CN114907590A - Synthetic rubber wet masterbatch and preparation method and application thereof - Google Patents
Synthetic rubber wet masterbatch and preparation method and application thereof Download PDFInfo
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- CN114907590A CN114907590A CN202210606067.4A CN202210606067A CN114907590A CN 114907590 A CN114907590 A CN 114907590A CN 202210606067 A CN202210606067 A CN 202210606067A CN 114907590 A CN114907590 A CN 114907590A
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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
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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
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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Abstract
The invention provides a synthetic rubber wet master batch and a preparation method thereof, wherein the method comprises the following steps: s1) preparing synthetic rubber glue solution by adopting a bulk polymerization method; s2) mixing the filler and/or the additive with the synthetic rubber glue solution, and uniformly dispersing to obtain a compound; s3) devolatilizing the compound to obtain the rubber master batch. Preparing wet masterbatch by adopting pure bulk polymerization glue solution, wherein in the process of synthesizing rubber glue solution by bulk polymerization reaction, in order to reduce the system viscosity, only 0-30% of organic solvent is used; it can be seen that the amount of organic solvent is very small or even can be eliminated. Compared with the dry-process masterbatch, the filler dispersibility is greatly improved; after the synthetic rubber master batch is subjected to banburying and roll milling and then vulcanized, the vulcanized rubber is found to have excellent mechanical property, wear resistance, rolling resistance and low heat generation.
Description
Technical Field
The invention belongs to the technical field of processing and production of rubber composite materials, and particularly relates to a synthetic rubber wet master batch, and a preparation method and application thereof.
Background
The usage amount of rubber in China area is over ten million tons per year, most of the rubber compounds are prepared by mixing raw rubber, filler and other auxiliary agents in the formula by an internal mixer, an open mill and other equipment in a dry method, the mixing energy consumption is high, dust is easy to fly, and environmental pollution is easy to cause by adopting the process, and the application performance of rubber products is influenced by poor dispersibility of the prepared rubber compound filler.
The masterbatch filler prepared by the wet mixing process has excellent dispersibility and application performance, and a great deal of research is carried out by a plurality of research institutions and production companies at home and abroad. Patent CN102314270A describes the use of a wet masterbatch rubber composition in tires, which describes the preparation process of the wet masterbatch by mixing two of a dispersion of a white turbid rubber auxiliary (anti-aging agent, stearic acid, resin, etc.), a rubber latex, and a filler slurry, and then mixing the two with another liquid, the preparation process is complicated, and the kinds of the rubber auxiliary are limited. The American cabot company develops a preparation process for continuously preparing natural rubber/carbon black master batch by liquid phase (US19970823411, CN97195156) by using natural latex and carbon black water slurry, simplifies the rubber mixing process, shortens the mixing time, reduces the energy consumption and the cost, but the variety of the master batch and the type of the filler are limited, and simultaneously, the polar components of the latex are adsorbed on the surface of the filler to destroy the interaction between the filler and the rubber, so that the application performance of the obtained rubber product is greatly reduced.
Disclosure of Invention
In view of the above, the present invention aims to provide a synthetic rubber wet masterbatch, a preparation method and applications thereof, wherein the amount of organic solvent used in the method is greatly reduced or even is not applicable, and the prepared synthetic rubber wet masterbatch has excellent mechanical properties, wear resistance, rolling resistance and low heat generation after vulcanization.
The invention provides a preparation method of a synthetic rubber wet master batch, which comprises the following steps:
s1) preparing synthetic rubber glue solution by adopting a bulk polymerization method;
s2) mixing the filler and/or the additive with the synthetic rubber glue solution, and uniformly dispersing to obtain a compound;
s3) devolatilizing the compound to obtain the rubber master batch.
The preparation method of the synthetic rubber wet masterbatch provided by the invention has the advantages that the amount of the used organic solvent is greatly reduced, even the preparation process does not involve the use of the organic solvent, a coagulation-free process adopts dry devolatilization, the preparation process is simple, and the energy consumption is low. The synthetic rubber masterbatch prepared by the technology has excellent filler dispersibility, and the rubber product prepared by the synthetic rubber wet masterbatch has excellent mechanical property, wear resistance, low rolling resistance and low heat generation.
The invention adopts a bulk polymerization method to prepare synthetic rubber glue solution; the method specifically comprises the following steps: the rubber cement is prepared by adopting a bulk polymerization method for a diolefin monomer and/or a monoolefine monomer, wherein the concentration of the synthetic rubber cement is 1-40 wt%, and preferably 5-25%; the concentration of the synthetic rubber glue solution is the concentration of the rubber dry glue in the glue solution. In the present invention, the diolefin monomers are selected from butadiene and isoprene. The synthetic rubber glue solution is obtained by mixing one rubber glue solution or two or more rubber glue solutions. In order to reduce the viscosity of the bulk polymerization system, the invention preferably adds a small amount of good solvent of rubber during the polymerization process; and taking the total mass of the olefin monomer and the good solvent as a reference, wherein the concentration of the good solvent is 0-30 wt%.
The invention mixes the filler and/or additive with the synthetic rubber, and obtains the compound after uniform dispersion. The invention can directly add the filler and/or the additive into the synthetic rubber liquid cement; the fillers and/or additives may be added to the elastomer cement after being suspended in a solvent. If the filler and/or additive is prepared into a suspension with a solvent, the solvent is preferably a good solvent for rubber; the kind of the good solvent may be the same as or different from the kind of the good solvent used in step S1).
In the present invention, the filler is a solid filler commonly used in rubber products; the filler is preferably one or more of carbon black, white carbon black, argil, calcium carbonate, graphene and carbon nanotubes, and more preferably carbon black and/or white carbon black; the particle size of the carbon black is preferably 1-500 nm, and more preferably 11-100 nm; the particle size of the white carbon black is 10-50 nm, and more preferably 15-40 nm.
In the present invention, the additive is selected from one or more of an active agent, an anti-aging agent, a plasticizer, a coupling agent, a flame retardant, a resin, and a dye.
The active agent is selected from zinc oxide and/or stearic acid;
the anti-aging agent is selected from one or more of amine anti-aging agents, phenol anti-aging agents, quinoline anti-aging agents and protective wax;
the plasticizer can improve the processability of the rubber; the plasticizer is selected from process oil and/or liquid rubber; the operation oil is selected from one or more of aromatic oil, paraffin oil and naphthenic oil; the weight average molecular weight of the liquid rubber is 3 x 10 3 ～1×10 5 ；
The coupling agent is used for improving the interaction between the filler (such as white carbon black) and the rubber matrix; the coupling agent is selected from one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent; the mass ratio of the filler to the coupling agent is (10:0.5) to (10:2.0), preferably 10: 1.
The resin is selected from tackifying resins and/or reinforcing resins.
In the invention, 0-150 parts of filler, preferably 10-120 parts, more preferably 20-100 parts, are used based on 100 parts of dry rubber in the synthetic rubber glue solution;
1-12 parts of an active agent, preferably 3-10 parts;
0.5-12 parts of an anti-aging agent, preferably 1-6 parts;
0-50 parts of plasticizer, preferably 2-40 parts, and more preferably 3-20 parts;
0.5 to 20 parts of resin, preferably 2 to 12 parts.
After the compound is obtained, the invention devolatilizes the compound to obtain the rubber masterbatch. In the present invention, the devolatilization is a dry devolatilization, which does not involve a coagulation process; refining the removed monomers which do not participate in the polymerization reaction, and then participating in the bulk polymerization reaction again to prepare rubber; the removed solvent can be recycled.
The invention preferably obtains rubber master batch and then carries out banburying and vulcanization; one or more of a vulcanizing agent, an accelerator, a scorch retarder and an anti-reversion agent are preferably added in the internal mixing.
In the invention, the vulcanizing agent is an auxiliary agent for crosslinking rubber molecular chains at high temperature and high pressure, and the vulcanizing agent is selected from one or more of sulfur, sulfur donor and peroxide. In a specific embodiment, in the case of the diene rubber, the vulcanizing agent is preferably sulfur and/or a sulfur donor; in the case of monoolefin rubber, the curing agent is a peroxide.
The accelerator is selected from one or more of thiazole accelerators, sulfenamide accelerators, thiuram accelerators, dithiocarbamate accelerators and benzoguanide accelerators; in specific embodiments, the accelerator is NS;
the scorch retarder is an auxiliary agent for slowing the occurrence of an early vulcanization reaction before vulcanization operation, and is selected from one or more of organic acids, nitroso compounds and thioacid amides.
In the invention, the anti-reversion agent is an auxiliary agent for preventing the reversion phenomenon of rubber in the vulcanization process.
Based on 100 parts of dry rubber in the synthetic rubber glue solution, the addition amounts of a vulcanizing agent, an accelerator, a scorch retarder and an anti-reversion agent are as follows:
0.2-12 parts of vulcanizing agent, preferably 0.5-6 parts; in the specific embodiment, the amount of the vulcanizing agent is 1.6 parts;
0.2-8 parts of an accelerator, preferably 0.5-5 parts; in the specific embodiment, the amount of the accelerator is 2.0 parts;
0-1 part of scorch retarder, preferably 0.1-0.5 part;
and 0-1 part of an anti-reversion agent, preferably 0.1-0.5 part.
In the invention, the synthetic rubber wet masterbatch is vulcanized to obtain vulcanized rubber; the vulcanized rubber has obvious advantages in mechanical strength, abrasion performance, rolling resistance and heat generation performance.
The process for preparing the synthetic rubber wet masterbatch adopts pure bulk polymerization glue solution to prepare the wet masterbatch, and only uses 0 to 30 percent of organic solvent in order to reduce the system viscosity in the process of synthesizing the rubber glue solution by bulk polymerization; it can be seen that the present invention uses very small or even no amounts of organic solvent. Meanwhile, the recovered unreacted monomer can be refined and then participate in polymerization reaction again, a small amount of used organic solvent can be recycled after recovery, and the process does not involve the generation of three wastes. The post-treatment process does not relate to a condensation process, and a dry devolatilization process different from the traditional wet masterbatch is adopted, so that the process is simplified.
Compared with the dry masterbatch, the wet masterbatch of the synthetic rubber prepared by the process has the advantages that the dispersibility of the filler is greatly improved; the synthetic rubber master batch is subjected to banburying and open mixing and sheet discharging, and a sample obtained after vulcanization is subjected to performance test, so that the vulcanized rubber has excellent mechanical property, wear resistance, rolling resistance and low heat generation.
Detailed Description
In order to further illustrate the present invention, a synthetic rubber wet master batch and a preparation method thereof provided by the present invention will be described in detail with reference to examples, which should not be construed as limiting the scope of the present invention.
Comparative example 1
Using a dry mixing technique: adopting an internal mixer to carry out internal mixing on 100 parts of trans-butadiene rubber, 5 parts of zinc oxide, 3 parts of stearic acid, 60 parts of white carbon black, 6 parts of silane coupling agent, 2 parts of anti-aging agent 4020, 1 part of anti-aging agent RD, 1 part of protective wax and 3 parts of environment-friendly aromatic oil, and then carrying out upper and lower sheet mixing on a mixed sample in an open mill to obtain a section of masterbatch; the first masterbatch was allowed to stand at room temperature for 2 h. Uniformly mixing the primary rubber batch, 2.0 parts of accelerator NS and 1.6 parts of sulfur by using an internal mixer, and standing the final rubber batch for 24 hours at room temperature after sheet discharging by using an open mill. The final batch was vulcanized at 150 ℃. Corresponding performance tests were performed according to the equipment, standards or methods described in table 1.
Example 1
Adopting a pure bulk polymerization process to obtain trans-butadiene-isoprene rubber glue solution (the mass of dry rubber accounts for 10 percent, and the balance is unreacted monomer) by polymerizing butadiene and isoprene monomers, adding 5 parts of zinc oxide, 3 parts of stearic acid, 60 parts of white carbon black, 6 parts of silane coupling agent, 2 parts of anti-aging agent 4020, 1 part of anti-aging agent RD, 1 part of protective wax and 3 parts of environment-friendly aromatic oil into 1000 parts of the trans-butadiene-isoprene rubber glue solution, carrying out devolatilization after uniformly dispersing under the stirring and shearing action, refining the monomers generated by the devolatilization, then entering a polymerization system for polymerization again, adding 2.0 parts of accelerator NS and 1.6 parts of sulfur into an internal mixer for uniformly mixing, feeding an open mill and discharging, and standing at room temperature for 24 hours. The final batch was vulcanized at 150 ℃. Corresponding performance tests were performed according to the equipment, standards or methods described in table 1.
Example 2:
adopting a pure bulk polymerization process to polymerize butadiene and isoprene monomers to obtain a trans-butadiene-isoprene rubber glue solution (the mass of dry rubber accounts for 25%, and the balance is unreacted monomers), adding 5 parts of zinc oxide, 3 parts of stearic acid, 60 parts of white carbon black, 6 parts of a silane coupling agent, 2 parts of an anti-aging agent 4020, 1 part of an anti-aging agent RD, 1 part of protective wax and 3 parts of environment-friendly aromatic oil into 300 parts of n-hexane, stirring to form a suspension, adding the n-hexane suspension containing the white carbon black and other rubber additives into 400 parts of the trans-butadiene-isoprene rubber glue solution, uniformly dispersing under the stirring and shearing action, devolatilizing, refining the monomers generated by devolatilization, then entering a polymerization system to perform polymerization reaction again, and recycling the purified n-hexane. The obtained wet masterbatch is uniformly mixed with 2.0 parts of accelerator NS and 1.6 parts of sulfur in an internal mixer, and the rubber compound is placed on and off a mill for 24 hours at room temperature. The final batch was vulcanized at 150 ℃. Corresponding performance tests were performed according to the equipment, standards or methods described in table 1.
Example 3:
adopting a bulk polymerization process of solvent viscosity reduction to obtain a trans-butadiene-isoprene rubber glue solution (16% of dry glue, 20% of solvent n-heptane and 64% of unreacted monomer) by polymerizing butadiene and isoprene monomers, putting 5 parts of zinc oxide, 3 parts of stearic acid, 60 parts of white carbon black, 6 parts of silane coupling agent, 2 parts of anti-aging agent 4020, 1 part of anti-aging agent RD, 1 part of protective wax and 3 parts of environment-friendly aromatic oil into 625 parts of trans-butadiene-isoprene rubber glue solution, dispersing uniformly under the action of stirring and shearing, performing devolatilization, refining the monomers generated by devolatilization, then entering a polymerization system for polymerization reaction again, and recycling purified n-hexane. The obtained wet masterbatch is uniformly mixed with 2.0 parts of accelerator NS and 1.6 parts of sulfur in an internal mixer, and the rubber compound is placed on and off a mill for 24 hours at room temperature. The final batch was vulcanized at 150 ℃. Corresponding performance tests were performed according to the equipment, standards or methods described in table 1.
Table 1 apparatus and standards or methods used
TABLE 2 Performance test results of examples 1 to 3 and comparative example 1
| Serial number | Comparative example 1 | Example 1 | Example 2 | Example 3 |
| Rubber compound filler dispersion grade | 5.0 | 7.9 | 8.2 | 8.9 |
| StretchingStrength, MPa | 24.4 | 25.6 | 25.2 | 26.8 |
| Tear Strength, KN/m | 45 | 52 | 55 | 53 |
| Rebound, is% | 58 | 66 | 67 | 65 |
| Heat generation by compression, DEG C | 27.2 | 20.2 | 19.5 | 21.2 |
| Tanδ@60℃ | 0.180 | 0.092 | 0.085 | 0.095 |
| DIN abrasion, mm 3 /40m | 37.2 | 25.6 | 24.3 | 26.7 |
From the above examples, compared with the sample prepared by the traditional dry rubber mixing process (comparative example 1), the filler dispersion grade is significantly improved; after the wet masterbatch prepared by the technology is vulcanized, the tensile strength is improved by 0.8-2.4 MPa, the tear strength is improved by 7-10 KN/m, the resilience performance is improved by 7-9 units, the compression heat generation is reduced by 6.0-7.7 ℃, the tan delta representing the rolling resistance is reduced by about 50% at 60 ℃, and the abrasion volume is reduced by about 30%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a synthetic rubber wet master batch comprises the following steps:
s1) preparing synthetic rubber glue solution by adopting a bulk polymerization method;
s2) mixing the filler and/or the additive with the synthetic rubber glue solution, and obtaining a compound after uniform dispersion;
s3) devolatilizing the compound to obtain the rubber master batch.
2. The preparation method according to claim 1, wherein the synthetic rubber cement prepared by the bulk polymerization method comprises:
preparing a diolefin monomer and/or a monoolefine monomer by a bulk polymerization method;
the concentration of the synthetic rubber glue solution is 1-40 wt%.
3. The preparation method according to claim 2, wherein a good solvent is added to the polymerization process or the prepared synthetic rubber cement in step S1);
the concentration of the good solvent is 0-30 wt%.
4. The process according to claim 1, characterized in that in step S2), the fillers and/or additives are added directly to the synthetic rubber cement;
or the filler and/or the additive and the solvent are prepared into a suspension and then added into the synthetic rubber glue solution.
5. The preparation method according to claim 1, wherein the filler is selected from one or more of carbon black, white carbon, china clay, calcium carbonate, graphene and carbon nanotubes;
the additive is selected from one or more of an active agent, an anti-aging agent, a plasticizer, a coupling agent, a flame retardant, resin and dye.
6. The method of claim 5, wherein the active agent is selected from zinc oxide and/or stearic acid;
the anti-aging agent is selected from one or more of amine anti-aging agents, phenol anti-aging agents, quinoline anti-aging agents and protective wax;
the plasticizer is selected from process oil and/or liquid rubber; the operation oil is selected from one or more of aromatic oil, paraffin oil and naphthenic oil; the weight average molecular weight of the liquid rubber is 3 x 10 3 ～1×10 5 ；
The coupling agent is selected from one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent;
the resin is selected from tackifying resins and/or reinforcing resins.
7. The preparation method according to claim 5, wherein the rubber dry glue is prepared by mixing the rubber dry glue with the synthetic rubber glue solution in an amount of 100 parts by mass,
0-150 parts of a filler;
1-12 parts of an active agent, 0.5-12 parts of an anti-aging agent, 0-50 parts of a plasticizer and 0.5-20 parts of a resin.
8. The preparation method according to claim 5, wherein the particle size of the carbon black is 1-500 nm, and the particle size of the white carbon black is 10-50 nm.
9. The method of claim 2, wherein the olefin monomer is selected from butadiene and isoprene.
10. A synthetic rubber wet masterbatch prepared by the preparation method of any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115160657A (en) * | 2022-08-17 | 2022-10-11 | 山东华聚高分子材料有限公司 | Rubber masterbatch and preparation method thereof |
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| CN115160657A (en) * | 2022-08-17 | 2022-10-11 | 山东华聚高分子材料有限公司 | Rubber masterbatch and preparation method thereof |
| CN115160657B (en) * | 2022-08-17 | 2024-01-26 | 山东华聚高分子材料有限公司 | Rubber masterbatch and preparation method thereof |
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