Wet coprecipitation rubber master batch, preparation method thereof and rubber product

Abstract

The invention relates to the technical field of rubber, and discloses a wet co-precipitation rubber master batch, a preparation method thereof and a rubber product. The preparation method comprises the following steps: (1) under a grinding condition, carrying out first contact on a filler and a solvent to obtain a filler dispersion liquid; (2) carrying out second contact on the filler dispersion liquid, a rubber solution and an auxiliary agent to obtain a rubber / filler mixed liquid; (3) performing third contact on the rubber / filler mixed solution and an anti-solvent, and performing polarity difference replacement to obtain a solid rubber / filler mixture; and (4) drying the solid rubber / filler mixture to obtain the wet co-precipitated rubber master batch. According to the preparation method, the stability of the glue solution / filler dispersion liquid can be obviously improved by introducing a simple pretreatment process, in addition, the devolatilization process is accelerated by utilizing the polarity difference between the solvent and the anti-solvent, and the prepared masterbatch has excellent filler dispersity and comprehensive performance.

Description

Technical Field

[0001] The invention relates to the technical field of rubber, and in particular to a wet co-precipitation rubber masterbatch and a preparation method thereof, as well as a rubber product. Background Art

[0002] The traditional rubber mixing process has disadvantages such as high mixing energy consumption and cost, poor dispersion of reinforcing fillers, and serious dust pollution. In order to fully comply with the concept of green manufacturing, wet mixing technology has become the focus of industry development.

[0003] In the prior art, in 2001, during the research and development of natural rubber and carbon black masterbatch preparation, Cabot Corporation added a material flow of granular filler and elastomer latex into the mixing zone of a coagulant reactor in a wet mixing step or section to obtain an elastomer / carbon black nanocomposite material.

[0004] CN103419292B, CN103419293B and CN103600435B disclose a series of continuous manufacturing methods for rubber masterbatches, which directly mix solid fillers with rubber liquid and cannot achieve efficient mixing effects.

[0005] CN114213730A discloses a rubber nanocomposite material and a preparation method thereof. The surface of the nanofiller is modified by a coupling agent. However, due to the limitation of the surface group content of the nanofiller, the filler cannot be fully pretreated.

[0006] The above patents lack optimized pretreatment of the filler itself, and the resulting rubber / filler dispersion has poor stability, resulting in a small operating window, and the dispersibility of the final masterbatch needs to be optimized.

[0007] Therefore, it is of great significance to study and develop a method for preparing wet co-precipitation rubber masterbatch. Summary of the invention

[0008] The purpose of the present invention is to overcome the defects of the prior art that the stability of the rubber / filler dispersion is poor, resulting in a small operating window and poor dispersibility of the final masterbatch, and to provide a wet co-precipitated rubber masterbatch and a preparation method thereof and a rubber product. The preparation method can significantly improve the stability of the rubber / filler dispersion by introducing a simple pretreatment process. In addition, a wet condensation devolatilization process is adopted to utilize the polarity difference between the solvent and the anti-solvent to reduce the dispersion-induced precipitation of the rubber / filler co-precipitated rubber in the solvent, thereby accelerating the devolatilization process. The prepared masterbatch has excellent filler dispersibility and comprehensive performance.

[0009] In order to achieve the above object, the first aspect of the present invention provides a method for preparing a wet co-precipitation rubber masterbatch, wherein the preparation method comprises:

[0010] (1) contacting the filler with the solvent under grinding conditions to obtain a filler dispersion;

[0011] (2) subjecting the filler dispersion, rubber solution and additive to a second contact to obtain a rubber / filler mixed solution;

[0012] (3) contacting the rubber / filler mixture with an anti-solvent for a third time to obtain a solid rubber / filler mixture by substitution due to polarity difference;

[0013] (4) drying the solid rubber / filler mixture to obtain a wet co-precipitation rubber masterbatch.

[0014] The second aspect of the present invention provides a wet co-precipitation rubber masterbatch prepared by the aforementioned preparation method.

[0015] A third aspect of the present invention provides a rubber product, wherein the rubber product comprises the wet co-precipitation rubber masterbatch described above.

[0016] Through the above technical solution, the present invention has the following advantages:

[0017] (1) The wet condensation and devolatilization process can significantly improve the stability of the adhesive / filler dispersion;

[0018] (2) Adopting wet coagulation devolatilization process, taking advantage of the polarity difference between solvent and anti-solvent, reducing the dispersibility of rubber / filler co-precipitation rubber in solvent and inducing precipitation;

[0019] (3) Wet co-precipitation rubber masterbatch can meet the needs of different rubber products by changing the types and amounts of rubber, fillers and additives. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a comparative schematic diagram of the sedimentation of the rubber / filler mixture prepared in Comparative Example 2 and Example 1 of the present invention after standing for one week.

[0021] Description of Reference Numerals

[0022] D - sample of Comparative Example 2; S - sample of Example 1. DETAILED DESCRIPTION

[0023] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0024] As mentioned above, the first aspect of the present invention provides a method for preparing a wet co-precipitation rubber masterbatch, wherein the preparation method comprises:

[0025] (1) contacting the filler with the solvent under grinding conditions to obtain a filler dispersion;

[0026] (2) subjecting the filler dispersion, rubber solution and additive to a second contact to obtain a rubber / filler mixed solution;

[0027] (3) contacting the rubber / filler mixture with an anti-solvent for a third time to obtain a solid rubber / filler mixture by substitution due to polarity difference;

[0028] (4) drying the solid rubber / filler mixture to obtain a wet co-precipitation rubber masterbatch.

[0029] The inventors of the present invention have discovered that the preparation process of the wet co-precipitation rubber masterbatch described in the present invention can significantly improve the stability of the rubber solution / filler dispersion by introducing a simple pretreatment process; in addition, a wet condensation devolatilization process is adopted to utilize the polarity difference between the solvent and the anti-solvent to reduce the dispersion of the rubber / filler co-precipitation rubber in the solvent and induce precipitation; further, when a high-boiling point anti-solvent is used, precipitation and solvent volatilization proceed simultaneously, thereby accelerating the devolatilization process.

[0030] According to the present invention, the anti-solvent is selected from alcohol and / or water; preferably, the anti-solvent is anti-solvent vapor. The anti-solvent can allow the glue to precipitate from the solvent. For example, in the present invention, water can be used as the anti-solvent for both SSBR and HNBR, and the solvents for SSBR and HNBR can be hexane and chlorobenzene, respectively.

[0031] According to the present invention, the solvent is the same or different but mutually soluble good rubber solvent; preferably, the solvent is selected from one or more of hydrocarbons, ethers, lipids and furans.

[0032] In the present invention, the hydrocarbon solvent is selected from one or more of aliphatic hydrocarbons, aromatic hydrocarbons and chlorinated hydrocarbons; wherein the aromatic hydrocarbons include one or more of benzene, toluene and xylene; and the aliphatic hydrocarbons include one or more of pentane, hexane and octane.

[0033] In the present invention, the ether solvent is selected from diethyl ether and / or propylene oxide.

[0034] In the present invention, the ester solvent is selected from one or more of methyl acetate, ethyl acetate and propyl acetate.

[0035] In the present invention, the furan solvent is tetrahydrofuran.

[0036] According to the present invention, in step (1), the grinding conditions include: grinding power of 5-80 Hz, time of 5 min-6 h; preferably, grinding power of 20-50 Hz, time of 10 min-1 h; more preferably, grinding power of 25-30 Hz, time of 10 min-1 h. In the present invention, the grinding can use general grinding and refining equipment, including but not limited to one or more of a sand mill, a grinder, a ball mill and a refiner.

[0037] According to the present invention, the conditions for the first contact are not particularly limited, and the contact temperature can be between room temperature and the boiling point of the solvent.

[0038] According to the present invention, the filler includes but is not limited to the solid reinforcing filling filler involved in the rubber product formula, for example, the filler is selected from one or more of silicon materials, carbon materials, oxides and salts; in the present invention, the silicon material is selected from one or more of silicon dioxide, silicon nitride, montmorillonite and diatomaceous earth; the carbon material is selected from one or more of carbon black (165N), graphene and carbon nanotubes; the oxide is selected from one or more of magnesium oxide, zinc oxide, aluminum oxide and rare earth oxides; the salt is selected from one or more of calcium carbonate, calcium sulfate, magnesium carbonate and zinc carbonate.

[0039] According to the present invention, the concentration of the filler in the filler dispersion is 0.1-70 wt %, preferably 5-30 wt %, and more preferably 15-20 wt %.

[0040] According to the present invention, as mentioned above, the filler can be a synchronous filler modified during the grinding process, or a modified filler. In the present invention, the filler can be modified by physical adsorption or chemical modification.

[0041] In the present invention, the physical adsorption is to use Van der Waals force to adsorb the adsorbent onto the particle surface.

[0042] In the present invention, the chemical modification includes one or more of coupling agent modification, grafting modification and surface growth modification.

[0043] According to the present invention, preferably, the coupling agent modification is selected from one or more of an organic halide coupling agent, a silane coupling agent, a silazane coupling agent and a titanate coupling agent.

[0044] According to the present invention, preferably, the coupling agent is selected from one or more of an organic halide coupling agent, a silane coupling agent, a silazane coupling agent and a titanate coupling agent, preferably a silane coupling agent (Si69).

[0045] According to the present invention, the amount of the coupling agent is 0-15 parts by weight relative to 50 parts by weight of the filler; preferably, the amount of the coupling agent is 4-8 parts by weight relative to 50 parts by weight of the filler.

[0046] According to the present invention, the rubber solution is a soluble production line rubber solution or a dry rubber solution; preferably, the rubber solution is selected from a solution containing a base rubber; the base rubber includes natural rubber and / or synthetic rubber; preferably, the synthetic rubber is selected from one or more of polybutadiene rubber, styrene-butadiene rubber, isoprene rubber, ethylene-propylene rubber, nitrile rubber, hydrogenated nitrile rubber, butyl rubber, halogenated butyl rubber, fluororubber, silicone rubber and polyurethane rubber.

[0047] According to the present invention, the concentration of rubber in the rubber solution is 1-50wt%, preferably 5-20wt%.

[0048] According to the present invention, in step (2), the second contacting conditions include: a stirring rate of 30-1000 rpm, a time of 5 min-6 h; preferably, the second contacting conditions are not particularly limited, and the contacting temperature can be between room temperature and the boiling point of the solvent.

[0049] According to the present invention, the stirring can use general stirring and dispersing equipment, including but not limited to one or more of paddle type, open turbine type, disc turbine type, propeller type, frame type agitator and planetary mixer.

[0050] According to the present invention, the auxiliary agent is one or more of the commonly used additives in rubber formulations, including but not limited to one or more of oil, liquid rubber, antioxidant, flame retardant, colorant, coupling agent, vulcanizer, vulcanization accelerator and softener.

[0051] According to the present invention, the rubber / filler mixture is left to stand for at least 24 hours without stratification, and the rubber / filler mixture has good stability.

[0052] According to the present invention, relative to 100 parts by weight of the base rubber, the amount of the filler is 10-120 parts by weight, and the amount of the auxiliary agent is 15-30 parts by weight; preferably, relative to 100 parts by weight of the base rubber, the amount of the filler is 40-60 parts by weight, and the amount of the auxiliary agent is 17-25 parts by weight.

[0053] According to the present invention, in step (3), the rubber / filler mixture can also be contacted with an anti-solvent or anti-solvent vapor for a third time, and the anti-solvent can be any anti-solvent that can reduce the solubility of the rubber / filler mixture in the solvent. When the boiling point of the anti-solvent is higher than that of the solvent, the anti-solvent can be heated to precipitate and cause the solvent to volatilize. Preferably, the anti-solvent is alcohol or water. More preferably, it is water vapor.

[0054] According to the present invention, after the anti-solvent and the solvent are separated from the rubber / filler mixture, they can be used in a recycling manner in conjunction with condensation, separation and recovery equipment.

[0055] According to the present invention, the drying can be one or more of heating drying, room temperature drying, reduced pressure drying and atmospheric pressure drying; general drying equipment can be used, including but not limited to one or more of a blast drying oven, a vacuum drying oven, an open mill, a kneader, an internal mixer, a screw extruder and a planetary extruder.

[0056] According to the present invention, the conditions for the third contact include: a time of 30 minutes to 2 hours.

[0057] The second aspect of the present invention provides a wet co-precipitation rubber masterbatch prepared by the aforementioned preparation method.

[0058] According to the present invention, the wet co-precipitation rubber masterbatch comprises a base rubber and a filler, and the base rubber comprises natural rubber and / or synthetic rubber.

[0059] According to the present invention, relative to 100 parts by weight of the base rubber, the content of the filler is 10-100 parts by weight, preferably 20-80 parts by weight.

[0060] According to the present invention, preferably, the wet co-precipitation rubber masterbatch also contains additives, which include but are not limited to oil, and optionally one or more of liquid rubber, antioxidant, flame retardant, colorant, coupling agent, vulcanizer, vulcanization accelerator and softener.

[0061] According to the present invention, relative to 100 parts by weight of the base rubber, the content of oil is 0-30 parts, the content of liquid rubber is 0-30 parts by weight, the content of antioxidant is 0-10 parts by weight, the content of flame retardant is 0-10 parts by weight, the content of colorant is 0-10 parts by weight, the content of coupling agent is 0-15 parts by weight, and the content of softener is 0-10 parts by weight.

[0062] In addition, in the present invention, the added amounts of the vulcanizing agent and the vulcanization accelerator can be determined according to the type of the rubber base.

[0063] According to the present invention, the present invention also provides a vulcanized rubber. In the present invention, there is no particular limitation on the preparation method of the vulcanized rubber, and the method can be a method well known to those skilled in the art. Specifically, in the present invention, the masterbatch is added to an internal mixer and mixed with optional additives to obtain a first-stage mixed rubber; after being parked for a period of time, the first-stage mixed rubber and the additive are mixed in the internal mixer for two stages and then discharged, and the mixed rubber is removed from the mixer to obtain the mixed rubber; and the mixed rubber is vulcanized in a flat vulcanizer to obtain the corresponding vulcanized rubber.

[0064] A third aspect of the present invention provides a rubber product, wherein the rubber product comprises the wet co-precipitation rubber masterbatch described above.

[0065] The present invention will be described in detail below through examples.

[0066] In the following examples and comparative examples:

[0067] Solution styrene butadiene rubber SSBR2636, butadiene rubber BR9000, Sinopec Yanshan Branch;

[0068] Hydrogenated nitrile Zetpol 2010, Zeon Co., Ltd., Japan;

[0069] Silica 165N, Solvay Rhodia Ltd.;

[0070] Silane coupling agent Si69, Nanjing Shuguang Chemical Softener;

[0071] TDAE is an environmentally friendly aromatic oil, Xindayang (Ningbo) Co., Ltd.;

[0072] Carbon black N330, zinc oxide ZnO, stearic acid SA, antioxidant 4010, PEG4000, liquid paraffin, plasticizer DOP, ordinary sulfur S, vulcanizing agent DCP, vulcanization accelerator D, vulcanization accelerator TBBS, and cross-linking agent TAC are all commercially available analytically pure products.

[0073] Example 1

[0074] This embodiment is intended to illustrate the wet co-precipitation rubber masterbatch and the corresponding vulcanized rubber prepared by the method of the present invention.

[0075] formula:

[0076] Solution styrene butadiene rubber SSBR2636 is 80 parts by weight, butadiene rubber BR9000 is 20 parts by weight;

[0077] 165N is 80 parts by weight, TDAE is 10 parts by weight, N330 is 10 parts by weight, Si69 is 7 parts by weight, SA is 2 parts by weight, 4010 is 2 parts by weight, liquid paraffin is 1 part by weight, PEG4000 is 6 parts by weight, ZnO is 2 parts by weight, sulfur is 1.5 parts by weight, vulcanization accelerator D is 2 parts by weight, and vulcanization accelerator TBBS is 2 parts by weight.

[0078] Preparation method:

[0079] (1) grinding a 30% 165N hexane dispersion in a sand mill at 20 Hz for 1 h at 25° C. to obtain a filler dispersion;

[0080] (2) Then, 30% hexane solution of SSBR2636 and BR9000, Si69 and TDAE were added to the filler dispersion obtained in step (1), and the mixture was mixed for 30 minutes at a stirring rate of 100 rpm in a stirrer, and then the mixture was added to a grinder and ground for 1 hour at a grinding power of 20 Hz to obtain a finely dispersed mixture 1;

[0081] (3) hot steam (water vapor) is then introduced into the mixture 1 to obtain precipitated rubber particles after 1 hour, and the rubber particles are refined in a mixing mill at 100° C. to obtain a masterbatch;

[0082] (4) Add the above masterbatch to an internal mixer, add N330, SA, 4010, PEG4000, ZnO and liquid paraffin, mix for 5 minutes to obtain a first-stage mixed rubber. After standing for 4 hours, perform a second-stage mixing. Add the first-stage mixed rubber and vulcanization accelerator D and vulcanization accelerator TBBS to the internal mixer and mix for 4 minutes before discharging. Open the mixer to obtain a mixed rubber. After standing for 12 hours, the obtained mixed rubber is vulcanized at 165°C on a flat vulcanizer to obtain the corresponding vulcanized rubber, which is recorded as S1.

[0083] Example 2

[0084] This embodiment is intended to illustrate the wet co-precipitation rubber masterbatch and the corresponding vulcanized rubber prepared by the method of the present invention.

[0085] Formula: The masterbatch and the corresponding vulcanized rubber were prepared according to the same formula as in Example 1.

[0086] (1) Grinding a 10% 165N hexane dispersion in a sand mill at 50 Hz for 15 min at 25° C. to obtain a filler dispersion;

[0087] (2) Then, 20% hexane solution of SSBR2636 and BR9000, Si69 and TDAE were added to the filler dispersion obtained in step (1), and the mixture was mixed for 20 minutes at a stirring rate of 1000 rpm in a stirrer, and then the mixture was added to a grinder and ground for 15 minutes at a grinding power of 50 Hz to obtain a finely dispersed mixture 2;

[0088] (3) Then, ethanol was added to the mixture 2, and after 2 hours, rubber particles were separated and the rubber particles were refined in a mill at 80° C. to obtain a masterbatch;

[0089] (4) Add the above masterbatch to an internal mixer, add N330, SA, 4010, PEG4000, ZnO and liquid paraffin, mix for 5 minutes to obtain a first-stage mixed rubber. After standing for 4 hours, perform a second-stage mixing. Add the first-stage mixed rubber and vulcanization accelerator D and vulcanization accelerator TBBS to the internal mixer and mix for 4 minutes before discharging. Open the mixer to obtain a mixed rubber. After standing for 12 hours, the obtained mixed rubber is vulcanized at 165°C on a flat vulcanizer to obtain the corresponding vulcanized rubber, which is recorded as S2.

[0090] Example 3

[0091] This embodiment is intended to illustrate the wet co-precipitation rubber masterbatch and the corresponding vulcanized rubber prepared by the method of the present invention.

[0092] Formula: The masterbatch and the corresponding vulcanized rubber were prepared according to the same formula as in Example 1.

[0093] (1) grinding a 20% 165N hexane dispersion in a sand mill at 30 Hz for 30 min at 25° C. to obtain a filler dispersion;

[0094] (2) Then, 18% SSBR2636 and BR9000 hexane solution, Si69 and TDAE were added to the filler dispersion obtained in step (1), and the mixture was mixed for 45 minutes at a stirring rate of 500 rpm in a stirrer, and then the mixture was added to a grinder and ground for 1 hour at a grinding power of 30 Hz to obtain a finely dispersed mixture S;

[0095] (3) hot steam (water vapor) is then introduced into the mixture S, and precipitated rubber particles are obtained after 45 minutes. The rubber particles are refined in an open mill at 100° C. to obtain a masterbatch;

[0096] (4) Add the above masterbatch to an internal mixer, add N330, SA, 4010, PEG4000, ZnO and liquid paraffin, mix for 5 minutes to obtain a first-stage mixed rubber. After standing for 4 hours, perform a second-stage mixing. Add the first-stage mixed rubber and vulcanization accelerator D and vulcanization accelerator TBBS to the internal mixer and mix for 4 minutes before discharging. Open the mixer to obtain a mixed rubber. After standing for 12 hours, the obtained mixed rubber is vulcanized at 165°C on a flat vulcanizer to obtain the corresponding vulcanized rubber, which is recorded as S3.

[0097] Example 4

[0098] This embodiment is intended to illustrate the wet co-precipitation rubber masterbatch and the corresponding vulcanized rubber prepared by the method of the present invention.

[0099] Formula: The masterbatch and the corresponding vulcanized rubber were prepared according to the same formula as in Example 1.

[0100] (1) grinding a 40% 165N hexane dispersion in a sand mill at 5 Hz for 2 h at 25° C. to obtain a filler dispersion;

[0101] (2) Then, 30% hexane solution of SSBR2636 and BR9000, Si69 and TDAE were added to the filler dispersion obtained in step (1), and the mixture was mixed for 2 h using a stirrer at a stirring rate of 50 rpm. The mixture was then added to a grinder and ground for 2 h at a grinding power of 5 Hz to obtain a finely dispersed mixture 4.

[0102] (3) hot steam (water vapor) is then introduced into the mixture 4, and precipitated rubber particles are obtained after 1 hour. The rubber particles are refined in a mixing mill at 100° C. to obtain a masterbatch;

[0103] (4) Add the above masterbatch to an internal mixer, add N330, SA, 4010, PEG4000, ZnO and liquid paraffin, mix for 5 minutes to obtain a first-stage mixed rubber. After standing for 4 hours, perform a second-stage mixing. Add the first-stage mixed rubber and vulcanization accelerator D and vulcanization accelerator TBBS to the internal mixer and mix for 4 minutes before discharging. Open the mixer to obtain a mixed rubber. After standing for 12 hours, the obtained mixed rubber is vulcanized at 165°C on a flat vulcanizer to obtain the corresponding vulcanized rubber, which is recorded as S4.

[0104] Example 5

[0105] This embodiment is intended to illustrate the wet co-precipitation rubber masterbatch and the corresponding vulcanized rubber prepared by the method of the present invention.

[0106] Formula: 100 parts by weight of HNBR, 50 parts by weight of carbon black N330, 10 parts by weight of white carbon black 165N, 3 parts by weight of ZnO, 2 parts by weight of SA, 10 parts by weight of plasticizer DOP, 5 parts by weight of vulcanizing agent DCP, and 2 parts by weight of TAC.

[0107] Preparation method:

[0108] (1) Grinding 20% ​​165N, N330, SA, ZnO and DOP chlorobenzene dispersion in a sand mill at 20 Hz for 1 h at 40° C. to obtain a filler dispersion;

[0109] (2) Then, 8% HNBR chlorobenzene solution was added to the filler dispersion obtained in step (1), and the mixture was mixed for 1 hour at a stirring rate of 300 rpm using a stirrer to obtain a mixture;

[0110] (3) Then, hot steam (water vapor) is introduced into the mixture to obtain precipitated particles after 1 hour. The particles are dried in a vacuum oven at 80° C. for 24 hours to obtain a masterbatch;

[0111] (3) Perform two-stage mixing, add the masterbatch and the vulcanizing agents DCP and TAC into the internal mixer and mix for 4 minutes before discharging. The mixed rubber is obtained by opening the mixer. After standing for 12 hours, the obtained mixed rubber is vulcanized on a flat vulcanizer at 160°C for 45 minutes to obtain the corresponding vulcanized rubber, which is recorded as S5.

[0112] Comparative Example 1

[0113] Comparative Example 1 is to prepare the vulcanized rubber by dry mixing method.

[0114] Formulation: The vulcanized rubber was prepared according to the same formulation as in Example 1.

[0115] Preparation method:

[0116] Add SSBR and BR to the internal mixer and plasticize for 30 seconds. Add 165N, TDAE and N330 and mix for 3 minutes. Then add Si69, SA, 4010, PEG4000, ZnO and liquid paraffin. Continue mixing for 5 minutes and then discharge to obtain a first-stage mixed rubber. After standing for 4 hours, carry out the second-stage mixing. Add the first-stage mixed rubber and sulfur, D and TBBS to the internal mixer and mix for 4 minutes before discharging. Open the mixer to obtain a mixed rubber. After standing for 12 hours, the obtained mixed rubber is vulcanized at 165°C on a flat vulcanizer to obtain the corresponding vulcanized rubber, which is recorded as D1.

[0117] Comparative Example 2

[0118] Formulation: The vulcanized rubber was prepared according to the same formulation as in Example 1.

[0119] Preparation method:

[0120] 165N, Si69, and TDAE were added to a 12% hexane solution of SSBR and BR, and mixed for 30 minutes using a stirrer at a stirring rate of 500 rpm. The mixture was then added to a grinder and ground for 1 hour at a grinding power of 30 Hz to obtain a finely dispersed mixture D. The mixture was then condensed by hot steam. The granules obtained after condensation were milled to obtain a masterbatch.

[0121] Add the above masterbatch to an internal mixer, add N330, SA, 4010, PEG4000, ZnO and liquid paraffin, mix for 5 minutes to obtain a first-stage mixed rubber. After standing for 4 hours, perform a second-stage mixing. Add the first-stage mixed rubber and sulfur, D-promoting agent, and TBBS-promoting agent to the internal mixer and mix for 4 minutes before discharging. Open the mixer to obtain a mixed rubber. After standing for 12 hours, the obtained mixed rubber is vulcanized at 165°C on a flat vulcanizer to obtain the corresponding vulcanized rubber, which is recorded as D2.

[0122] Comparative Example 3

[0123] Formulation: The vulcanized rubber was prepared according to the same formulation as in Example 5.

[0124] Preparation method:

[0125] Add HNBR to the internal mixer and plasticize for 30 seconds. Add 165N, N330, SA and ZnO and mix for 3 minutes to obtain the first-stage mixed rubber. After standing for 4 hours, the second-stage mixing is carried out. Add the first-stage mixed rubber and the vulcanizing agents DCP and TAC to the internal mixer and mix for 4 minutes before discharging. The mixed rubber is obtained by opening the mixer. After standing for 12 hours, the obtained mixed rubber is vulcanized on a flat vulcanizer at 160°C for 45 minutes to obtain the corresponding vulcanized rubber, which is recorded as D3.

[0126] Test Case

[0127] The vulcanized rubbers prepared in Examples 1-5 and Comparative Examples 1-3 were characterized, and the results are shown in Table 1.

[0128] Table 1

[0129]

[0130]

[0131] It can be seen from Table 1 that the dispersion degree of the vulcanized rubber prepared by the method of the present invention is significantly improved, the mechanical properties are significantly improved, and the abrasion is significantly reduced; the masterbatch prepared by the method of the present invention has excellent filler dispersibility, stability and mechanical properties.

[0132] in addition, Figure 11 is a schematic diagram of the comparison of the sedimentation of the rubber / filler mixture prepared in Comparative Example 2 and Example 1 of the present invention after standing for one week, D represents the sample of Comparative Example 2, and S represents the sample of Example 1; Figure 1 It can be seen that the rubber / filler mixed solution prepared in Example 1 is clear and has no sedimentation, which indicates that the rubber / filler mixed solution prepared in Example 1 has good stability.

[0133] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing a wet co-precipitation rubber masterbatch, characterized in that: The preparation method comprises: (1) contacting the filler with the solvent under grinding conditions to obtain a filler dispersion; (2) subjecting the filler dispersion, rubber solution and additive to a second contact to obtain a rubber / filler mixed solution; (3) contacting the rubber / filler mixture with an anti-solvent for a third time to obtain a solid rubber / filler mixture by substitution due to polarity difference; (4) drying the solid rubber / filler mixture to obtain a wet co-precipitation rubber masterbatch.

2. The preparation method according to claim 1, wherein The anti-solvent is alcohol and / or water; Preferably, the anti-solvent is anti-solvent vapor.

3. The preparation method according to claim 1, wherein The solvents are the same or different but mutually soluble rubber good solvents; Preferably, the solvent is selected from one or more of hydrocarbons, ethers, lipids and furans.

4. The preparation method according to claim 1, wherein In step (1), the grinding conditions include: grinding power of 5-80 Hz, time of 1 min-6 h; Preferably, the grinding power is 20-50 Hz and the grinding time is 5 min-1 h.

5. The preparation method according to claim 1, wherein The filler is selected from one or more of silicon materials, carbon materials, oxides and salts; Preferably, the silicon material is selected from one or more of silicon dioxide, silicon nitride, montmorillonite and diatomaceous earth; Preferably, the carbon material is selected from one or more of carbon black, graphene and carbon nanotubes; Preferably, the oxide is selected from one or more of magnesium oxide, zinc oxide, aluminum oxide and rare earth oxides; Preferably, the salt is selected from one or more of calcium carbonate, calcium sulfate, magnesium carbonate and zinc carbonate.

6. The preparation method according to claim 1, wherein The rubber solution is a solution of a polymerized rubber production line or a dry rubber solution; Preferably, the rubber solution is selected from a solution containing a base rubber; the base rubber includes natural rubber and / or synthetic rubber; Preferably, the synthetic rubber is selected from one or more of polybutadiene rubber, styrene-butadiene rubber, isoprene rubber, ethylene-propylene rubber, nitrile rubber, hydrogenated nitrile rubber, butyl rubber, halogenated butyl rubber, fluororubber, silicone rubber and polyurethane rubber; And / or, the concentration of rubber in the rubber solution is 1-50wt%, preferably 5-20wt%.

7. The preparation method according to claim 1, wherein The conditions of the second contact include: a stirring rate of 30-1000 rpm, a grinding power of 5-80 Hz, and a time of 5 min-6 h; And / or, the conditions of the third contact include: time is 30min-2h.

8. A wet co-precipitation rubber masterbatch prepared by the preparation method described in any one of claims 1 to 7.

9. The wet co-precipitation rubber masterbatch according to claim 8, wherein: The wet co-precipitation rubber masterbatch comprises a base rubber and a filler, wherein the base rubber comprises natural rubber and / or synthetic rubber; And / or, relative to 100 parts by weight of the base rubber, the content of the filler is 10-100 parts by weight.

10. A rubber product, characterized in that: The rubber product comprises the wet co-precipitation rubber masterbatch according to claim 8 or 9.

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