CN104211837A - Preparation method of carbon-black-containing butadiene styrene rubber master batch - Google Patents
Preparation method of carbon-black-containing butadiene styrene rubber master batch Download PDFInfo
- Publication number
- CN104211837A CN104211837A CN201410337186.XA CN201410337186A CN104211837A CN 104211837 A CN104211837 A CN 104211837A CN 201410337186 A CN201410337186 A CN 201410337186A CN 104211837 A CN104211837 A CN 104211837A
- Authority
- CN
- China
- Prior art keywords
- carbon black
- master batch
- preparation
- rubber master
- latex
- 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.)
- Granted
Links
Abstract
The invention belongs to the field of preparation of a rubber master batch and discloses a preparation method of a carbon-black-containing butadiene styrene rubber master batch. The preparation method includes following steps: preparing raw materials including a dry rubber, carbon black, water, operation oil, a wrapping agent, and a flocculant with a weight ratio being 100:(40-100):(1500-3000):(0-30):(1-5):(1-5) according to the weight of a latex; preparing a carbon black suspension; mixing the latex with the carbon black and performing a thermal treatment; carrying out a coagulation process; and carrying out a post process to a coagulated product. The preparation method of the carbon-black-containing butadiene styrene rubber master batch is free of addition of surfactants and is simple, stable and reliable in processes. A product is free of a contact polluting property and is stable when being stored. A vulcanized robber of the product is excellent in physical and mechanical performances and particularly is excellent in a dynamic mechanical performance.
Description
Technical field
The invention belongs to rubber rubber master batch preparation field, be specifically related to a kind of preparation method of carbon black extended SBR rubber master batch.
Background technology
Fill black rubber rubber master batch also referred to as carbon black filled type rubber, the premix being a kind of rubber and carbon black is fit, two large classes can be divided into: a class adopts rubber latex/carbon black method by preparation method, namely with rubber latex and carbon black for raw material, the rubber/carbon black premix zoarium (carbon black rubber master batch) prepared; Another kind of is the rubber masterbatch containing carbon black adopting mechanical mixing method (as mixer mixing) to obtain.Compared with the latter, carbon black dispersion is made carbon black slurry by the former in water, rubber/carbon black mixture is mixed to form again with latex, it is the main method preparing carbon black rubber master batch, and do not have carbon black to fly upward in preparation process, carbon black disperse in rubber matrix evenly, shorten mixing time and reduce power consumption.
Adopt the standby gordian technique of filling carbon black rubber master batch of rubber latex/carbon black legal system to be the dispersion of carbon black in rubber, this determined primarily of the dispersion level of carbon black in water.Rubber grade carbon black is typical lipophilicity powder, is easy to reunite in water-based system, therefore often adds tensio-active agent (also referred to as emulsifying agent) and improve the dispersion of carbon black in water.We notice, adding of tensio-active agent has significant advantage, namely the dispersion of carbon black in rubber improves, the prepared carbon black rubber master batch that fills also has good comprehensive mechanical property, but owing to being difficult to all to be washed away from filling carbon black rubber master batch by all tensio-active agents in the preparation process filling carbon black rubber master batch, the tensio-active agent remained in rubber may destroy the interaction between rubber and carbon black, such as: may cause degradation under the stress at definite elongation of cross-linked rubber; On the other hand, after filling and being entered waste water system by the partial emulsifier come out carbon black rubber master batch, the cost increase of wastewater treatment will be caused.
Summary of the invention
The object of the invention is to overcome in the technology of preparing of existing carbon black extended SBR rubber master batch, owing to adding tensio-active agent as carbon black disperser, remain in rubber stress at definite elongation that the tensio-active agent in rubber causes and the deficiency that intensity reduces and the deficiency that tensio-active agent causes cost for wastewater treatment to increase, a kind of preparation method being suitable for the carbon black extended SBR rubber master batch of contactless pollution not adding tensio-active agent is provided.
Object of the present invention is achieved through the following technical solutions:
A preparation method for carbon black extended SBR rubber master batch, comprises the steps:
(1) get the raw materials ready: by following component and weight batching:
Styrene-butadiene latex: 100 parts (by dry glue gauge); Carbon black: 40 ~ 100 parts; Water: 1500 ~ 3000 parts; Process oil: 0 ~ 30 part; Coating: 1 ~ 5 part; Flocculation agent: 1 ~ 5 part;
(2) prepare carbon black suspension: add carbon black in a kettle., then add concentration to 2.0 ~ 5.0wt% that part water regulates carbon black, high-speed stirring is disperseed, and obtains carbon black suspension;
(3) the mixing and thermal treatment of latex and carbon black: add styrene-butadiene latex under stirring at normal temperature condition in above-mentioned carbon black suspension, mix to obtain latex/carbon black mixed system, add water and make the solids total content in described latex/carbon black mixed system be 3 ~ 5wt%; Then reactor is heated to 70 ~ 90 DEG C, then adds the hot water suspension that mass concentration is the coating of 1%, continue stirring 10 ~ 15 minutes, obtain the latex after thermal treatment/carbon black mixed system;
(4) agglomeration process: under agitation, the mass concentration adding metering in the latex after above-mentioned thermal treatment/carbon black mixed system is the flocculation agent aqueous solution of 20%, there is the coprecipitated phenomenon of cohesion, with Powdered precipitation condensation product, continuing to stir keeps temperature to be 70 ~ 90 DEG C, if containing process oil in formula, under agitation add process oil, continue stirring 10 ~ 15 minutes;
(5) aftertreatment of solidifying condensation product: the condensation product after agglomeration process is obtained wet particle product through filter-cloth filtering, wash three to four times with water, dehydration, the gained particle product that wets is dried to moisture content below 1% with 80 ~ 90 DEG C in air dry oven, obtains described carbon black extended SBR rubber master batch.
Preferably, described styrene-butadiene latex is universal styrene butadiene rubber latex;
Preferably, described carbon black is super-high wear-resistant carbon black (SAF), intermediate super abrasion furnace black (ISAF), high wear-resistant carbon black (HAF) or semi-reinforcing hydrocarbon black (SRF);
Preferably, described process oil is that rubber industry commonly uses process oil or extending oil, is specially machine oil, naphthenic oil or aromatic hydrocarbon oil;
Preferably, described coating is the fatty acid alkali metal salt that can be dissolved in more than 70 DEG C hot water; Preferred, described coating is sodium stearate or the potassium stearate that can be dissolved in more than 70 DEG C hot water;
Preferably, described flocculation agent is one or more the mixture in calcium chloride, zinc chloride, nitrocalcite or zinc nitrate;
Described coating is can produce water-fast divalent metal salt on the spot in 60 ~ 90 DEG C and the calcium in flocculation agent, zine ion, and the divalent metal salt pair rubber particles generated plays isolation coating function;
Preferably, the stirring velocity of the described high-speed stirring dispersion of step (2) is 3000 ~ 6000rpm, and the time is 30 ~ 120 minutes.
Principle of the present invention:
The preparation method of the novel carbon black extended SBR rubber master batch that the present invention states, the tensio-active agent (having another name called: emulsifying agent) for improving carbon black dispersion is not added, by means of only improving preparation technology and obtaining uniform and stable carbon black dispersion by stronger mechanical shearing and mechanical agitation in preparation process.After carbon black disperses to form stable carbon black suspension in water, add latex and form carbon black/rubber mix system, coating (as: sodium stearate solution or potassium stearate solution) is added in this system, then with water-soluble divalent metal cohesion, stearate reacts with it and generates insoluble divalent metal salt and cover the surface of the macroscopic particle that rubber and carbon black are formed and isolated; The carbon black extended SBR rubber master batch particle obtained only contains minute quantity divalent metal salt in particle after washing, therefore the carbon black filled powder rubber utilizing the method to prepare is pure especially, and not containing tensio-active agent in its washes, reduce the processing cost of waste water; Again owing to not adding tensio-active agent in preparation process, not containing tensio-active agent in therefore obtained carbon black extended SBR rubber master batch particle, effectively overcome the shortcoming adding rubber stress at definite elongation caused by emulsifying agent and strength degradation.
The present invention has following advantage and effect relative to prior art:
(1) the inventive method is adopted to prepare carbon black extended SBR rubber master batch, do not need to add for improving carbon black tensio-active agent dispersed in water, but obtain good, stable carbon black dispersion by improving preparation technology, preparation method is simple and reproducible, low to the requirement of production unit, and cost is low.
(2) the inventive method is adopted to prepare carbon black extended SBR rubber master batch, owing to not adding tensio-active agent, overcome the reduction because adding the cross-linked rubber stress at definite elongation that causes of tensio-active agent and intensity, and the shortcoming that emulsifying agent causes cost for wastewater treatment to increase.
(3) adopt the inventive method to prepare carbon black extended SBR rubber master batch, the particle diameter of product can be controlled by the drop rate controlling flocculation agent.
(4) the carbon black extended SBR rubber master batch adopting the inventive method to prepare, subsequent treatment process is simple, the contactless pollution of its surface.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1 ~ 8
(1) get the raw materials ready
By the proportion ingredient in table 1.
The reagent dosage of table 1 embodiment and processing condition
(2) carbon black suspension is prepared
By formula listed in table 1 and control condition, water and the carbon black of metering is added in reactor, regulate concentration to 2.0 ~ 5.0% of carbon black, dispersed with stirring under the effect of high speed dispersor, rate of dispersion is set to 3000 ~ 6000rpm, after carbon black dispersion 30 ~ 120min, the carbon black suspension of uniform and stable dispersion can be obtained.
(3) the mixing and thermal treatment of latex and carbon black
By the formula listed by table 1, the reactor that scattered carbon black suspension is housed is moved in water-bath and stirs, the distilled water of latex and metering is added in carbon black suspension, in regulation system, the solids total content of latex is 3 ~ 5%, mix rear heating in water bath to 70 ~ 90 DEG C, the concentration adding metering is the hot water suspension of the sodium stearate of 1%, continues stirring 10 ~ 15 minutes, obtains the latex after thermal treatment/carbon black mixed system.
(4) agglomeration process
By formula listed in table 1, the concentration adding metering in the latex after above-mentioned thermal treatment/carbon black mixed system is the calcium chloride water of 20%, vigorous stirring (stirring velocity is 1200 ~ 1400rpm) simultaneously, emulsion is made all to be condensed into particle, system temperature is made to remain on 70 ~ 90 DEG C in this process, if containing process oil in formula, under agitation add process oil, continue stirring 10 ~ 15 minutes.
(5) aftertreatment of condensation product
Condensation product after agglomeration process is obtained wet particle product through filter-cloth filtering, wash three to four times with water, dehydration, the gained particle product that wets is dried to moisture content less than 1% with 80 ~ 90 DEG C in air dry oven, obtains the carbon black extended SBR rubber master batch of suitable particle diameter.
Particle (powder) shape of described carbon black extended SBR rubber master batch form to be particle diameter be 0.5mm ~ 3mm, its physical and mechanical properties is as shown in table 2:
The physical and mechanical properties of table 2 carbon black extended SBR rubber master batch
Note: 1, the sulfurizing formula of carbon black extended SBR: rubber (not containing carbon black) 100, carbon black (N234) variable, stearic acid 1, zinc oxide 3, antioxidant 4010NA 1.5, accelerator NS 1, sulphur 1.75; 2, cure conditions is: 145 DEG C × 30min.
From table 2, the physical and mechanical properties of carbon black extended SBR rubber master batch of the present invention is good.
Claims (8)
1. a preparation method for carbon black extended SBR rubber master batch, is characterized in that comprising the steps:
(1) get the raw materials ready: by following component and weight batching:
Styrene-butadiene latex: 100 parts (by dry glue gauge); Carbon black: 40 ~ 100 parts; Water: 1500 ~ 3000 parts; Process oil: 0 ~ 30 part; Coating: 1 ~ 5 part; Flocculation agent: 1 ~ 5 part;
(2) prepare carbon black suspension: add carbon black in a kettle., then add concentration to 2.0 ~ 5.0wt% that part water regulates carbon black, high-speed stirring is disperseed, and obtains carbon black suspension;
(3) the mixing and thermal treatment of latex and carbon black: add styrene-butadiene latex under stirring at normal temperature condition in above-mentioned carbon black suspension, mix to obtain latex/carbon black mixed system, add water and make the solids total content in described latex/carbon black mixed system be 3 ~ 5wt%; Then reactor is heated to 70 ~ 90 DEG C, then adds the hot water suspension that mass concentration is the coating of 1%, continue stirring 10 ~ 15 minutes, obtain the latex after thermal treatment/carbon black mixed system;
(4) agglomeration process: under agitation, the mass concentration adding metering in the latex after above-mentioned thermal treatment/carbon black mixed system is the flocculation agent aqueous solution of 20%, there is the coprecipitated phenomenon of cohesion, with Powdered precipitation condensation product, continuing to stir keeps temperature to be 70 ~ 90 DEG C, if containing process oil in formula, under agitation add process oil, continue stirring 10 ~ 15 minutes;
(5) aftertreatment of solidifying condensation product: the condensation product after agglomeration process is obtained wet particle product through filter-cloth filtering, wash three to four times with water, dehydration, the gained particle product that wets is dried to moisture content below 1% with 80 ~ 90 DEG C in air dry oven, obtains described carbon black extended SBR rubber master batch.
2. the preparation method of carbon black extended SBR rubber master batch according to claim 1, is characterized in that: described styrene-butadiene latex is universal styrene butadiene rubber latex.
3. the preparation method of carbon black extended SBR rubber master batch according to claim 1, is characterized in that: described carbon black is super-high wear-resistant carbon black, intermediate super abrasion furnace black, high wear-resistant carbon black or semi-reinforcing hydrocarbon black.
4. the preparation method of carbon black extended SBR rubber master batch according to claim 1, is characterized in that: described process oil is machine oil, naphthenic oil or aromatic hydrocarbon oil.
5. the preparation method of carbon black extended SBR rubber master batch according to claim 1, is characterized in that: described coating is the fatty acid alkali metal salt that can be dissolved in more than 70 DEG C hot water.
6. the preparation method of carbon black extended SBR rubber master batch according to claim 5, is characterized in that: described coating is sodium stearate or the potassium stearate that can be dissolved in more than 70 DEG C hot water.
7. the preparation method of carbon black extended SBR rubber master batch according to claim 1, is characterized in that: described flocculation agent is one or more the mixture in calcium chloride, zinc chloride, nitrocalcite or zinc nitrate.
8. the preparation method of carbon black extended SBR rubber master batch according to claim 1, is characterized in that: the stirring velocity of the described high-speed stirring dispersion of step (2) is 3000 ~ 6000rpm, and the time is 30 ~ 120 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410337186.XA CN104211837B (en) | 2014-07-15 | 2014-07-15 | A kind of preparation method of carbon black extended SBR rubber master batch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410337186.XA CN104211837B (en) | 2014-07-15 | 2014-07-15 | A kind of preparation method of carbon black extended SBR rubber master batch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104211837A true CN104211837A (en) | 2014-12-17 |
| CN104211837B CN104211837B (en) | 2016-05-04 |
Family
ID=52093769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410337186.XA Active CN104211837B (en) | 2014-07-15 | 2014-07-15 | A kind of preparation method of carbon black extended SBR rubber master batch |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104211837B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183751A (en) * | 2019-07-02 | 2019-08-30 | 江苏通用科技股份有限公司 | A kind of racing tread glue formula and preparation method thereof |
| CN111592694A (en) * | 2020-05-14 | 2020-08-28 | 华南理工大学 | Natural rubber masterbatch filled with carbon black and preparation method and application thereof |
| CN113004588A (en) * | 2021-04-19 | 2021-06-22 | 中科院长春应化所黄埔先进材料研究院 | Aircraft tire tread composition and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3380958A (en) * | 1966-12-23 | 1968-04-30 | Manton Gaulin Mfg Company Inc | Method of incorporating carbon black and other materials into elastomers |
| CN1415653A (en) * | 2002-11-29 | 2003-05-07 | 华南理工大学 | Method for preparing powdered rubber with carbon black stuffing |
| CN1415648A (en) * | 2002-11-29 | 2003-05-07 | 华南理工大学 | Method for preparing powdered rubber in stuffing type with extra fine calcium carbonate |
| CN102816265A (en) * | 2012-07-30 | 2012-12-12 | 华南理工大学 | Hydrometallurgy method for preparing natural rubber/carbon black compound rubber |
| CN103819760A (en) * | 2014-03-18 | 2014-05-28 | 北京化工大学 | Process method for preparing high-performance carbon black masterbatch |
-
2014
- 2014-07-15 CN CN201410337186.XA patent/CN104211837B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3380958A (en) * | 1966-12-23 | 1968-04-30 | Manton Gaulin Mfg Company Inc | Method of incorporating carbon black and other materials into elastomers |
| CN1415653A (en) * | 2002-11-29 | 2003-05-07 | 华南理工大学 | Method for preparing powdered rubber with carbon black stuffing |
| CN1415648A (en) * | 2002-11-29 | 2003-05-07 | 华南理工大学 | Method for preparing powdered rubber in stuffing type with extra fine calcium carbonate |
| CN102816265A (en) * | 2012-07-30 | 2012-12-12 | 华南理工大学 | Hydrometallurgy method for preparing natural rubber/carbon black compound rubber |
| CN103819760A (en) * | 2014-03-18 | 2014-05-28 | 北京化工大学 | Process method for preparing high-performance carbon black masterbatch |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183751A (en) * | 2019-07-02 | 2019-08-30 | 江苏通用科技股份有限公司 | A kind of racing tread glue formula and preparation method thereof |
| CN111592694A (en) * | 2020-05-14 | 2020-08-28 | 华南理工大学 | Natural rubber masterbatch filled with carbon black and preparation method and application thereof |
| CN111592694B (en) * | 2020-05-14 | 2021-03-30 | 华南理工大学 | Natural rubber masterbatch filled with carbon black and preparation method and application thereof |
| CN113004588A (en) * | 2021-04-19 | 2021-06-22 | 中科院长春应化所黄埔先进材料研究院 | Aircraft tire tread composition and preparation method thereof |
| CN113004588B (en) * | 2021-04-19 | 2022-07-05 | 广东粤港澳大湾区黄埔材料研究院 | Aircraft tire tread composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104211837B (en) | 2016-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104334616B (en) | Rubber wet masterbatch | |
| CN104059245A (en) | Method for preparation of rubber vulcanization activator by seed deposition | |
| DE112012005526B4 (en) | Production process for rubber composition | |
| CN108026315A (en) | The method for the elastomeric compound that manufacture is strengthened with silica and the product for including it | |
| CN105199171A (en) | Preparation method of white carbon black masterbatch, obtained product and application of product to high-wear-resistance white carbon black reinforcing material for rubber | |
| CN103819760B (en) | A kind of processing method preparing high-performance carbon black rubber master batch | |
| CN105419009B (en) | A kind of method that semi-open type superheated steam spray drying process prepares high filled composite rubber master batch | |
| DE112014005088T5 (en) | Production process for rubber composition | |
| CN102775654A (en) | Preparation method for liquid phase stirring and mixing of white carbon black and natural rubber | |
| CN106750389A (en) | A kind of method that wet method prepares white carbon black/solution polymerized butadiene styrene rubber rubber master batch | |
| DE102017120084B4 (en) | Method of manufacturing a tire element | |
| CN104211837A (en) | Preparation method of carbon-black-containing butadiene styrene rubber master batch | |
| JP6295374B2 (en) | Functionalized silica with elastomeric binder | |
| CN104072789B (en) | A kind of method that wet method is mixing | |
| JP5094135B2 (en) | Method for producing natural rubber and / or synthetic isoprene rubber masterbatch using powder rubber and filler | |
| JP2010209175A (en) | Method for manufacturing wet masterbatch and vulcanized rubber obtained using the wet masterbatch | |
| JPS5827709A (en) | Manufacture of powdery emulsion polymerization butadiene rubber | |
| CN1168770C (en) | Method for preparing powdered rubber with carbon black stuffing | |
| CN1206268C (en) | Method for preparing powdered rubber in stuffing type with extra fine calcium carbonate | |
| CN108250453A (en) | The manufacturing method of rubber wet masterbatch | |
| WO2016014037A1 (en) | A process to prepare high-quality natural rubber-silica masterbatch by liquid phase mixing | |
| CN106459428B (en) | The manufacturing method of rubber wet masterbatch | |
| CN104072831A (en) | Oil-extended carbon-nanotubes-extended binary emulsion coprecipitation rubber and preparation method thereof | |
| JP2008231152A (en) | Wet master batch, method for producing the same and rubber composition by using the same | |
| JP2011032373A (en) | Manufacturing method for wet master batch |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |