CN113980372A - Compound accelerator pre-dispersed masterbatch and preparation method thereof - Google Patents
Compound accelerator pre-dispersed masterbatch and preparation method thereof Download PDFInfo
- Publication number
- CN113980372A CN113980372A CN202111461362.7A CN202111461362A CN113980372A CN 113980372 A CN113980372 A CN 113980372A CN 202111461362 A CN202111461362 A CN 202111461362A CN 113980372 A CN113980372 A CN 113980372A
- Authority
- CN
- China
- Prior art keywords
- parts
- accelerator
- plasticizer
- masterbatch
- rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/205—Compounds containing groups, e.g. carbamates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a compound accelerator pre-dispersed masterbatch and a preparation method thereof, wherein the compound accelerator pre-dispersed masterbatch comprises the following raw materials in parts by weight: 25-32 parts of ethyl carbamate, 15-20 parts of a masterbatch carrier, 3-10 parts of a dispersing agent, 3-6 parts of a plasticizer, 1-1.5 parts of nano calcium oxide, 2-3 parts of a defoaming agent, 3-4 parts of an accelerator, 3-8 parts of an adhesive and 2-3 parts of zinc oxide. Mixing ethyl carbamate, a masterbatch carrier, a dispersing agent and zinc oxide for 5-8 minutes at the temperature of 85-95 ℃ and the rotating speed of 50-70 r/min, then adding a plasticizer and nano calcium oxide into an internal mixer, continuously mixing for 3-5 minutes under the condition of keeping the temperature and the rotating speed unchanged, finally adding an accelerator and an adhesive into the internal mixer, continuously mixing for 1-2 minutes under the condition of keeping the temperature and the rotating speed unchanged to obtain a premix, and loading the premix into a container; according to the invention, the defoaming agent is added into the raw materials, and the problem of high bubble rate of the rubber product in the mixing process is solved by means of ultrasonic vibration defoaming.
Description
Technical Field
The invention belongs to the technical field of masterbatch particle production, and particularly relates to a compound accelerator pre-dispersed masterbatch particle and a preparation method thereof.
Background
In recent years, with the development of the rubber industry in the world, the variety of the accelerator has changed correspondingly. The latest trend of the development of accelerators in the international rubber industry is high efficiency, low toxicity and low cost, and the development and application of compound accelerators are an important approach. Most of the conventional rubber additives are powdery chemicals and thus have many problems in use, for example: a large amount of dust, the emission of bad smell, toxic volatile substances and the like are generated, and the influence on safety, sanitation and environmental protection is caused; in addition, some chemicals are poor in compatibility with rubber, and are difficult to uniformly disperse, which affects the quality stability of rubber products, and if the mixing time is prolonged or the mixing temperature is increased, the improvement may affect the increase of the process cost or some side reactions of the physical properties of the products.
Various auxiliaries are required in the production of rubber products, such as rubber vulcanizing agents, rubber peroxide crosslinking auxiliaries, rubber accelerators, rubber antioxidants, rubber fillers and reinforcing agents, rubber plasticizers or softeners, phenolic resins, hydrocarbon resins, rubber adhesion promoters, rubber foaming agents, rubber pigments, rubber colorants, and the like. In the process of refining the masterbatch prefabricated raw materials, due to the mixing and stirring of various raw materials, the prefabricated rubber materials form bubbles inside the masterbatch during mixing, stirring and banburying, so that the product quality of extruded masterbatch particles is influenced, and the performance of subsequent rubber products is unstable and uniform when the masterbatch particles exist in a rubber system in aggregates with different sizes.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the pre-dispersed master batch particle of the compound accelerator and the preparation method thereof are improved, and the pre-dispersed master batch particle can eliminate the internal foaming of a master batch particle molded product and ensure the stable and uniform performance of a subsequent rubber product.
In order to solve the technical problems, the invention is realized by the following technical scheme: the compound accelerator pre-dispersed masterbatch comprises the following raw materials in parts by weight: 25-32 parts of ethyl carbamate, 15-20 parts of a masterbatch carrier, 3-10 parts of a dispersing agent, 3-6 parts of a plasticizer, 1-1.5 parts of nano calcium oxide, 2-3 parts of a defoaming agent, 3-4 parts of an accelerator, 3-8 parts of an adhesive and 2-3 parts of zinc oxide.
Preferably, the masterbatch carrier is styrene butadiene rubber, and the plasticizer is an aromatic base rubber plasticizer.
Preferably, the masterbatch carrier is ethylene propylene diene monomer, and the plasticizer is paraffin-based rubber plasticizer.
Preferably, the dispersing agent is an ethylene oxide condensate, and the defoaming agent is a water-based organic silicon defoaming agent.
Preferably, the accelerator is N-cyclohexyl-2-benzothiazole sulfonamide.
The preparation method of the pre-dispersed master batch particles of the compound accelerator comprises the following steps,
A. weighing ethyl carbamate, a masterbatch carrier, a dispersant, a plasticizer, nano calcium oxide, a defoaming agent, an accelerator, an adhesive and zinc oxide according to the weight percentage;
B. mixing ethyl carbamate, a masterbatch carrier, a dispersing agent and zinc oxide for 5-8 minutes at the temperature of 85-95 ℃ and the rotating speed of 50-70 r/min, then adding a plasticizer and nano calcium oxide into an internal mixer, continuously mixing for 3-5 minutes under the condition of keeping the temperature and the rotating speed unchanged, finally adding an accelerator and an adhesive into the internal mixer, continuously mixing for 1-2 minutes under the condition of keeping the temperature and the rotating speed unchanged, and obtaining a premix and loading the premix in a container;
C. putting the defoaming agent into a container loaded with the premix, stirring for 5-10 minutes by using a stirring device at the rotating speed of 60-80 r/min, then placing the premix into the container loaded with the premix in an ultrasonic generator, and defoaming the premix in the container for 15-20 minutes under the action of ultrasonic waves to obtain a prefabricated rubber material;
D. putting the prefabricated rubber material into a screw extruder for extrusion, and putting the extruded rubber material into a granulator for granulation;
E. putting the granulated granular rubber material into a cooling machine for cooling, and adjusting the temperature of the cooling machine to 10-20 ℃;
F. and (5) putting the cooled granular sizing material into a full-automatic granule packaging machine for quantitative packaging.
Preferably, the frequency of the ultrasonic generator is 25KHZ-40 KHZ.
Compared with the prior art, the invention has the advantages that: the invention provides a pre-dispersed masterbatch particle of a compound accelerator, which is prepared by adding a defoaming agent into raw materials and improving the problem of high bubble rate of a rubber product in the mixing process in an ultrasonic vibration defoaming mode. Meanwhile, the ageing resistance and the crack resistance of the rubber product can be improved.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to specific embodiments below:
the compound accelerator pre-dispersed masterbatch comprises the following raw materials in parts by weight: 25-32 parts of ethyl carbamate, 15-20 parts of a masterbatch carrier, 3-10 parts of a dispersing agent, 3-6 parts of a plasticizer, 1-1.5 parts of nano calcium oxide, 2-3 parts of a defoaming agent, 3-4 parts of an accelerator, 3-8 parts of an adhesive and 2-3 parts of zinc oxide. The rubber dispersant is an indispensable excellent auxiliary agent for rubber processing, the dispersant has excellent internal and external lubricating functions for an ethylene oxide condensate, so that the product has excellent and uniform effects, and the overall performance of rubber products is greatly improved. The rubber accelerator is particularly suitable for normal pressure vulcanized rubber production lines, is one of essential auxiliaries, and is a rubber vulcanization accelerator. Rubber vulcanization is mainly performed using sulfur, but sulfur reacts with rubber very slowly, and therefore a vulcanization accelerator is produced at the same time. The accelerator is added into the rubber material to promote the activation of the vulcanizing agent, so that the crosslinking reaction of the vulcanizing agent and rubber molecules is accelerated, and the effects of shortening the vulcanizing time and reducing the vulcanizing temperature are achieved. The main vulcanization accelerators used are primarily sulfenamides, thiazoles, thiurams, and also some guanidines, thioureas, and dithiocarbamates, depending on their chemical structure. The sulfenamide has the best comprehensive performance and is widely used, and the accelerator is N-cyclohexyl-2-benzothiazole sulfenamide.
The master batch carrier is Styrene Butadiene Rubber (SBR), also known as polystyrene butadiene copolymer. The physical and mechanical properties, the processing property and the product use property are close to those of natural rubber, some properties such as wear resistance, heat resistance, aging resistance and vulcanization speed are better than those of the natural rubber, the rubber can be used together with the natural rubber and various synthetic rubbers, and can be widely applied to the fields of production of tires, adhesive tapes, rubber tubes, electric wires and cables, medical appliances, various rubber products and the like, the rubber is the largest general synthetic rubber variety, and the plasticizer is an aromatic base rubber plasticizer.
The master batch carrier is ethylene propylene diene monomer, the ethylene propylene diene monomer is a copolymer of ethylene, propylene and a small amount of non-conjugated diene, is one of ethylene propylene rubbers, is represented by EPDM (ethylene propylene diene monomer), has excellent aging resistance such as ozone resistance, heat resistance, weather resistance and the like because the main chain of the ethylene propylene diene monomer is composed of chemically stable saturated hydrocarbon and only contains unsaturated double bonds in the side chain, and can be widely applied to the fields of automobile parts, waterproof materials for buildings, wire and cable sheaths, heat-resistant rubber tubes, adhesive tapes, automobile sealing elements and the like, and the plasticizer is paraffin-based rubber plasticizer.
Example (a): the preparation method of the pre-dispersed masterbatch particle by using the aromatic base rubber plasticizer as the plasticizer when the masterbatch carrier is used as the styrene butadiene rubber as the raw material comprises the following steps,
A. weighing ethyl carbamate, a masterbatch carrier, a dispersant, a plasticizer, nano calcium oxide, a defoaming agent, an accelerator, an adhesive and zinc oxide according to the weight percentage;
B. mixing ethyl carbamate, a master batch carrier, a dispersing agent and zinc oxide for 8 minutes at the temperature of 90 ℃ and the rotating speed of 70r/min, then adding a plasticizer and nano calcium oxide into an internal mixer, continuously mixing for 5 minutes under the condition of keeping the temperature and the rotating speed unchanged, finally adding an accelerator and an adhesive into the internal mixer, continuously mixing for 2 minutes under the condition of keeping the temperature and the rotating speed unchanged, obtaining a premix, and loading the premix into a container;
C. putting the defoaming agent into a container loaded with the premix, stirring for 9 minutes at the rotating speed of 70r/min by using a stirring device, then placing the premix into the container loaded with the premix into an ultrasonic generator, wherein the frequency of the ultrasonic generator is 40KHZ, and defoaming the premix in the container for 20 minutes under the action of ultrasonic waves to obtain a prefabricated sizing material;
D. putting the prefabricated rubber material into a screw extruder for extrusion, and putting the extruded rubber material into a granulator for granulation;
E. putting the granulated granular rubber material into a cooling machine for cooling, and adjusting the temperature of the cooling machine to 12 ℃;
F. and (5) putting the cooled granular sizing material into a full-automatic granule packaging machine for quantitative packaging.
Example (b): the preparation method of the master batch particles by taking a master batch carrier as an ethylene propylene diene monomer raw material and a plasticizer as a paraffin-based rubber plasticizer and pre-dispersing a compound accelerator comprises the following steps,
A. weighing ethyl carbamate, a masterbatch carrier, a dispersant, a plasticizer, nano calcium oxide, a defoaming agent, an accelerator, an adhesive and zinc oxide according to the weight percentage;
B. mixing ethyl carbamate, a master batch carrier, a dispersing agent and zinc oxide for 6 minutes at the temperature of 86 ℃ and the rotating speed of 55r/min, then adding a plasticizer and nano calcium oxide into an internal mixer, continuously mixing for 4 minutes under the condition of keeping the temperature and the rotating speed unchanged, finally adding an accelerant and an adhesive into the internal mixer, continuously mixing for 1 minute under the condition of keeping the temperature and the rotating speed unchanged, obtaining a premix, and loading the premix into a container;
C. putting the defoaming agent into a container of a container for loading the premix, stirring for 7 minutes at the rotating speed of 65r/min by using a stirring device, then placing the container for loading the premix into an ultrasonic generator, wherein the frequency of the ultrasonic generator is 30KHZ, and defoaming the premix in the container for 16 minutes under the action of ultrasonic waves to obtain a prefabricated sizing material;
D. putting the prefabricated rubber material into a screw extruder for extrusion, and putting the extruded rubber material into a granulator for granulation;
E. putting the granulated granular rubber material into a cooling machine for cooling, and adjusting the temperature of the cooling machine to 13 ℃;
F. and (5) putting the cooled granular sizing material into a full-automatic granule packaging machine for quantitative packaging.
It is to be emphasized that: it will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (7)
1. The pre-dispersed masterbatch particle of the compound accelerator is characterized in that: the material comprises the following raw materials in parts by weight: 25-32 parts of ethyl carbamate, 15-20 parts of a masterbatch carrier, 3-10 parts of a dispersing agent, 3-6 parts of a plasticizer, 1-1.5 parts of nano calcium oxide, 2-3 parts of a defoaming agent, 3-4 parts of an accelerator, 3-8 parts of an adhesive and 2-3 parts of zinc oxide.
2. The pre-dispersed masterbatch of compounded accelerator as claimed in claim 1, wherein: the master batch carrier is styrene butadiene rubber, and the plasticizer is an aromatic base rubber plasticizer.
3. The pre-dispersed masterbatch of compounded accelerator as claimed in claim 1, wherein: the master batch carrier is ethylene propylene diene monomer, and the plasticizer is paraffin-based rubber plasticizer.
4. The pre-dispersed masterbatch of compounded accelerator as claimed in claim 1, wherein: the dispersing agent is an ethylene oxide condensation product, and the defoaming agent is a water-based organic silicon defoaming agent.
5. The pre-dispersed masterbatch of compounded accelerator as claimed in claim 1, wherein: the accelerator is N-cyclohexyl-2-benzothiazole sulfonamide.
6. The method for preparing the pre-dispersed masterbatch particle of the compound accelerator according to any one of claims 1 to 5, wherein: comprises the following steps of (a) carrying out,
A. weighing ethyl carbamate, a masterbatch carrier, a dispersant, a plasticizer, nano calcium oxide, a defoaming agent, an accelerator, an adhesive and zinc oxide according to the weight percentage;
B. mixing ethyl carbamate, a masterbatch carrier, a dispersing agent and zinc oxide for 5-8 minutes at the temperature of 85-95 ℃ and the rotating speed of 50-70 r/min, then adding a plasticizer and nano calcium oxide into an internal mixer, continuously mixing for 3-5 minutes under the condition of keeping the temperature and the rotating speed unchanged, finally adding an accelerator and an adhesive into the internal mixer, continuously mixing for 1-2 minutes under the condition of keeping the temperature and the rotating speed unchanged, and obtaining a premix and loading the premix in a container;
C. putting the defoaming agent into a container loaded with the premix, stirring for 5-10 minutes by using a stirring device at the rotating speed of 60-80 r/min, then placing the premix into the container loaded with the premix in an ultrasonic generator, and defoaming the premix in the container for 15-20 minutes under the action of ultrasonic waves to obtain a prefabricated rubber material;
D. putting the prefabricated rubber material into a screw extruder for extrusion, and putting the extruded rubber material into a granulator for granulation;
E. putting the granulated granular rubber material into a cooling machine for cooling, and adjusting the temperature of the cooling machine to 10-20 ℃;
F. and (5) putting the cooled granular sizing material into a full-automatic granule packaging machine for quantitative packaging.
7. The preparation method of the pre-dispersed masterbatch particle of the compound accelerator as claimed in claim 6, wherein: the frequency of the ultrasonic generator is 25KHZ-40 KHZ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111461362.7A CN113980372A (en) | 2021-12-03 | 2021-12-03 | Compound accelerator pre-dispersed masterbatch and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111461362.7A CN113980372A (en) | 2021-12-03 | 2021-12-03 | Compound accelerator pre-dispersed masterbatch and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113980372A true CN113980372A (en) | 2022-01-28 |
Family
ID=79733053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111461362.7A Withdrawn CN113980372A (en) | 2021-12-03 | 2021-12-03 | Compound accelerator pre-dispersed masterbatch and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113980372A (en) |
-
2021
- 2021-12-03 CN CN202111461362.7A patent/CN113980372A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Akiba et al. | Vulcanization and crosslinking in elastomers | |
| US3915907A (en) | Chlorothio-sulfonamide-modified rubbery terpolymers and their blends | |
| CS198130B2 (en) | Gurable rubbery mixture and method of producing the same | |
| RU2689630C2 (en) | Modified filler for preparation of rubber mixture and master batch made from it | |
| CN103374149A (en) | Activated resol cure rubber composition | |
| CN110591175B (en) | Non-filled rubber composition with high mechanical property and low hysteresis loss and preparation method thereof | |
| US20170121511A1 (en) | A process to prepare high-quality natural rubber silica masterbatch by liquid phase mixing | |
| CN101448892B (en) | Rubber compositions | |
| CN115926361A (en) | SEBS carrier silicone master batch and preparation method thereof | |
| JP2005529207A (en) | Elastic resin composition | |
| JP2021046554A (en) | Tire rubber composition | |
| CN113980372A (en) | Compound accelerator pre-dispersed masterbatch and preparation method thereof | |
| JP2005502754A (en) | Masterbatch containing rubber compound, filler, plasticizer and curing agent | |
| CN108570121A (en) | A kind of preparation method of the polymer support of pre-dispersed rubber chemicals | |
| JP2011012096A (en) | Vulcanized rubber and production method of the same | |
| US5137981A (en) | Halogenated polybutadiene series elastomers, method of producing the same and rubber compositions for tire containing this elastomer | |
| JP2002212342A (en) | Rubber composition and method for producing the same | |
| JP6711076B2 (en) | Polybutadiene rubber, method for producing the same, and rubber composition using the same | |
| US3562303A (en) | Process of increasing the green strength of high-cis polyisoprene rubbers and facilitating the fabrication thereof | |
| JP4308019B2 (en) | Cement for rubber product modification and its manufacturing method | |
| KR20220143891A (en) | rubber formulation | |
| Sya’bani et al. | Studies of geothermal silica as rubbers compounds reinforcing filler | |
| JP2017095561A (en) | Method for producing wet master batch, method for producing rubber composition and method for producing pneumatic tire | |
| US3704276A (en) | Process for the preparation of elastomeric composition containing methanol treated carbon black | |
| JP2850963B2 (en) | Flowable elastomer composition and vulcanized rubber thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20220128 |