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; and (3) carrying out devolatilization and solvent removal on the rubber / filler mixed solution, and then carrying out drying treatment to obtain the wet-process co-precipitated rubber master batch. According to the preparation method, by introducing a simple pretreatment process, the stability of a glue solution / filler dispersion liquid can be obviously improved, and the prepared masterbatch has excellent filler dispersity, stability and mechanical properties.

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] In the rubber production process, mixing is one of the most basic and important processing processes. Due to the high viscosity of rubber, the traditional dry mixing process consumes a lot of energy and there is serious dust pollution during the mixing process of fillers.

[0003] Wet mixing technology has become the focus of industry development by simplifying procedures, reducing investment in equipment, manpower and resources, and greatly reducing refining costs. In addition, wet mixing is expected to improve filler dispersion, ensure uniform composition and performance, and obtain good comprehensive performance.

[0004] 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.

[0005] 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.

[0006] 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.

[0007] 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.

[0008] Therefore, it is of great significance to study and develop a method for preparing wet co-precipitation rubber masterbatch. Summary of the invention

[0009] 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-precipitation 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, and the prepared masterbatch has excellent filler dispersibility, stability and mechanical properties.

[0010] 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:

[0011] (1) contacting the filler with the solvent under grinding conditions to obtain a filler dispersion;

[0012] (2) subjecting the filler dispersion, rubber solution and additive to a second contact to obtain a rubber / filler mixed solution;

[0013] (3) After the rubber / filler mixture is devolatilized and the solvent is removed, it is dried 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 mechanical properties and dispersion degree of the rubber compound prepared by the method are significantly improved, and the stability of the rubber liquid / filler dispersion can be significantly improved;

[0018] (2) obtaining a wet co-precipitation rubber masterbatch by a devolatilization process;

[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 schematic diagram comparing the sedimentation of the rubber / filler mixed solution prepared in Comparative Example 2 and Example 1 of the present invention after standing for one week;

[0021] Figure 2 It is a strain scanning schematic diagram of the wet co-precipitation rubber masterbatch prepared by Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3 and Example 4 of the present invention.

[0022] Description of Reference Numerals

[0023] D-sample of comparative example 2; S-sample of example 1;

[0024] D1-Comparative Example 1; D2-Comparative Example 2;

[0025] S1 - Example 1; S2 - Example 2; S3 - Example 3; S4 - Example 4. DETAILED DESCRIPTION

[0026] 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.

[0027] 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:

[0028] (1) contacting the filler with the solvent under grinding conditions to obtain a filler dispersion;

[0029] (2) subjecting the filler dispersion, rubber solution and additive to a second contact to obtain a rubber / filler mixed solution;

[0030] (3) After the rubber / filler mixture is devolatilized and the solvent is removed, it is dried to obtain a wet co-precipitation rubber masterbatch.

[0031] The inventors of the present invention have discovered that the preparation process of the wet co-precipitation rubber masterbatch of the present invention introduces a simple pretreatment process, and the pre-treated filler dispersion is then mixed with a rubber solution and an additive using a dispersing device to obtain a stable rubber / filler dispersion, which can be combined with a devolatilization process to obtain a wet co-precipitation rubber masterbatch.

[0032] According to the present invention, in step (1), the grinding conditions include: grinding power of 5-80 Hz, time of 1 min-6 h; preferably, grinding power of 20-50 Hz, time of 5 min-1 h; more preferably, grinding power of 25-30 Hz, time of 5 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.

[0033] 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.

[0034] 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.

[0035] 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 %.

[0036] 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.

[0037] In the present invention, the physical adsorption is to use Van der Waals force to adsorb the adsorbent onto the particle surface.

[0038] In the present invention, the chemical modification includes one or more of coupling agent modification, grafting modification and surface growth modification.

[0039] 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).

[0040] 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.

[0041] 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, esters and furans.

[0042] 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.

[0043] In the present invention, the ether solvent is selected from diethyl ether and / or propylene oxide.

[0044] In the present invention, the ester solvent is selected from one or more of methyl acetate, ethyl acetate and propyl acetate.

[0045] In the present invention, the furan solvent is tetrahydrofuran.

[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, and 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] The vulcanization accelerator may be vulcanization accelerator TS and / or vulcanization accelerator TBBS.

[0052] The antioxidant may be antioxidant 4010.

[0053] 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.

[0054] 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 20-80 parts by weight, and the amount of the auxiliary agent is 17-25 parts by weight.

[0055] According to the present invention, in step (3), preferably, the solvent can be removed by devolatilization through twin-screw extrusion. After the solvent is separated from the rubber / filler mixture, it can be recycled in conjunction with condensation, separation and recovery equipment.

[0056] 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.

[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 10-120 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 Nd40, BR9000, Sinopec Yanshan Branch;

[0068] Isoprene rubber IR SKI-3, Russia;

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

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

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

[0072] Zinc oxide ZnO, stearic acid SA, antioxidant 4010, ordinary sulfur S, vulcanization accelerator TS, and vulcanization accelerator TBBS 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] 15 parts by weight of solution styrene butadiene rubber SSBR2636, 70 parts by weight of butadiene rubber BR Nd40, and 15 parts by weight of isoprene rubber IRSKI-3;

[0077] Filler white carbon black 165N is 50 parts by weight, Si69 is 4 parts by weight;

[0078] TDAE is 5 parts by weight, stearic acid SA is 2 parts by weight, ZnO is 5 parts by weight, ordinary sulfur S is 2 parts by weight, vulcanization accelerator TS is 1.5 parts by weight, vulcanization accelerator TBBS is 1.5 parts by weight, and antioxidant 4010 is 1.5 parts by weight.

[0079] Preparation method:

[0080] (1) Si69 is added to a 10% 165N hexane dispersion and ground in a sand mill at 20 Hz for 1 hour to obtain a filler dispersion; then 18% SSBR, BR Nd40 and IR SKI-3 hexane solutions, TDAE, SA, 4010 and ZnO are added, and mixed in a stirrer at 200 rpm for 45 minutes, and then the mixture is added to a grinder and ground at 20 Hz for 1 hour to obtain a finely dispersed mixture, and then the mixture is extruded through a twin-screw devolatilizer to remove the solvent to obtain a masterbatch;

[0081] (2) Perform two-stage mixing. Add the first-stage mixed rubber and sulfur, TS promoter, and TBBS promoter into the internal mixer and mix for 4 minutes before discharging. Remove the mixed rubber from the mixer to obtain the mixed rubber. After standing for 12 hours, the mixed rubber is vulcanized on a flat vulcanizer at 150°C for 45 minutes to obtain the corresponding vulcanized rubber, which is recorded as S1.

[0082] Example 2

[0083] 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.

[0084] Formula: The wet co-precipitation rubber masterbatch and the corresponding vulcanized rubber were prepared according to the same formula as in Example 1.

[0085] Preparation method:

[0086] (1) Si69 is added to a 20% 165N hexane dispersion and ground in a sand mill at 50 Hz for 5 minutes to obtain a filler dispersion; then 18% SSBR, BR Nd40 and IR SKI-3 hexane solutions, TDAE, SA, 4010 and ZnO are added, and mixed in a stirrer at 700 rpm for 15 minutes, and then the mixture is added to a grinder at 60 Hz for 10 minutes for fine dispersion to obtain a finely dispersed mixture, and then the mixture is extruded through a twin-screw devolatilizer to remove the solvent to obtain a masterbatch;

[0087] (2) Perform two-stage mixing. Add the first-stage mixed rubber and sulfur, TS promoter, and TBBS promoter into the internal mixer and mix for 4 minutes before discharging. Remove the mixed rubber from the mixer to obtain the mixed rubber. After standing for 12 hours, the mixed rubber is vulcanized on a flat vulcanizer at 150°C for 45 minutes to obtain the corresponding vulcanized rubber, which is recorded as S2.

[0088] Example 3

[0089] 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.

[0090] Formula: The wet co-precipitation rubber masterbatch and the corresponding vulcanized rubber were prepared according to the same formula as in Example 1.

[0091] Preparation method:

[0092] (1) Si69 is added to a 25% 165N hexane dispersion, and ground in a sand mill at 30 Hz for 30 minutes to obtain a filler dispersion; then 18% SSBR, BR Nd40 and IR SKI-3 hexane solutions, TDAE, SA, 4010 and ZnO are added, and mixed in a stirrer at 500 rpm for 30 minutes, and then the mixture is added to a grinder and ground at 30 Hz for 40 minutes to obtain a finely dispersed mixture, and then the mixture is extruded through a twin-screw devolatilizer to remove the solvent to obtain a masterbatch;

[0093] (2) Perform two-stage mixing. Add the first-stage mixed rubber and sulfur, TS promoter, and TBBS promoter into the internal mixer and mix for 4 minutes before discharging. Remove the mixed rubber from the mixer to obtain the mixed rubber. After standing for 12 hours, the mixed rubber is vulcanized on a flat vulcanizer at 150°C for 45 minutes to obtain the corresponding vulcanized rubber, which is recorded as S3.

[0094] Example 4

[0095] 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.

[0096] Formula: The wet co-precipitation rubber masterbatch and the corresponding vulcanized rubber were prepared according to the same formula as in Example 1.

[0097] Preparation method:

[0098] (1) Si69 was added to 40% 165N hexane dispersion and ground in a sand mill at 5 Hz for 20 minutes to obtain a filler dispersion; then 18% SSBR, BR Nd40 and IR SKI-3 hexane solutions, TDAE, SA, 4010 and ZnO were added, and mixed in a stirrer at 100 rpm for 5 minutes, and then the mixture was passed through a twin-screw extruder devolatilizer to remove the solvent to obtain a masterbatch;

[0099] (2) Perform two-stage mixing. Add the first-stage mixed rubber and sulfur, TS promoter, and TBBS promoter into the internal mixer and mix for 4 minutes before discharging. Remove the mixed rubber from the mixer to obtain the mixed rubber. After standing for 12 hours, the mixed rubber is vulcanized on a flat vulcanizer at 150°C for 45 minutes to obtain the corresponding vulcanized rubber, which is recorded as S4.

[0100] Comparative Example 1

[0101] This comparative example 1 is to illustrate the use of dry mixing to prepare vulcanized rubber.

[0102] formula:

[0103] 15 parts by weight of solution styrene butadiene rubber SSBR2636, 70 parts by weight of butadiene rubber BR Nd40, and 15 parts by weight of isoprene rubber IRSKI-3;

[0104] Filler white carbon black 165N is 50 parts by weight, Si69 is 4 parts by weight;

[0105] TDAE is 5 parts by weight, stearic acid SA is 2 parts by weight, ZnO is 5 parts by weight, ordinary sulfur S is 2 parts by weight, vulcanization accelerator TS is 1.5 parts by weight, vulcanization accelerator TBBS is 1.5 parts by weight, and antioxidant 4010 is 1.5 parts by weight.

[0106] Preparation method:

[0107] Add SSBR, BR Nd40 and IR SKI-3 to the internal mixer and mix for 30 seconds. Add 165N and mix for 3 minutes. Then add Si69, SA, ZnO, TDAE and 4010. Continue mixing for 5 minutes and then discharge to obtain the first-stage mixed rubber. After standing for 4 hours, carry out the second-stage mixing. Add the first-stage mixed rubber and sulfur, TS promoter and TBBS promoter to the internal mixer and mix for 4 minutes and then discharge. Open the mixer to obtain the mixed rubber. After standing for 12 hours, the obtained mixed rubber is vulcanized on a flat vulcanizer at 150°C for 45 minutes to obtain the corresponding vulcanized rubber, which is recorded as D1.

[0108] Comparative Example 2

[0109] Formulation: The vulcanized rubber was prepared according to the same formulation as in Comparative Example 1.

[0110] 165N, Si69, and TDAE were added to a hexane solution of 10% SSBR, BR Nd40, and IR SKI-3. After initial mixing in a stirrer for 45 minutes, the mixture was added to a grinder for fine dispersion to obtain a finely dispersed mixture D. The mixture was then extruded through a twin-screw devolatilizer to remove the solvent to obtain a masterbatch.

[0111] Add the above masterbatch to an internal mixer, add SA, ZnO, TDAE and 4010, and mix for 5 minutes to obtain a first-stage mixed rubber. After standing for 4 hours, perform a second-stage mixed rubber. After standing for 4 hours, perform a second-stage mixed rubber. Add the first-stage mixed rubber and sulfur, TS promoter, and TBBS promoter 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 on a flat vulcanizer at 150°C for 45 minutes to obtain the corresponding vulcanized rubber, which is recorded as D2.

[0112] Test Case

[0113] The samples prepared in Examples 1-4 and Comparative Examples 1-2 were characterized, and the results are shown in Table 1.

[0114] Table 1

[0115] project D1 D2 S1 S2 S3 S4 Tensile strength MPa 9.80 10.9 11.7 11.5 12.2 11.0 Elongation at break 394 369 428 420 411 415 Compression temperature rise / ℃ 46.0 42.1 41.1 40.8 39.7 41.6 Carbon black dispersion X / Y 7.2 / 6.8 7.9 / 8.3 8.5 / 9.2 9.0 / 8.2 9.5 / 9.0 8.7 / 8.0 <![CDATA[DIN wear / mm 3 > 37 38 32 33 30 35

[0116] It can be seen from Table 1 that the dispersion degree of the vulcanized rubber obtained by using Examples 1-4 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.

[0117] in addition, Figure 1 1 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.

[0118] Figure 2 It is a strain scan schematic diagram of the wet co-precipitation rubber masterbatch prepared by Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3 and Example 4 of the present invention, wherein D1 represents the sample of Comparative Example 1, D2 represents the sample of Comparative Example 2, S1 represents the sample of Example 1, S2 represents the sample of Example 2, S3 represents the sample of Example 3, and S4 represents the sample of Example 4; from the Payne effect results, specifically, the smaller the modulus difference, the smaller the Payne effect, the better the dispersion, it can be seen that the dispersion degree of the mixed rubber prepared by this method is significantly improved.

[0119] 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) After the rubber / filler mixture is devolatilized and the solvent is removed, it is dried to obtain a wet co-precipitation rubber masterbatch.

2. 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.

3. The preparation method according to claim 1 or 2, 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.

4. 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, esters and furans.

5. 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, and 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%.

6. The preparation method according to claim 1, wherein The conditions for 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.

7. The preparation method according to any one of claims 1 to 6, wherein: Relative to 100 parts by weight of the base rubber, the amount of the filler is 10-100 parts by weight, and the amount of the auxiliary agent is 15-30 parts by weight.

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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