CN117801329A - Full-formula water-based wet-process mixed rubber composite masterbatch and preparation method thereof - Google Patents
Full-formula water-based wet-process mixed rubber composite masterbatch and preparation method thereof Download PDFInfo
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- 239000005060 rubber Substances 0.000 title claims abstract description 153
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 25
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- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 2
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- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a full-formula water-based wet-mixed rubber composite master batch, which comprises all components for forming the composite master batch, wherein the components are dispersed in various water-based dispersion liquid, and the various water-based dispersion liquid comprises a water-based dispersion liquid I, a water-based dispersion liquid II and a water-based dispersion liquid III; and (3) feeding various water-based dispersion liquid into a reactor in a parallel flow mode, and mixing and demulsifying under stirring to obtain the composite masterbatch. The invention carries out flocculation precipitation on the filler, various rubber additives and rubber latex through liquid phase, and has the advantages of reducing mixing energy consumption, simplifying process steps, improving the uniformity of filler dispersion and rubber additive dispersion, enhancing the performance of rubber composite materials and the like.
Description
Technical Field
The invention belongs to the technical field of rubber materials, and particularly relates to a full-formula (multi-component) water-based wet mixing rubber composite masterbatch and a preparation method thereof.
Background
In the rubber processing, the compounding step plays a critical role in the quality and performance of the final rubber product. The aim of mixing is to ensure that the filler and auxiliary agent in the rubber are uniformly dispersed, and simultaneously, the mixing time is shortened as much as possible so as to improve the production efficiency and reduce the energy consumption.
Currently, wet milling technology is considered to be an excellent method that can solve both the problems of white carbon black milling and optimal dispersibility. Compared with the traditional dry mixing mode, the white carbon black/rubber composite material prepared by adopting the wet mixing mode has lower energy consumption, better dispersibility and excellent processability. Various research institutions and companies, such as Beijing university of chemical industry, yiweiyi rubber institute, beijing confetti company, zhongzhen, north China tire, etc., have developed industrially applicable wet mixing techniques for rubber and have obtained various related patents. For example, one patent at Beijing university of chemical industry relates to a method of preparing a carbon black masterbatch by wet mixing (CN 109517195A), a patent at Suzhou intelligent science and technology Co., ltd, relates to a low energy wet mixing rubber and a preparation method thereof (CN 114316388A), and a patent at Yiweiyi rubber institute Co., ltd relates to a technique of wet mixing and preparing a masterbatch with various fillers (CN 105237832A) and the like.
However, the existing wet mixing process only comprises wet mixing of reinforcing fillers (carbon black and white carbon black) and rubber, and other various processing aids (such as softening agents, anti-aging agents, accelerators, activators and the like) in the rubber composite material are still added through an open mill or an internal mixer (dry mixing), and the open mill or the internal mixer still consume huge energy in the processing process. In order to perfect the study of wet mixing, further optimize the process and expand the application range of wet mixing, the application is developed.
Disclosure of Invention
In order to overcome the technical performance bottleneck of the existing wet mixing technology on limited components, the invention provides a full-formula water-based wet mixing rubber composite masterbatch, which is prepared by dispersing an organic rubber auxiliary agent in water and simultaneously providing a rubber flocculation demulsification process for wet mixing.
The invention also provides a preparation method of the full-formula water-based wet mixing rubber composite master batch, which is characterized in that all the filler, various rubber additives and rubber latex are subjected to flocculation precipitation through a liquid phase, so that the preparation method has the advantages of reducing mixing energy consumption, simplifying process steps, improving the dispersion uniformity degree of the filler and the rubber additives, enhancing the performance of the rubber composite material and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the full-formula water-based wet-mixed rubber composite masterbatch, wherein all components constituting the composite masterbatch are dispersed in a plurality of water-based dispersion liquids, wherein the plurality of water-based dispersion liquids comprise a water-based dispersion liquid I, a water-based dispersion liquid II and a water-based dispersion liquid III; and (3) feeding various water-based dispersion liquid into a reactor in a parallel flow mode, and mixing and demulsifying under stirring to obtain the composite masterbatch.
Specifically, the water-based dispersion liquid I comprises natural rubber emulsion, synthetic rubber emulsion and the like. The sum of the solids content of the rubber component in the water-based dispersion one is 1% to 60% (mass percent), preferably 10% to 30%; the temperature is 10-75deg.C, preferably 20-65deg.C. Natural rubber emulsions can be fresh latex and concentrated latex; the dry gel content is 10% -65%, preferably 20% -60%. The concentrated latex needs to be added with preservative (accounting for 0.1 to 2 percent of the mass of the natural latex aqueous solution). The synthetic rubber latex includes one or more of styrene-butadiene rubber latex, nitrile rubber latex, chloroprene rubber latex, butadiene latex, acrylic rubber latex, isoprene rubber latex, acrylic ester latex, polyvinyl chloride latex, vinylidene chloride latex, styrene-acrylic latex, butyl latex, polyisoprene latex, ethylene-propylene latex, polyurethane latex, polyethylene latex, etc., and the concentration is preferably 10-30%.
Specifically, the water-based dispersion liquid II comprises a reinforcing filler and a hydrophilic rubber auxiliary agent, and the mass ratio of the reinforcing filler to the hydrophilic rubber auxiliary agent is preferably 1:4-4:1. The hydrophilic rubber auxiliary comprises: one or more of accelerator, filler, activator, silane coupling agent, dispersant, etc.; the total mass of the rubber dry adhesive is calculated by 100 parts, the dosage of the amphiphilic filler is 30-100 parts, and the total dosage of the rest components except the reinforcing agent is 5-30 parts. Further preferably, the accelerator is 0.1-10 parts and the activator is 0.1-10 parts.
Further, the reinforcing filler comprises carbon black, white carbon black, double-phase carbon black, calcium carbonate, titanium dioxide and nano SiO 2 Amphiphilic nano SiO 2 One or more of the reinforcing materials can be nano or micro particle powder or slurry with the surface modified by an organic compound and the amphiphilic property; or may be a nano-or microparticle powder or slurry that has not been surface modified. The reinforcing filler participates in the wet mixing processing process after the water phase is dispersed. The accelerator comprises one or more of accelerator CZ, accelerator D, accelerator M, accelerator DM, accelerator TBBS, accelerator TMTD and the like; the filler comprises one or more of calcium carbonate, clay, montmorillonite and the like; the whitening agent includes titanium dioxide and the like, and the activator includes zinc oxide and the like.
Further, the silane coupling agent comprises an organic chain segment containing 1-3 silicon-carbon bonds and a functional group, wherein the organic chain contains 1-12 carbon atoms, and the functional group comprises one or more of mercapto, polysulfide, epoxy, amino, double bond and the like. The dispersant comprises: dodecyl benzene sulfonic acid, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, alkylphenol polyoxyethylene ether, and the like.
Specifically, the water-based dispersion liquid III is a water-based emulsion formed by a lipophilic rubber auxiliary agent, a surfactant and a proper solvent; the lipophilic rubber auxiliary comprises: one or more of an anti-aging agent, a softening agent, a toughening agent and a cosolvent; the softener comprises one or more of paraffin, microcrystalline wax, naphthenic oil, coumarone resin and the like; the toughening agent comprises one or two of a cutting resistant resin (LSB 601) and a tearing resistant resin (SL-6903); the cosolvent comprises stearic acid; the total mass of the rubber dry adhesive is calculated as 100 parts, and the dosage of the lipophilic rubber auxiliary agent is 0.1-10 parts.
Further, mixing the lipophilic rubber auxiliary agent and the surfactant in a proper solvent, stirring and dispersing at 30-100 ℃, distilling to remove the oily solvent to obtain the surfactant hybridized rubber auxiliary agent, and adding water to form emulsion, namely water-based dispersion liquid III; the suitable solvent includes one or more of aromatic hydrocarbon solvents, ether solvents, ester solvents, water, etc., preferably xylene, toluene, etc.; surfactants include, but are not limited to, dodecylbenzenesulfonic acid, cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), alkylphenol polyoxyethylene ether (OP-10), and the like; dodecylbenzenesulfonic acid is preferred. The mass ratio of the proper solvent to the lipophilic rubber auxiliary agent is 2-7:1.
specifically, the plurality of water-based dispersions further comprises a demulsifier solution I, wherein the demulsifier solution I is prepared by dissolving demulsifiers in water; the demulsifier comprises one or more of zinc sulfate, calcium chloride and magnesium chloride; the total mass of the rubber dry adhesive is calculated as 100 parts, and the dosage of the demulsifier is 1-20 parts.
The preparation method of the full-formula water-based wet-process mixing rubber composite master batch comprises the following three processing methods:
the method comprises the following steps: preparing a water-based dispersion liquid I, a water-based dispersion liquid II, a water-based dispersion liquid III and a demulsifier solution I respectively, enabling the water-based dispersion liquid I, the water-based dispersion liquid III and the demulsifier solution I to flow into a mixing stirrer in parallel at the same time, and obtaining the fully-formulated rubber composite material through mixing and flocculating settling;
the second method is as follows: preparing a first water-based dispersion liquid, a second water-based dispersion liquid, a third water-based dispersion liquid and a first demulsifier solution respectively, mixing the first demulsifier solution, the second water-based dispersion liquid and the third water-based dispersion liquid, then flowing the first water-based dispersion liquid and the third water-based dispersion liquid into a mixing stirrer together, and obtaining the fully-formulated rubber composite material through mixing and flocculating settling;
and a third method: preparing a water-based dispersion liquid I, a water-based dispersion liquid II and a water-based dispersion liquid III, mixing the water-based dispersion liquid II and the water-based dispersion liquid III, then flowing the mixture and the water-based dispersion liquid into a mixing stirrer, demulsifying rubber by means of demulsifying properties of the mixture of the water-based dispersion liquid II and the water-based dispersion liquid III, and obtaining the fully-formulated rubber composite material through mixing and flocculating precipitation;
and extruding, granulating, dehydrating and drying the flocculated and precipitated full-formula rubber composite material to obtain the full-formula rubber composite master batch.
The invention provides a preparation method of a preferable full-formula water-based wet-process mixed rubber composite masterbatch, which comprises the following steps:
step 1: preparation of a water-based dispersion one (rubber emulsion):
preparing water-based rubber emulsion with the solid content of 10-30% by taking 100 parts of total mass of the natural rubber dry adhesive, wherein the water-based rubber emulsion contains 100 parts of natural rubber dry adhesive;
step 2: preparation of a water-based dispersion II:
adding 50 parts of amphiphilic white carbon black, 2 parts of accelerator CZ, 1 part of accelerator D and 5 parts of zinc oxide into 400-600 parts of water, stirring and mixing for 20-60 min (the speed is 500-2500 rad/min) by a stirrer to obtain a water-based dispersion liquid II;
step 3: preparation of a water-based dispersion liquid III: adding 1.5 parts of an anti-aging agent 4020, 1.5 parts of microcrystalline wax, 1.5 parts of stearic acid and 0.04-0.1 part of dodecylbenzenesulfonic acid into 20 parts of toluene, heating and stirring for 30-60 min (speed 500-1000 rad/min) at 30-100 ℃, then carrying out reduced pressure distillation at 80-120 ℃ to obtain a surfactant hybridized rubber auxiliary agent, and adding the surfactant hybridized rubber auxiliary agent into 45-120 parts of water to obtain a water-based dispersion liquid III;
step 4: preparation of demulsifier solution one: dissolving 4-8 parts of zinc sulfate heptahydrate or calcium chloride in 36-72 parts of water to prepare a solution, so as to obtain a demulsifier solution I;
step 5: preparation of a mixed dispersion: mixing the demulsifier solution I, the water-based dispersion liquid II and the water-based dispersion liquid III, and stirring for 20-60 min (the speed is 500-2500 rad/min) by a stirrer to prepare a mixed dispersion liquid;
step 6: the mixed dispersion liquid and the water-based dispersion liquid are simultaneously and co-current flowed into a mixing stirrer, and the fully-formulated rubber composite material is obtained through mixing and flocculating settling;
step 7: and extruding, granulating, dehydrating and drying the flocculated and precipitated full-formula rubber composite material to obtain the full-formula rubber composite master batch.
The full-wet mixing technology is full-liquid-phase wet mixing, and requires that the filler, the demulsifier and the rubber auxiliary agent all complete flocculation precipitation with rubber latex in liquid phase, and the full-formula rubber composite master batch is obtained after drying and dehydration. Can control the demulsification time to be 0.1-5min, the temperature to be 0-90 ℃, the rubber concentration to be 10-65%, the proper viscosity and the demulsifier to be 0-20%. Firstly, uniformly mixing, and then flocculating to form the rubber master batch. The dispersing temperature is 10-100 ℃, and the dispersing process needs to be carried out by a sand mill, a pulverizer, an emulsifying machine, a stirrer, an ultrasonic dispersing device and other devices.
As a preferable mode, the full-formula water-based wet mixing rubber composite master batch comprises the following components:
(A) The method comprises the following steps Water-based dispersion one (rubber emulsion),
(B) The method comprises the following steps Water-based dispersion II (amphiphilic filler and hydrophilic rubber auxiliary agent),
(C) The method comprises the following steps Water-based dispersion three (lipophilic rubber auxiliary),
(D) The method comprises the following steps Demulsifier solution I (solution containing divalent metal salt, wherein the divalent metal salt comprises zinc sulfate heptahydrate, magnesium chloride, calcium chloride, etc.).
The invention prepares all rubber, filler and various rubber processing aids into aqueous solution, and all necessary components and rubber latex are mixed and demulsified by a full wet method. Compared with the traditional process, the invention reduces mixing energy consumption, simplifies the processing flow, improves the dispersion degree of each component in rubber and improves the mechanical property. According to the invention, rubber processing aids are classified into different categories by different methods, and according to the characteristics of the rubber processing aids, the rubber processing aids participate in the wet mixing process in different modes, so that the water-based wet mixing rubber composite master batch with a full formula, namely the full wet mixing, is realized. The total wet mixing is to disperse all rubber processing aids except sulfur in water in the form of emulsion on the basis of wet mixing, and then to coagulate and precipitate the rubber processing aids together with rubber materials and the like by the wet mixing mode to prepare the rubber composite material with the total formulation.
Compared with the prior art, the invention has the following beneficial effects:
1) Dispersing various rubber auxiliary agents (hydrophilic type and lipophilic type) in water in different modes to enable the rubber auxiliary agents to participate in a wet mixing process, further perfecting a wet mixing system, enabling various rubber processing auxiliary agents except sulfur to participate in wet mixing, and improving the dispersibility of the rubber auxiliary agents in rubber;
2) Compared with the existing dry mixing, the full-formula wet mixing has no dust pollution and almost no waste water, so that the energy consumption in the processing process is greatly saved (in the dry mixing, the energy consumption for producing each ton of rubber material is about 400 ℃, and the energy consumption for producing the same product is lower than 100 ℃);
3) Compared with the existing wet mixing, the full-formula wet mixing of the invention ensures that various rubber processing aids participate in the wet mixing process, expands the application range of the wet mixing process, further saves energy, reduces emission, reduces the hardness of the composite material and facilitates subsequent processing.
4) The preparation method is simple in preparation process, can be used for continuous production, is environment-friendly in production process, and has potential large-scale industrial prospect.
Detailed Description
The following description of the embodiments of the present invention will be provided in a complete and clear manner, and the embodiments described are merely some, but not all, of the embodiments of the present invention. The following examples are given for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
All materials used, unless otherwise specified, are either commercially available products which are commercially available as such or can be prepared by methods conventional in the art. For example, amphiphilic nano-silica is purchased from Henan river large nano-materials engineering research center Co., ltd, model DNS-110E25; the anti-aging agent was purchased from san jose chemical technology limited, model 4020.
In the embodiments, processes not specifically mentioned, such as extrusion granulation, dehydration and drying, etc., are adopted by conventional techniques in the art, and are not essential and innovative in the present application, and thus will not be described in detail. In the examples, phr refers to parts by mass.
Example 1
A full-formula water-based wet-process mixing rubber composite masterbatch comprises the following preparation method:
1) Based on 100phr of dry rubber mass of natural rubber. 166.7phr of concentrated natural latex (preservative ammonia content: 0.6%, hainan Natural rubber industry group Co., ltd., hereinafter the same) with a solids content of 60% was diluted to 30% to obtain a water-based dispersion I;
2) 50phr of amphiphilic nano-silica SiO 2 5phr of silicon 69 (silane coupling agent), 2phr of accelerator CZ, 1phr of accelerator D and 5phr of zinc oxide, adding 540phr of pure water, and stirring at 70 ℃ for reaction for 1h (speed 1000 rad/min) to obtain water-based dispersion II;
3) 1.5phr of antioxidant, 1.5phr of microcrystalline wax, 1.5phr of stearic acid, and 0.2phr of dodecylbenzenesulfonic acid (all commercial technical grade products) were added to 25phr of xylene and stirred at 60℃for 1 hour (speed 800 rad/min). Then, carrying out reduced pressure distillation at 100 ℃, and then adding 100phr of pure water for dispersion to obtain a water-based dispersion liquid III;
4) Adding 4phr of calcium chloride into 36phr of pure water to prepare a solution, and obtaining a demulsifier solution I;
5) Mixing the demulsifier solution I, the water-based dispersion solution II and the water-based dispersion solution III to obtain mixed dispersion liquid, enabling the mixed dispersion liquid and the water-based dispersion liquid to flow into a mixing stirrer in parallel at the same time, enabling the temperature to be 25 ℃, the rotating speed to be 500rad/min, and the time to be 20s-30s, and obtaining the fully-formulated rubber composite material through mixing and flocculating precipitation; and extruding, granulating, dehydrating and drying to obtain the full-formula rubber composite master batch.
167.5phr of the prepared full-formula rubber composite master batch is taken, 1.5phr of sulfur is added on an open mill to obtain a full-formula rubber composite rubber compound, then vulcanization (vulcanization temperature: 150 ℃, vulcanization time: T90+3min, vulcanization pressure: 20 MPa) is carried out, a vulcanization test piece is prepared, and relevant performance tests are carried out, and the results are shown in Table 1.
Example 2
A full-formula water-based wet-process mixing rubber composite masterbatch comprises the following preparation method:
1) The weight of the emulsion polymerized styrene-butadiene rubber is 100phr, wherein the weight of the emulsion polymerized styrene-butadiene rubber is 80 phr. 133.3phr of concentrated natural latex having a solids content of 60% was diluted to 30%; 100phr of an emulsion polymerized styrene-butadiene rubber emulsion having a solids content of 20% was taken (model 1502). Mixing the two latices at 25 ℃ at 500rad/min for 3min to obtain a water-based dispersion liquid I;
2) 50phr of amphiphilic nano-silica SiO 2 5phr of silicon 69 (silane coupling agent), 2phr of accelerator CZ, 1phr of accelerator D and 5phr of zinc oxide, adding 540phr of pure water, and stirring at 70 ℃ for reaction for 1h (speed 2000 rad/min) to obtain a water-based dispersion II;
3) 1.5phr of antioxidant, 1.5phr of microcrystalline wax, 1.5phr of stearic acid, and 0.2phr of dodecylbenzenesulfonic acid (all commercial technical grade products) were added to 25phr of xylene and stirred at 60℃for 1 hour (speed 800 rad/min). Then, distillation was carried out at 100℃under reduced pressure, followed by addition of 100phr of pure water for dispersion, to obtain a water-based dispersion III.
4) Adding 4phr of calcium chloride into 36phr of pure water to prepare a solution, and obtaining a demulsifier solution I;
5) Mixing the demulsifier solution I, the water-based dispersion solution II and the water-based dispersion solution III to obtain mixed dispersion liquid, enabling the mixed dispersion liquid and the water-based dispersion liquid to flow into a mixing stirrer in parallel at the same time, enabling the temperature to be 25 ℃, the rotating speed to be 500rad/min, and the time to be 20s-30s, and obtaining the fully-formulated rubber composite material through mixing and flocculating precipitation; and extruding, granulating, dehydrating and drying to obtain the full-formula rubber composite master batch.
167.5phr of the prepared full-formula rubber composite master batch is taken, 1.5phr of sulfur is added on an open mill to obtain a full-formula rubber composite rubber compound, then vulcanization (vulcanization temperature: 150 ℃, vulcanization time: T90+3min, vulcanization pressure: 20 MPa) is carried out, a vulcanization test piece is prepared, and relevant performance tests are carried out, and the results are shown in Table 1.
Example 3
A full-formula water-based wet-process mixing rubber composite masterbatch comprises the following preparation method:
1) Based on 100phr of dry emulsion styrene-butadiene rubber. Taking 500phr of emulsion polymerized styrene-butadiene rubber emulsion (1502 model) with 20% of solid content to obtain water-based dispersion I;
2) 50phr of amphiphilic nano-silica SiO 2 2phr of accelerator CZ, 1phr of accelerator D, 5phr of zinc oxide and 5phr of silicon 69 (silane coupling agent), adding 540phr of pure water, and stirring at 70 ℃ for reaction for 1h (speed 1500 rad/min) to obtain a water-based dispersion II;
3) 1.5phr of antioxidant, 1.5phr of microcrystalline wax, 1.5phr of stearic acid, and 0.2phr of dodecylbenzenesulfonic acid (all commercial technical grade products) were added to 25phr of xylene and stirred at 60℃for 1 hour (speed 1000 rad/min). Then, carrying out reduced pressure distillation at 100 ℃, and then adding 100phr of pure water for dispersion to obtain a water-based dispersion liquid III;
4) Adding 4phr of calcium chloride into 36phr of pure water to prepare a solution, and obtaining a demulsifier solution I;
5) Mixing the demulsifier solution I, the water-based dispersion solution II and the water-based dispersion solution III to obtain mixed dispersion liquid, enabling the mixed dispersion liquid and the water-based dispersion liquid to flow into a mixing stirrer in parallel at the same time, enabling the temperature to be 25 ℃, the rotating speed to be 500rad/min, and the time to be 20s-30s, and obtaining the fully-formulated rubber composite material through mixing and flocculating precipitation; and extruding, granulating, dehydrating and drying to obtain the full-formula rubber composite master batch.
167.5phr of the prepared full-formula rubber composite master batch is taken, 1.5phr of sulfur is added on an open mill to obtain a full-formula rubber composite rubber compound, then vulcanization (vulcanization temperature: 150 ℃, vulcanization time: T90+3min, vulcanization pressure: 20 MPa) is carried out, a vulcanization test piece is prepared, and relevant performance tests are carried out, and the results are shown in Table 1.
Example 4
A full-formula water-based wet-process mixing rubber composite masterbatch comprises the following preparation method:
1) Based on 100phr of dry rubber mass of natural rubber. 166.7phr of concentrated natural latex having a solids content of 60% was diluted to 30% to obtain a water-based dispersion one;
2) 40phr of amphiphilic nano-silica SiO 2 And 10phr of N220 carbon black, 2phr of accelerator CZ, 1phr of accelerator D, 5phr of zinc oxide and 5phr of silicon 69 (silane coupling agent), adding 540phr of pure water, and stirring and reacting for 1h at 70 ℃ at a speed of 1500 rad/min to obtain a water-based dispersion liquid II;
3) 1.5phr of antioxidant, 1.5phr of microcrystalline wax, 1.5phr of stearic acid, and 0.2phr of dodecylbenzenesulfonic acid (all commercial technical grade products) were added to 20phr of xylene and stirred at 60℃for 1 hour (speed 800 rad/min). Then, carrying out reduced pressure distillation at 100 ℃, and then adding 100phr of pure water for dispersion to obtain a water-based dispersion liquid III;
4) Adding 4phr of calcium chloride into 36phr of pure water to prepare a solution, and obtaining a demulsifier solution I;
5) Mixing the demulsifier solution I, the water-based dispersion solution II and the water-based dispersion solution III to obtain mixed dispersion liquid, enabling the mixed dispersion liquid and the water-based dispersion liquid to flow into a mixing stirrer in parallel at the same time, enabling the temperature to be 25 ℃, the rotating speed to be 500rad/min, and the time to be 20s-30s, and obtaining the fully-formulated rubber composite material through mixing and flocculating precipitation; and extruding, granulating, dehydrating and drying to obtain the full-formula rubber composite master batch.
Comparative example 1
100phr of natural rubber dry rubber is weighed and 50phr of amphiphilic nano silicon dioxide SiO is added to the mixture based on 100phr of natural rubber dry rubber 2 And various rubber additives are added by dry mixing (rubber additive formula: accelerator CZ 2phr, accelerator D1 phr, zinc oxide 5phr, silicon 695phr, anti-aging agent 1.5phr and microcrystalline wax 1.5 p)hr, stearic acid 1.5phr, sulphur 1.5 phr) to obtain a mix, and then vulcanization (vulcanization temperature: 150 ℃, vulcanizing time: t90+3min, vulcanization pressure 20 MPa), and the related properties were tested, and the results are shown in Table 1.
Comparative example 2
80phr of natural rubber dry rubber is weighed, 20phr of styrene-butadiene rubber dry rubber is weighed, and 50phr of amphiphilic nano silicon dioxide SiO is added 2 And various rubber additives were added by dry mixing (rubber additive formulation: accelerator CZ 2phr, accelerator D1 phr, zinc oxide 5phr, silicon 695phr, anti-aging agent 1.5phr, microcrystalline wax 1.5phr, stearic acid 1.5phr, sulfur 1.5 phr) to obtain a rubber compound, and then vulcanized (vulcanization temperature: 150 ℃ C., vulcanization time: T90+3min, vulcanization pressure 20 MPa) to prepare vulcanized test pieces, and the results are shown in Table 1.
Comparative example 3
Based on 100phr of total mass of the styrene-butadiene rubber, weighing 100phr of the styrene-butadiene rubber, and 50phr of amphiphilic nano silicon dioxide SiO 2 And various rubber additives were added by dry mixing (rubber additive formulation: accelerator CZ 2phr, accelerator D1 phr, zinc oxide 5phr, silicon 695phr, anti-aging agent 1.5phr, microcrystalline wax 1.5phr, stearic acid 1.5phr, sulfur 1.5 phr) to obtain a rubber compound, and then vulcanized (vulcanization temperature: 150 ℃ C., vulcanization time: T90+3min, vulcanization pressure 20 MPa) to prepare vulcanized test pieces, and the results are shown in Table 1.
The wet-compounded rubber prepared in the above examples and comparative examples was tested for tensile strength, tear strength, 100% elongation stress, 300% elongation stress, elongation at break, rebound resilience and hardness, and the test results are shown in table 1.
1. The tensile strength and the stretching stress test method of the rubber are according to GB/T528-2009;
2. the rubber tearing experimental method is according to GB/T529-2008;
3. the rubber rebound test method is according to GB/T1681-2009;
4. the rubber hardness test method is according to GB/T531-2009.
TABLE 1 Performance index of different example products
The formulations containing water-based rubber in different proportions were subjected to different modes of mixing processing, and the performance differences of the wet mixing and dry mixing of the full formulation of the invention were compared, and the results are shown in Table 1. For the same formulas (example 1 and comparative example 1, example 2 and comparative example 2, and example 3 and comparative example 3), the fully-formulated water-based wet-process rubber compound masterbatch prepared by the invention is compared with the dry-process rubber compound masterbatch, the tensile strength, the tearing strength, the elongation at break and the like of the test rubber are improved, the comprehensive performance of the rubber is superior to that of the dry-process rubber, and the mixing energy consumption (the energy consumption for producing each ton of rubber material is reduced from 400 ℃ to less than 100 ℃) and the dust pollution problem are reduced. It should be noted that, since the mechanical properties of the natural rubber are relatively good, but the mechanical properties of the styrene-butadiene rubber are relatively poor, the mechanical properties of the composite masterbatch of examples 2 and 3 are gradually reduced as the content of the styrene-butadiene rubber increases, which is slightly worse than that of example 1.
Claims (10)
1. The full-formula water-based wet-mixed rubber composite master batch is characterized in that all components forming the composite master batch are dispersed in a plurality of water-based dispersion liquids, wherein the plurality of water-based dispersion liquids comprise a water-based dispersion liquid I, a water-based dispersion liquid II and a water-based dispersion liquid III; and (3) feeding various water-based dispersion liquid into a reactor in a parallel flow mode, and mixing and demulsifying under stirring to obtain the composite masterbatch.
2. The fully formulated water-based wet-mixed rubber composite masterbatch of claim 1 wherein said water-based dispersion comprises a natural rubber emulsion and a synthetic rubber emulsion; the sum of the solids content of the rubber component in the water-based dispersion one is 1% to 60%.
3. The fully formulated water-based wet mix rubber composite masterbatch of claim 1 wherein said water-based dispersion comprises a reinforcing filler and a hydrophilic rubber aid comprising: one or more of a promoter, a filler, an activator, a silane coupling agent, and a dispersant; the total mass of the rubber dry adhesive is calculated by 100 parts, the consumption of the reinforcing agent is 30-100 parts, and the total consumption of the rest components except the reinforcing agent is 5-30 parts.
4. The full-formula water-based wet-mixed rubber composite masterbatch according to claim 3, wherein the reinforcing filler comprises carbon black, white carbon black, double-phase carbon black, calcium carbonate, titanium dioxide and nano SiO 2 Amphiphilic nano SiO 2 One or more of the following; the accelerator comprises one or more of accelerator CZ, accelerator D, accelerator M, accelerator DM, accelerator TBBS and accelerator TMTD; the filler comprises one or more of calcium carbonate, clay and montmorillonite; the whitening agent comprises titanium dioxide and the activator comprises zinc oxide.
5. The fully formulated water-based wet-mixed rubber composite masterbatch of claim 3 wherein said silane coupling agent comprises an organic chain segment containing 1-3 silicon-carbon bonds and a functional group, the organic chain containing 1-12 carbon atoms, the functional group comprising one or more of mercapto, polysulfide, epoxy, amino, double bonds.
6. The fully formulated water-based wet-mixed rubber composite masterbatch according to claim 1, characterized in that the water-based dispersion liquid III is a water-based emulsion composed of a lipophilic rubber auxiliary agent, a surfactant and a proper solvent; the lipophilic rubber auxiliary comprises: one or more of an anti-aging agent, a softening agent, a toughening agent and a cosolvent; the softener comprises one or more of paraffin, microcrystalline wax, naphthenic oil and coumarone resin; the toughening agent comprises one or two of a cut-resistant resin and a tearing-resistant resin; the cosolvent comprises stearic acid; the total mass of the rubber dry adhesive is calculated as 100 parts, and the dosage of the lipophilic rubber auxiliary agent is 0.1-10 parts.
7. The full-formula water-based wet-mixed rubber composite master batch according to claim 6, wherein the lipophilic rubber auxiliary agent and the surfactant are mixed in a proper solvent, stirred and dispersed at 30-100 ℃, and then the oily solvent is removed by distillation to obtain the surfactant hybridized rubber auxiliary agent, and an emulsion, namely a water-based dispersion liquid III, is formed after water is added; the suitable solvent comprises one or more of aromatic hydrocarbon solvents, ether solvents, ester solvents and water; the surfactant comprises dodecylbenzene sulfonic acid, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride and alkylphenol polyoxyethylene ether; the mass ratio of the proper solvent to the lipophilic rubber auxiliary agent is 2-5:1.
8. the fully formulated water-based wet mix rubber composite masterbatch of claim 1 wherein said plurality of water-based dispersions further comprises a first emulsion breaker solution made of an emulsion breaker dissolved in water; the demulsifier comprises one or more of zinc sulfate, calcium chloride and magnesium chloride; the total mass of the rubber dry adhesive is calculated as 100 parts, and the dosage of the demulsifier is 1-20 parts.
9. The preparation method of the full-formula water-based wet-mixed rubber composite master batch according to any one of claims 1 to 8, which is characterized by comprising the following three processing methods:
the method comprises the following steps: preparing a water-based dispersion liquid I, a water-based dispersion liquid II, a water-based dispersion liquid III and a demulsifier solution I respectively, enabling the water-based dispersion liquid I, the water-based dispersion liquid III and the demulsifier solution I to flow into a mixing stirrer in parallel at the same time, and obtaining the fully-formulated rubber composite material through mixing and flocculating settling;
the second method is as follows: preparing a first water-based dispersion liquid, a second water-based dispersion liquid, a third water-based dispersion liquid and a first demulsifier solution respectively, mixing the first demulsifier solution, the second water-based dispersion liquid and the third water-based dispersion liquid, then flowing the first water-based dispersion liquid and the third water-based dispersion liquid into a mixing stirrer together, and obtaining the fully-formulated rubber composite material through mixing and flocculating settling;
and a third method: preparing a water-based dispersion liquid I, a water-based dispersion liquid II and a water-based dispersion liquid III, mixing the water-based dispersion liquid II and the water-based dispersion liquid III, then flowing the mixture and the water-based dispersion liquid into a mixing stirrer, demulsifying rubber by means of demulsifying properties of the mixture of the water-based dispersion liquid II and the water-based dispersion liquid III, and obtaining the fully-formulated rubber composite material through mixing and flocculating precipitation;
and extruding, granulating, dehydrating and drying the flocculated and precipitated full-formula rubber composite material to obtain the full-formula rubber composite master batch.
10. The method for preparing the full-formula water-based wet-mixed rubber composite masterbatch according to claim 9, which is characterized by comprising the following steps:
step 1: preparation of a water-based dispersion: preparing water-based rubber emulsion with the solid content of 10-30% by taking 100 parts of total mass of the natural rubber dry adhesive, wherein the water-based rubber emulsion contains 100 parts of natural rubber dry adhesive;
step 2: preparation of a water-based dispersion II: adding 50 parts of white carbon black, 2 parts of accelerator CZ, 1 part of accelerator D and 5 parts of zinc oxide into 400-600 parts of water, and stirring and mixing for 20-60 min to obtain a water-based dispersion liquid II;
step 3: preparation of a water-based dispersion liquid III: adding 1.5 parts of an anti-aging agent, 1.5 parts of microcrystalline wax, 1.5 parts of stearic acid and 0.04-0.1 part of dodecylbenzenesulfonic acid into 20 parts of toluene, heating and stirring for 30-60 min at 30-100 ℃, then carrying out reduced pressure distillation at 80-120 ℃ to obtain a surfactant hybridized rubber auxiliary agent, and adding the surfactant hybridized rubber auxiliary agent into 45-120 parts of water to obtain a water-based dispersion liquid III;
step 4: preparation of demulsifier solution one: dissolving 4-8 parts of zinc sulfate heptahydrate or calcium chloride in 36-72 parts of water to prepare a solution, so as to obtain a demulsifier solution I;
step 5: preparation of a mixed dispersion: mixing the demulsifier solution I, the water-based dispersion liquid II and the water-based dispersion liquid III, and stirring for 20-60 min by a stirrer to prepare a mixed dispersion liquid;
step 6: the mixed dispersion liquid and the water-based dispersion liquid are simultaneously and co-current flowed into a mixing stirrer, and the fully-formulated rubber composite material is obtained through mixing and flocculating settling;
step 7: and extruding, granulating, dehydrating and drying the flocculated and precipitated full-formula rubber composite material to obtain the full-formula rubber composite master batch.
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