in the step (1) is ultrahigh wear-resistant carbon black, medium and ultrahigh wear-resistant carbon black, high wear-resistant carbon black or semi-reinforcing carbon black.
3. The method of claim 1, wherein:
the operating oil in the step (1) is alkane oil or aromatic oil; the coagulant is one or more of calcium chloride, sulfuric acid and acetic acid.
4. The production method according to claim 1, 2 or 3, characterized in that:
and (3) grinding for 30-90 min in the step (2).
5. The method of claim 1, wherein: the high-speed stirring speed in the step (3) is 3000-6000 rpm; and (4) keeping the temperature of the heat preservation reaction in the step (3) at 70-90 ℃ for 10-15 min.
6. The method of claim 1, wherein: and (3) when the formula in the step (1) contains the operation oil, adding the operation oil after the aggregate is separated out in the step (3), and continuously stirring for 10-15 min.
7. The carbon black-filled natural rubber masterbatch prepared by the method according to any one of claims 1 to 6.
8. The use of the carbon black-filled natural rubber master batch according to claim 7 in tread rubber of truck radial tires, tread rubber of engineering machinery tires and rubber air springs.
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| CN114407266A (en) * | 2022-01-10 | 2022-04-29 | 青岛科技大学 | Preparation method of carbon black/natural latex composite material |
| CN115256685A (en) * | 2022-06-22 | 2022-11-01 | 青岛黑猫新材料研究院有限公司 | Wet mixing continuous dehydration process |
| CN115871121A (en) * | 2023-01-31 | 2023-03-31 | 青岛黑猫新材料研究院有限公司 | Wet process masterbatch production line based on high-speed flow reaction |
| CN117683278B (en) * | 2024-02-02 | 2024-05-07 | 广东粤港澳大湾区黄埔材料研究院 | Liquid phase coprecipitation adhesive and preparation method thereof |
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| CN102492065A (en) * | 2011-11-11 | 2012-06-13 | 茂名鲁华化工有限公司 | Dehydrating and drying method for producing isoprene rubber through solution polymerization process |
| CN102816265A (en) * | 2012-07-30 | 2012-12-12 | 华南理工大学 | Hydrometallurgy method for preparing natural rubber/carbon black compound rubber |
| CN104211837A (en) * | 2014-07-15 | 2014-12-17 | 华南理工大学 | Preparation method of carbon-black-containing butadiene styrene rubber master batch |
| CN109517195A (en) * | 2017-09-18 | 2019-03-26 | 北京化工大学 | A kind of method that wet process is kneaded preparation carbon black rubber master batch |
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| CN102492065A (en) * | 2011-11-11 | 2012-06-13 | 茂名鲁华化工有限公司 | Dehydrating and drying method for producing isoprene rubber through solution polymerization process |
| CN102816265A (en) * | 2012-07-30 | 2012-12-12 | 华南理工大学 | Hydrometallurgy method for preparing natural rubber/carbon black compound rubber |
| CN104211837A (en) * | 2014-07-15 | 2014-12-17 | 华南理工大学 | Preparation method of carbon-black-containing butadiene styrene rubber master batch |
| CN109517195A (en) * | 2017-09-18 | 2019-03-26 | 北京化工大学 | A kind of method that wet process is kneaded preparation carbon black rubber master batch |
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