A wet masterbatch and preparation method thereof

Abstract

The invention relates to the technical field of masterbatch preparation, and discloses a wet masterbatch and a preparation method thereof, which solves the problems of high energy consumption, serious pollution and incompatibility of physical properties of polymers in the conventional mechanical mixing in the prior art, improves production efficiency and reduces energy consumption. The specific process comprises dissolving solid synthetic rubber in an organic solvent to obtain liquid synthetic latex; immersing carbon material in an aqueous solution of a small molecule solvent to obtain carbon material slurry; adding the liquid synthetic latex, carbon material slurry and natural latex to a composite reaction chamber in a spraying manner for high-speed mixing to obtain a mixed solution; adding a flocculant to the mixed solution, stirring until flocculation, heating, drying and granulating to obtain a wet masterbatch. The method has simple process, high production efficiency and low equipment energy consumption, and meets the requirements of "green production".

Description

Technical Field

[0001] The invention relates to the technical field of masterbatch preparation, in particular to a wet masterbatch and a preparation method thereof. Background Art

[0002] Synthetic rubber and natural rubber are one of the main basic materials in the rubber products industry. Synthetic rubber is superior to natural rubber in terms of wear resistance, aging resistance and heat resistance, but is inferior to natural rubber in terms of strength, elasticity, flex crack resistance and processing performance. Therefore, blending synthetic rubber with natural rubber in rubber products can synergistically improve the performance of rubber products.

[0003] Mixing is the most critical process in the processing of rubber products. Its purpose is to fully mix the rubber and rubber and the rubber additives in the formula, and to make the various materials dispersed as evenly as possible. At present, the traditional mixing method in the rubber industry is to use a multi-stage kneading or shearing mixing method using an internal mixer or an open mixer. Due to the different physical properties of polymers, there are process compatibility issues. Process compatibility refers to the ability of multiple polymers to form a stable homogeneous system when blended in any proportion. It mainly relies on the heating effect of the internal mixer and the strong shear force to knead carbon black into the rubber. It is a high-energy, low-efficiency, and dust-prone process. From a thermodynamic point of view, most of the currently known polymer blends have incompatibility issues, and it is difficult to achieve molecular or segment level mixing.

[0004] With the introduction of the national "green manufacturing" policy, wet mixing has gradually emerged and grown. In order to break through the shackles of traditional mechanical mixing and the physical properties of the polymer itself, the wet mixing process can be used to improve the performance of rubber, which has the advantages of being green, environmentally friendly and low energy consumption. Summary of the invention

[0005] In view of this, the present invention provides a wet masterbatch and a preparation method thereof to solve the technical problems of traditional mechanical mixing and the physical properties of the polymer itself, as well as high energy consumption and serious dust pollution.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0007] On the one hand, a wet masterbatch is provided, comprising natural latex, solid synthetic rubber, carbon material and flocculant; wherein,

[0008] The mass ratio of the natural latex, the solid synthetic rubber and the carbon material is 5-9:1-5:5; the added amount of the flocculant is 1-10% of the total mass of the natural latex and the solid synthetic rubber.

[0009] Preferably, in the wet masterbatch, the flocculant is selected from any one of calcium chloride, sodium chloride, potassium chloride, sodium sulfate, cyclohexylamine acetate, magnesium oxide and zinc oxide.

[0010] Preferably, the wet masterbatch further comprises an organic solvent for dissolving the solid synthetic rubber into liquid synthetic latex.

[0011] Preferably, in the above wet masterbatch, the organic solvent is any one of cyclohexane, gasoline, pentane, dichloroethane, trichloroethane, hexane, heptane, dichloromethane, and phenol, and the amount of the organic solvent added is 1-15 times the mass of the solid synthetic rubber.

[0012] Preferably, the wet masterbatch further comprises white carbon black, and the mass ratio of the white carbon black to the carbon black is 3-5:0-2.

[0013] Preferably, in the above-mentioned wet masterbatch, the carbon material includes any one or more of carbon black, carbon nanotubes, graphene, fullerene, and nanographite; the carbon black is selected from any one or more of N220, N330, N550, N660, N990, N110, N115, N134, N234, N326, N339, and N375; the carbon nanotube is any one or more of single-walled carbon nanotube, multi-walled carbon nanotube, and modified carbon nanotube.

[0014] Preferably, in the above wet masterbatch, the solid synthetic rubber includes any one or more of butadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, isoprene rubber, chloroprene rubber, butyl rubber, brominated butyl rubber, nitrile rubber, hydrogenated nitrile rubber, and butylpyrrolidone rubber.

[0015] On the other hand, a method for preparing the wet masterbatch is provided, comprising the following steps:

[0016] S1: dissolving solid synthetic rubber in an organic solvent to obtain liquid synthetic latex;

[0017] S2: immersing the carbon material in an aqueous solution of a small molecule solvent to obtain a carbon material slurry;

[0018] S3: adding the liquid synthetic latex, carbon material slurry, and natural latex into the composite reaction chamber in a spraying manner and mixing them at high speed to obtain a mixed solution;

[0019] S4: adding a flocculant to the mixed solution, stirring until flocculation, heating, drying and granulating to obtain a wet masterbatch.

[0020] Preferably, in the above-mentioned method for preparing wet masterbatch, the dissolution in S1 is carried out under heating conditions, the heating temperature is 55-80° C., and the time is 2-3 h.

[0021] Preferably, in the above-mentioned method for preparing wet masterbatch, the small molecule solvent in S2 is any one of methanol, ethanol, propanol, tetrahydrofuran, acetone and butanone, or a mixture of several of them.

[0022] Preferably, in the above-mentioned method for preparing wet masterbatch, the injection speed of the carbon material slurry in S3 is 15-50 m / s, the flow rate of the natural latex is 4-5 m / s, and the flow rate of the liquid synthetic latex is 8-10 m / s.

[0023] Preferably, in the above-mentioned method for preparing wet masterbatch, the heating and drying temperature in S4 is 50-200° C., and the granulation is extrusion granulation in a twin-screw extruder.

[0024] The present invention provides a wet masterbatch and a preparation method thereof. Compared with the prior art, the present invention has the following beneficial effects:

[0025] (1) The present invention mixes and flocculates natural latex, solid synthetic rubber and carbon material, and uses a wet mixing process to prepare a composite material with uniform quality and high processing performance for mixing. The physical properties and dynamic mechanical properties of the obtained wet masterbatch are significantly improved compared with the mixed rubber prepared by the traditional mixing process, and the production cycle is also shortened, solving the problem of polymer process compatibility.

[0026] (2) The wet masterbatch preparation method of the present invention significantly improves the dusty construction environment during dry mixing, and the organic solvent and flocculant used can be separated and recycled by a simple extraction method, which meets the requirements of "green production";

[0027] (3) The wet masterbatch of the present invention can be prepared in a simple carbon material natural composite reaction chamber, which simplifies the mixing procedure. The method has simple operation steps and a continuous processing method, and has the advantages of high production efficiency and low equipment energy consumption. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0029] Figure 1 It is a schematic diagram of the main cross-sectional structure of the carbon material natural latex composite reaction chamber of the present invention;

[0030] Figure 2 It is a partially enlarged schematic diagram of the carbon material natural latex composite reaction chamber of the present invention.

[0031] In the figure, 100, composite reaction chamber; 110, control unit; 120, mixing unit; 121, carbon material slurry input pipe; 122, natural latex input pipe; 123, liquid synthetic latex input pipe; 124, valve; 130, flow guide unit; 131, other small material input pipe; 132, sealing door; 133, push rod; 140, stirring unit; 141, generator; 142, stirring rod; 143, stirring rod; 144, discharge pipe; 150, heating jacket. DETAILED DESCRIPTION

[0032] The specific implementation of the present invention is further described in detail below in conjunction with the accompanying drawings and examples. The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0033] In the description of the present application, it should be understood that the terms "center", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present application.

[0034] The terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of this application, unless otherwise specified, "plurality" means two or more.

[0035] In the description of this application, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0036] Some embodiments of the present invention provide a wet masterbatch comprising natural latex, solid synthetic rubber, carbon material and flocculant.

[0037] In some embodiments of the present invention, the mass ratio of natural latex, solid synthetic rubber and carbon material is 5-9:1-5:5, preferably 8:2:5. The rubber material within the ratio range is easier to mix. The flocculant is selected from any one of calcium chloride, sodium chloride, potassium chloride, sodium sulfate, cyclohexyl acetate, magnesium oxide and zinc oxide, preferably calcium chloride, more preferably sodium chloride, which is conducive to flocculating the rubber material into new solid substances. It can also be separated and recycled by a simple method during the production process, which is beneficial to environmental protection. The amount of flocculant added is 1-10% of the total mass of natural latex and solid synthetic rubber.

[0038] In some embodiments of the present invention, the wet masterbatch further includes an organic solvent for dissolving the solid synthetic rubber into liquid synthetic latex, and the organic solvent is any one of cyclohexane, gasoline, pentane, dichloroethane, trichloroethane, hexane, heptane, dichloromethane, and phenol, and the amount of the organic solvent added is 1-15 times the mass of the solid synthetic rubber, preferably cyclohexane, hexane or dichloromethane, which is conducive to the dissolution of the solid synthetic rubber and can be separated from it for recycling, which is beneficial to green environmental protection.

[0039] In some embodiments of the present invention, the wet masterbatch further comprises white carbon black, and the mass ratio of white carbon black to carbon black is 3-5:0-2.

[0040] In some embodiments of the present invention, the carbon material includes any one or more of carbon black, carbon nanotubes, graphene, fullerene, and nanographite, preferably carbon black; the carbon black is selected from any one or more of N220, N330, N550, N660, N990, N110, N115, N134, N234, N326, N339, and N375; the carbon nanotube is any one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, and modified carbon nanotubes. The addition of the carbon material enhances the mechanical properties and durability of the wet masterbatch and extends the service life of the wet masterbatch.

[0041] In some embodiments of the present invention, the solid synthetic rubber includes any one or more of butadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, isoprene rubber, chloroprene rubber, butyl rubber, brominated butyl rubber, nitrile rubber, hydrogenated nitrile rubber, and butylpyrrolidone rubber, preferably butadiene rubber and styrene-butadiene rubber. The addition of the solid synthetic rubber improves the heat resistance and aging resistance of the wet masterbatch.

[0042] Some other embodiments of the present invention provide a method for preparing a wet masterbatch, the steps of which are as follows:

[0043] S1: dissolving the solid synthetic rubber in an organic solvent at a heating temperature of 55-80° C. for 2-3 hours to obtain a liquid synthetic latex;

[0044] S2: immersing the carbon material in an aqueous solution of a small molecule solvent selected from any one of methanol, ethanol, propanol, tetrahydrofuran, acetone, and butanone, or a mixture of several of them, to obtain a carbon material slurry;

[0045] S3: adding the liquid synthetic latex, carbon material slurry, and natural latex into a mixing unit through a liquid synthetic latex input pipe, a carbon material slurry input pipe, and a natural latex input pipe at a spraying speed of 8-10 m / s, 15-50 m / s, and 4-5 m / s, respectively, for high-speed mixing to obtain a mixed solution;

[0046] S4: The mixed solution and flocculant are added to the diversion unit through the valve and other small material input pipes for mixing, and then poured into the stirring unit for secondary stirring, stirred until flocculation, heated to 50-200° C. by the heating jacket for heating and drying, and discharged through the discharge pipe, and then extruded into strips by a twin-screw extruder and cut into granules for granulation to obtain the wet masterbatch.

[0047] like Figure 1-2 As shown, in some embodiments of the present invention, the composite reaction chamber 100 of the equipment for preparing wet masterbatch in S3 includes a mixing unit 120, a flow guide unit 130, a stirring unit 140, a control unit 110 and a heating jacket 150; wherein,

[0048] The mixing unit 120 is arranged inside the composite reaction chamber 100; the guide unit 130 is arranged below the mixing unit 120; the stirring unit 140 is arranged below the guide unit 130; the control unit 110 is arranged inside the composite reaction chamber 100, including a collection module, a processing module and a control module, and the control unit 110 automatically controls the operation of the mixing unit 120, the guide unit 130 and the stirring unit 140; the heating jacket 150 is arranged outside the composite reaction chamber 100.

[0049] In some embodiments of the present invention, the side wall of the mixing unit 120 is connected to a carbon material slurry input pipe 121 , a natural latex input pipe 122 and a liquid synthetic latex input pipe 123 , and the side wall of the guide unit 130 is connected to other small material input pipes 131 .

[0050] In some embodiments of the present invention, the stirring unit drives the stirring rod 142 and the stirring rod 143 to rotate via the generator 141 .

[0051] In some embodiments of the present invention, the mixing unit 120 and the diversion unit 130 are connected by a valve 124 , and the mixed solution is added into the diversion unit 130 by pulling the valve 124 .

[0052] In some embodiments of the present invention, the guide unit 130 is connected to the stirring unit 140 via a sealing door 132 , and the mixed solution is poured into the stirring unit 140 by pulling the push rod 133 to drive the sealing door 132 .

[0053] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0054] Example 1

[0055] The wet masterbatch of this embodiment includes the following components in parts by weight: 50 parts of natural latex, 50 parts of solid chloroprene rubber, 50 parts of N330 carbon black, and 2 parts of flocculant.

[0056] The wet masterbatch is prepared according to the following method, comprising the steps of:

[0057] S1: dissolving solid chloroprene rubber in 500 parts of dichloromethane, stirring at 55°C for 3 hours, and cooling naturally to obtain liquid chloroprene rubber latex;

[0058] S2: immersing N330 carbon black in an aqueous solution of methanol to obtain N330 carbon black slurry;

[0059] S3: adding liquid chloroprene rubber latex, N330 carbon black slurry, and natural latex into a mixing unit at injection speeds of 8 m / s, 15 m / s, and 4 m / s, respectively, for high-speed mixing to obtain a mixed solution;

[0060] S4: Add the mixed solution and calcium chloride flocculant into the diversion unit, mix and pour into the stirring unit for secondary stirring and mixing. At the same time, heat to 50°C through the heating jacket for heating and drying and discharge through the discharge pipe, and then granulate through a twin-screw extruder to obtain the wet masterbatch.

[0061] Example 2

[0062] The wet masterbatch of this embodiment includes the following components in parts by weight: 90 parts of natural latex, 10 parts of solid styrene-butadiene rubber, 50 parts of single-walled carbon nanotubes, and 9 parts of flocculant.

[0063] The wet masterbatch is prepared according to the following method, comprising the steps of:

[0064] S1: dissolving solid styrene butadiene rubber in 100 parts of hexane, stirring at 68°C for 2.5 hours, and cooling naturally to obtain liquid styrene butadiene rubber latex;

[0065] S2: immersing the single-walled carbon nanotubes in an aqueous solution of methanol to obtain a single-walled carbon nanotube slurry;

[0066] S3: adding liquid styrene-butadiene rubber latex, single-walled carbon nanotube slurry, and natural latex into a mixing unit at injection speeds of 9 m / s, 35 m / s, and 4.5 m / s, respectively, for high-speed mixing to obtain a mixed solution;

[0067] S4: adding the mixed solution and sodium chloride flocculant into the diversion unit, and pouring into the stirring unit after mixing for secondary stirring and mixing. Meanwhile, the mixed solution is heated to 200°C by the heating jacket for drying and discharged through the discharge pipe, and then granulated by a twin-screw extruder to obtain the wet masterbatch.

[0068] Example 3

[0069] The wet masterbatch of this embodiment includes the following components in parts by weight: 80 parts of natural latex, 20 parts of solid butadiene rubber, 50 parts of N550 carbon black, and 5 parts of flocculant.

[0070] The wet masterbatch is prepared according to the following method, comprising the steps of:

[0071] S1: dissolving solid butadiene rubber in 200 parts of cyclohexane, stirring at 80°C for 2 hours, and cooling naturally to obtain liquid butadiene rubber latex;

[0072] S2: immersing N550 carbon black in an aqueous solution of methanol to obtain N550 carbon black slurry;

[0073] S3: adding liquid butadiene rubber latex, N550 carbon black slurry, and natural latex into a mixing unit at injection speeds of 10 m / s, 50 m / s, and 5 m / s, respectively, for high-speed mixing to obtain a mixed solution;

[0074] S4: Add the mixed solution and calcium chloride flocculant into the diversion unit, mix and pour into the stirring unit for secondary stirring and mixing. At the same time, heat to 125°C through the heating jacket for heating and drying and discharge through the discharge pipe, and then granulate through a twin-screw extruder to obtain the wet masterbatch.

[0075] Example 4

[0076] The wet masterbatch of this embodiment includes the following components in parts by weight: 80 parts of natural latex, 20 parts of solid butadiene rubber, 40 parts of multi-walled carbon nanotubes, 10 parts of white carbon black, and 5 parts of flocculant.

[0077] The wet masterbatch is prepared according to the following method, comprising the steps of:

[0078] S1: dissolving solid butadiene rubber in 200 parts of hexane, stirring at 80°C for 2 hours, and cooling naturally to obtain liquid butadiene rubber latex;

[0079] S2: immersing the multi-walled carbon nanotubes and white carbon black in an aqueous solution of tetrahydrofuran to obtain a multi-walled carbon nanotube slurry and a white carbon black slurry;

[0080] S3: adding liquid butadiene rubber latex, multi-walled carbon nanotube slurry, white carbon black slurry and natural latex into a mixing unit at injection speeds of 10 m / s, 50 m / s, 50 m / s and 5 m / s, respectively, for high-speed mixing to obtain a mixed solution;

[0081] S4: Add the mixed solution and sodium chloride flocculant into the diversion unit, mix and pour into the stirring unit for secondary stirring and mixing. At the same time, heat to 125°C through the heating jacket for heating and drying and discharge through the discharge pipe, and then granulate through a twin-screw extruder to obtain the wet masterbatch.

[0082] Example 5

[0083] The wet masterbatch of this embodiment includes the following components in parts by weight: 80 parts of natural latex, 20 parts of solid styrene-butadiene rubber, 30 parts of N550 carbon black, 20 parts of white carbon black, and 5 parts of flocculant.

[0084] The wet masterbatch is prepared according to the following method, comprising the steps of:

[0085] S1: dissolving solid styrene butadiene rubber in 200 parts of cyclohexane, stirring at 80°C for 2 hours, and cooling naturally to obtain liquid styrene butadiene rubber latex;

[0086] S2: immersing N550 carbon black and white carbon black in an aqueous solution of tetrahydrofuran to obtain N550 carbon black slurry and white carbon black slurry;

[0087] S3: adding liquid styrene-butadiene rubber latex, N550 carbon black slurry, white carbon black slurry and natural latex into a mixing unit at injection speeds of 10 m / s, 50 m / s, 50 m / s and 5 m / s, respectively, for high-speed mixing to obtain a mixed solution;

[0088] S4: Add the mixed solution and calcium chloride flocculant into the diversion unit, mix and pour into the stirring unit for secondary stirring and mixing. At the same time, heat to 125°C through the heating jacket for heating and drying and discharge through the discharge pipe, and then granulate through a twin-screw extruder to obtain the wet masterbatch.

[0089] Comparative Example 1

[0090] The difference between this comparative example and Example 1 is that only white carbon black is added to the carbon material in the wet masterbatch component, as follows:

[0091] The wet masterbatch of this comparative example comprises the following components in parts by weight: 50 parts of natural latex, 50 parts of solid styrene-butadiene rubber, 50 parts of white carbon black, and 2 parts of flocculant.

[0092] The wet masterbatch is prepared according to the following method, comprising the steps of:

[0093] S1: dissolving solid styrene butadiene rubber in 500 parts of dichloromethane, stirring at 55°C for 3 hours, and cooling naturally to obtain liquid styrene butadiene rubber latex;

[0094] S2: immersing the white carbon black in an aqueous solution of methanol to obtain a white carbon black slurry;

[0095] S3: adding liquid styrene-butadiene rubber latex, white carbon black slurry and natural latex into a mixing unit at injection speeds of 8 m / s, 15 m / s and 4 m / s, respectively, for high-speed mixing to obtain a mixed solution;

[0096] S4: Add the mixed solution and calcium chloride flocculant into the diversion unit, mix and pour into the stirring unit for secondary stirring and mixing. At the same time, heat to 50°C through the heating jacket for heating and drying and discharge through the discharge pipe, and then granulate through a twin-screw extruder to obtain the wet masterbatch.

[0097] Comparative Example 2

[0098] The difference between this comparative example and Example 2 lies in the mass ratio of natural latex to solid synthetic rubber, which is as follows:

[0099] The wet masterbatch of this comparative example comprises the following components in parts by weight: 40 parts of natural latex, 60 parts of solid styrene-butadiene rubber, 50 parts of single-walled carbon nanotubes, and 9 parts of flocculant.

[0100] The wet masterbatch is prepared according to the following method, comprising the steps of:

[0101] S1: dissolving solid styrene butadiene rubber in 600 parts of hexane, stirring at 68°C for 2.5 hours, and cooling naturally to obtain liquid styrene butadiene rubber latex;

[0102] S2: immersing the single-walled carbon nanotubes in an aqueous solution of methanol to obtain a single-walled carbon nanotube slurry;

[0103] S3: adding liquid styrene-butadiene rubber latex, single-walled carbon nanotube slurry, and natural latex into a mixing unit at injection speeds of 9 m / s, 35 m / s, and 4.5 m / s, respectively, for high-speed mixing to obtain a mixed solution;

[0104] S4: adding the mixed solution and sodium chloride flocculant into the diversion unit, and pouring into the stirring unit after mixing for secondary stirring and mixing. Meanwhile, the mixed solution is heated to 200°C by the heating jacket for drying and discharged through the discharge pipe, and then granulated by a twin-screw extruder to obtain the wet masterbatch.

[0105] Comparative Example 3

[0106] The difference between this comparative example and Example 3 is that only natural rubber latex and carbon material N550 carbon black are added to the components of the wet masterbatch, as follows:

[0107] The wet masterbatch of this comparative example includes the following components in parts by weight: 80 parts of natural rubber latex, 50 parts of N550 carbon black, and 5 parts of flocculant.

[0108] The wet masterbatch is prepared according to the following method, comprising the steps of:

[0109] S1: immersing N550 carbon black in an aqueous solution of methanol to obtain N550 carbon black slurry;

[0110] S2: adding N550 carbon black slurry and natural rubber latex into a mixing unit at injection speeds of 50 m / s and 5 m / s respectively for high-speed mixing to obtain a mixed solution;

[0111] S3: Add the mixed solution and calcium chloride flocculant into the diversion unit, mix and pour into the stirring unit for secondary stirring and mixing. At the same time, heat to 125°C through the heating jacket for heating and drying and discharge through the discharge pipe, and then granulate through a twin-screw extruder to obtain the wet masterbatch.

[0112] Comparative Example 4

[0113] The difference between this comparative example and Example 3 lies in the temperature and time of dissolution of the solid synthetic rubber, which are as follows:

[0114] The wet masterbatch of this comparative example includes the following components in parts by weight: 80 parts of natural rubber latex, 20 parts of solid butadiene rubber, 50 parts of N550 carbon black, and 5 parts of flocculant.

[0115] The wet masterbatch is prepared according to the following method, comprising the steps of:

[0116] S1: dissolving solid butadiene rubber in 200 parts of cyclohexane, stirring at 40°C for 3 hours, and cooling naturally to obtain liquid butadiene rubber latex;

[0117] S2: immersing N550 carbon black in an aqueous solution of methanol to obtain N550 carbon black slurry;

[0118] S3: adding liquid butadiene rubber latex, N550 carbon black slurry, and natural latex into a mixing unit at injection speeds of 10 m / s, 50 m / s, and 5 m / s, respectively, for high-speed mixing to obtain a mixed solution;

[0119] S4: Add the mixed solution and calcium chloride flocculant into the diversion unit, mix and pour into the stirring unit for secondary stirring and mixing. At the same time, heat to 125°C through the heating jacket for heating and drying and discharge through the discharge pipe, and then granulate through a twin-screw extruder to obtain the wet masterbatch.

[0120] Comparative Example 5

[0121] The difference between this comparative example and Example 4 lies in the injection speed of the solid synthetic rubber, carbon material, and natural latex, which is as follows:

[0122] The wet masterbatch of this comparative example includes the following components in parts by weight: 80 parts of natural latex, 20 parts of solid butadiene rubber, 40 parts of multi-walled carbon nanotubes, 10 parts of white carbon black, and 5 parts of flocculant.

[0123] The wet masterbatch is prepared according to the following method, comprising the steps of:

[0124] S1: dissolving solid butadiene rubber in 200 parts of hexane, stirring at 80°C for 2 hours, and cooling naturally to obtain liquid butadiene rubber latex;

[0125] S2: immersing the multi-walled carbon nanotubes and white carbon black in an aqueous solution of tetrahydrofuran to obtain a multi-walled carbon nanotube slurry and a white carbon black slurry;

[0126] S3: adding liquid butadiene rubber latex, multi-walled carbon nanotube slurry, white carbon black slurry and natural latex into a mixing unit at injection speeds of 6 m / s, 10 m / s, 10 m / s and 3 m / s, respectively, for high-speed mixing to obtain a mixed solution;

[0127] S4: Add the mixed solution and sodium chloride flocculant into the diversion unit, mix them and pour them into the stirring unit for secondary stirring and mixing. At the same time, heat them to 125°C in the heating jacket for drying and discharge them through the discharge pipe, and then granulate them through the twin-screw extruder to obtain the wet masterbatch.

[0128] Comparative Example 6

[0129] The difference between this comparative example and Example 5 is that the mixing method is dry mixing, which is as follows:

[0130] The wet masterbatch comprises the following components in parts by weight: 80 parts of natural latex, 20 parts of solid styrene-butadiene rubber, 30 parts of N550 carbon black, 20 parts of white carbon black, and 5 parts of flocculant.

[0131] The wet masterbatch is prepared according to the following method, comprising the steps of:

[0132] S1: solid styrene-butadiene rubber, N550 carbon black, white carbon black and natural latex are added into a stirring kettle, 200 parts of cyclohexane organic solvent is added during the stirring process, and the temperature is controlled at 80°C and stirred for 2 hours, and then naturally cooled to obtain a mixed solution;

[0133] S2: adding the mixed solution described in S1 into a mixing device to obtain a masterbatch;

[0134] S3: adding the masterbatch and calcium chloride flocculant described in S2 into a mixing device, mixing, and removing the glue.

[0135] The wet masterbatch obtained in Examples 1 to 5 and Comparative Examples 1 to 6 was mixed according to the formula in Table 1, and the main properties of the wet masterbatch were tested, wherein the detection standard of Mooney viscosity ML (1+4) 100 is GB / T 1232.1-2016, the detection standard of vulcanization characteristics 150°C T90 and MH-ML is GB / T 16584-1996, the detection standard of Shore A hardness is GB / T 531.1-2008, the detection standard of tensile strength, 100% tensile stress, 300% tensile stress, and elongation at break is GB / T 528-2009, the detection standard of tear strength is GB / T 529-2008, the detection standard of rebound performance is GB / T 1681-2009, and the detection standard of low hysteresis performance compression heat rise is GB / T 1687-2016, the test standard for wear resistance Akron wear volume is GB / T1689-2014, and the test standard for DIN wear volume is GB / T 9867-2008. The specific test results are shown in Table 2 and Table 3.

[0136] Table 1

[0137]

[0138] The test results of various properties of Examples 1 to 5 are shown in the following table:

[0139] Table 2

[0140]

[0141] The test results of various properties of Comparative Examples 1 to 6 are shown in the following table:

[0142] Table 3

[0143]

[0144]

[0145] It can be seen from the above embodiments that the present invention provides a wet masterbatch and a method for preparing the wet masterbatch by using a wet mixing process.

[0146] It should be noted that, from the test results of Comparative Examples 1 to 3 and Examples 1 to 3 in Tables 2 and 3, it can be seen that the Mooney viscosity, compression heat temperature rise, Akron wear volume and DIN wear volume of the wet masterbatch prepared by the components provided by the present invention are lower, which proves that the composite carbon material provided by the present invention has low mixing energy consumption, is conducive to processing, and has better low hysteresis performance and wear resistance of the rubber; the vulcanization characteristic T90 time is shorter, which means that the vulcanization speed of the wet masterbatch prepared by the present invention is faster, which is conducive to improving production efficiency.

[0147] It should be further explained that, from the test results of Comparative Examples 4 to 5 and Examples 3 to 4 in Tables 2 and 3, it can be seen that the dissolution temperature, time and injection speed of the components in Comparative Examples 4 to 5 are beyond the parameter range provided by the present invention, and the mechanical properties of the prepared wet masterbatch such as tensile strength, tensile strength, tear strength, hardness and elongation at break are similar, but the Mooney viscosity and compression heat temperature rise are high, and the MH-ML and rebound performance are low. The performance of the prepared wet masterbatch is lower than that of the wet masterbatch prepared in Examples 3 to 4 of the present invention, and the wet masterbatch carbon material of the present invention has better bonding performance with rubber, and the low hysteresis performance of the carbon material is also better.

[0148] In addition, from the comparison of the test results of Comparative Examples 1 to 6 with Examples 1 to 5 in Tables 2 and 3, it can be seen that the low hysteresis performance and wear resistance of the wet masterbatch prepared by the components and equipment provided by the present invention are greatly improved, and the mixing method of the present invention greatly improves the production efficiency and reduces energy consumption. Among them, Comparative Example 6 adopts dry mixing, dust is flying during the preparation process, seriously polluting the environment, and the obtained wet masterbatch has low performance. In Example 5, wet mixing is adopted, there is no dust in the preparation process, and the solvent and flocculant can be recycled, which is beneficial to protecting the environment and reducing energy consumption. At the same time, the performance of the obtained wet masterbatch is better.

[0149] In summary, the wet masterbatch prepared by the mixing method of the present invention and the components and equipment provided by the present invention has better performance such as low hysteresis performance and wear resistance. Compared with the prior art, the preparation process of the present invention is green and environmentally friendly, the rubber is easier to mix, the problem of polymer process compatibility is solved, and the production efficiency is improved and the energy consumption is reduced.

[0150] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0151] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and intent of the present invention.

Claims

1. A wet masterbatch, characterized in that: The method comprises the following components by weight: 80 parts of natural latex, 20 parts of solid styrene-butadiene rubber, 30 parts of N550 carbon black, 20 parts of white carbon black, and 5 parts of flocculant; the preparation method comprises the following steps: S1: dissolving solid styrene butadiene rubber in 200 parts of cyclohexane, stirring at 80°C for 2 hours, and cooling naturally to obtain liquid styrene butadiene rubber latex; S2: immersing N550 carbon black and white carbon black in an aqueous solution of tetrahydrofuran to obtain N550 carbon black slurry and white carbon black slurry; S3: adding liquid styrene-butadiene rubber latex, N550 carbon black slurry, white carbon black slurry and natural latex into a mixing unit at injection speeds of 10 m / s, 50 m / s, 50 m / s and 5 m / s, respectively, for high-speed mixing to obtain a mixed solution; S4: Add the mixed solution and calcium chloride flocculant into the diversion unit, mix and pour into the stirring unit for secondary stirring and mixing. At the same time, heat to 125°C through the heating jacket for heating and drying and discharge through the discharge pipe, and then granulate through a twin-screw extruder to obtain the wet masterbatch.

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