CN103819760B - A kind of processing method preparing high-performance carbon black rubber master batch - Google Patents
A kind of processing method preparing high-performance carbon black rubber master batch Download PDFInfo
- Publication number
- CN103819760B CN103819760B CN201410101669.XA CN201410101669A CN103819760B CN 103819760 B CN103819760 B CN 103819760B CN 201410101669 A CN201410101669 A CN 201410101669A CN 103819760 B CN103819760 B CN 103819760B
- Authority
- CN
- China
- Prior art keywords
- carbon black
- latex
- master batch
- rubber master
- 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.)
- Active
Links
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of processing method preparing high-performance carbon black rubber master batch relates to the fabricating technology field of carbon black rubber master batch.The invention provides a kind of technique simple, less energy consumption, the processing method of the wet-layer preparation carbon black rubber master batch of excellent performance, selects the carbon black powder of the non-granulation of the solution immersion of small molecules easy volatile solvent to prepare finely dispersed carbon black slurry; Select certain stirring linear velocity, do not add other flocculation agent and glue and carbon black are wadded a quilt with cotton out, filter, dry.Carbon black in the rubber master batch adopting this technique to prepare reaches nano-dispersed, mechanical property of vulcanized rubber is excellent, resilience is good, and heat-dissipating is low, and wear resistance is high, preparation technology is simple, facility investment is few, and energy consumption is little, and cost is low, environmental protection, avoids the impact on rubber performance such as tensio-active agent and flocculation agent and the pollution of environment.
Description
Technical field
The present invention relates to the fabricating technology field of carbon black rubber master batch, particularly utilize the processing method of wet-layer preparation carbon black rubber master batch.
Background technology
So far carbon black remains irreplaceable strengthening agent in rubber industry, and its outstanding other strengthening agent of comprehensive reinforcing property still cannot reach.Normal use dry process carbon black rubber master batch in industrial production, some shortcomings of the mixing existence of dry method, such as: the dispersion of carbon black is bad, utilization ratio is low and when mixing, easily make rubber molecule splitting of chain serious, both caused refining, this has serious impact to the performance of rubber.
In view of the shortcoming be dry mixed, people attempt to prepare rubber master batch by wet-mixed and overcome these shortcomings.Wet-mixed generally comprises spray-drying process, emulsion flocculence etc.Carbon black, zinc oxide, stearic acid, sulphur, promotor etc. are mainly made into carbon black suspension by spray-drying process by a certain percentage, then natural rubber latex is joined, use spray-drier to be atomized by spraying gun by the mixed solution of preparation after stirring, droplet obtains dry carbon black rubber master batch through moisture eliminator removing moisture again.The advantage of this technique is that he can continuous seepage, but energy consumption is large, and equipment is complicated, and bad control, cost is higher.Also can there is adverse influence to the performance of rubber in the tensio-active agent added in slurry production process in addition and emulsifying agent etc., also easily cause environmental pollution.It is simple that emulsion flocculence prepares rubber master batch technics comparing, the P(NR/CB that South China Science & Engineering University Zhang Anqiang utilizes flocculence to prepare) excellent performance, its preparation method is: first use dispersion agent by carbon black dispersion in water, prevent carbon black from reuniting, the carbon black of resin to dispersion is used to carry out coated, obtain the carbon black of stable dispersion like this, then carbon black slurry is mixed with natural rubber latex, finally add flocculation agent and make the uniform natural rubber latex co-coagulation of carbon black dispersion out.This processing method still cannot avoid the use of dispersion agent, flocculation agent, seriously polluted, and technique is still very loaded down with trivial details, and energy consumption is large, cost is high, industrialization difficulty.The standby CEC rubber master batch of Cabot Inc. puts into production, and this production method utilizes colloidal mill that carbon black is worn into uniform carbon black slurry in water, and the mechanical shearing effect that slurry stream and emulsion flow correlation produce realizes mixing and flocculation of carbon black and latex.This technological effect is good, but equipment is complicated, and the method is bought out, commercially cannot buy.
Wet-layer preparation carbon black rubber master batch technology key is carbon black slurry preparation, the preparation carbon black slurry such as carbon black pellet utilizes Mechanical Crushing such as to grind by present major part, ultrasonic, consume energy so high, the final fineness of dispersion of carbon black of preparation is larger, cause the dispersion effect of carbon black poor, performance is bad.
Summary of the invention
The invention provides a kind of a kind of method solved the problem, mainly utilize the carbon black of non-granulation in aqueous molten, be then uniformly mixed autoflocculation with natural rubber latex and go out.Rubber master batch prepared by the method has given full play to the strengthening action of carbon black, excellent in mechanical performance, and facility investment is few, and energy consumption is low, and cost is little, and does not add any tensio-active agent, and acid or salt flocculation agent are a kind of methods of environmental protection.
In order to solve the technical problem of above-mentioned existence, present invention employs following proposal:
1. select the solution immersion carbon black powder of small molecules easy volatile solvent to prepare finely dispersed carbon black slurry, the mass percent 2.5% ~ 10% of carbon black slurry; Latex is added carbon black slurry and stir 20-60min at 100 ~ 300m/min after rotating speed 10 ~ 40m/min stirs 10 ~ 30min, latex and carbon black are wadded a quilt with cotton out, filter, dry; Described small molecules easy volatile solvent is methyl alcohol, ethanol, propyl alcohol, tetrahydrofuran (THF), acetone, butanone, or their mixture; Be 100 parts in dry glue quality in latex, the add-on of carbon black is at 30 parts ~ 80 parts; Treating compound adds 10 parts ~ 300 parts.
2. as preferred: the volatile carbon black treating compound of small molecules preferably ethanol;
3 as preferred: latex is fresh natural emulsion or concentrated natural latex, styrene-butadiene latex, nitrile rubber, neoprene latex, fourth pyrrole and butylbenzene pyrrole latex, and above mixed latex;
4 as preferred: when the mass percent concentration of latex is 5% ~ 40%, the mobility of latex is better easily disperseed;
When utilizing granulation carbon black to prepare carbon black slurry, carbon black is not easily broken, be difficult to prepare homodisperse carbon black slurry, and energy consumption is high.This technology utilization carbon black powder prepares carbon black slurry, the aqueous solution that have selected small molecules easy volatile solvent does treating compound, treating compound reduces the surface energy between the particle of carbon black, the surface tension of carbon black is reduced, therefore speed soluble in water is accelerated, the reunion degree of carbon black is weakened, dispersiveness in water improves the carbon black dissolved in pure water as seen from Figure 1 and assembles closely, do not see the form of spheroidal particle completely, the arrangement of dissolving in ethanol is more loose, spherical particle is obvious and particle is less, the carbon black particle arrangement of dissolving in tetrahydrofuran (THF) is also more loose, but particle is larger, visible treating compound significantly reduces the self aggregation degree of carbon black, improve the dispersiveness of carbon black to a certain extent, after adding latex, on the one hand because treating compound has dehydration to go steady demulsification, carbon black has on the other hand has strong adsorption to make rubber latex go surely to latex, originally the carbon black particle that arrangement is loose, under the power that pulls carbon black produced due to adsorption at rubber molecular chain and mechanical shear stress effect, absorption one deck rubber molecular chain of surface uniform, define little rubber coated carbon black fine particle, further increasing mechanical shear stress, mutually collide between rubber coated carbon black fine particle, be bonded together, finally define the carbon black rubber master batch that carbon black becomes nano-dispersed, after leaching, the treating compound remained in during oven dry in rubber master batch can remove due to volatile, have like this and eliminate the impact for the treatment of compound on rubber performance.Fig. 2 is the scatter diagram of carbon black in black rubber rubber master batch of wadding a quilt with cotton out, and the carbon black pellet size as seen from the figure in rubber master batch is at 80 ~ 100nm, and this is the original size of high structural carbon black N234, and is evenly distributed.After sulfuration carbon black significantly do not reassociate phenomenon (as Fig. 4,5) therefore mechanical property improve greatly.
Beneficial effect of the present invention:
1, the present invention uses volatile small molecule solvent to do treating compound, has discharged the impact added rubber performance of other materials, and improves the solvability of carbon black in water and dispersiveness.
2, the present invention utilizes treating compound to destroy the stability of latex, less mechanical shear stress achieves the mixing of the dispersion of carbon black in water, carbon black slurry and natural rubber latex slurries, and larger shearing force achieves carbon black and latex sharp impacts thus flocculates, enormously simplify technological process, discharge the impact of flocculation agent on rubber performance and environment.
3, technique involved in the present invention is simple, energy consumption is few, security is good, reduce tooling cost, is applicable to industrial production.
Accompanying drawing illustrates:
Fig. 1, different solvents soaked the accumulation shape comparison diagram of carbon black pellet, wherein carbon black respectively in (1) water, the microscopic pattern figure of molten mistake in (2) ethanol, (3) tetrahydrofuran (THF).
Carbon black dispersion SEM figure in Fig. 2, wadding plastic emitting, wherein (1) is the surface topography of rubber particles of wadding a quilt with cotton out, and (2) are the partial enlarged drawings of (1); (3) be the sectional elevation of particle of wadding a quilt with cotton out, (4) are the partial enlarged drawings of (3).
Fig. 3, process flow sheet
The atomic force microscope modulus figure of Fig. 4, example 1
The atomic force microscope modulus figure of Fig. 5, example 2
The atomic force microscope modulus figure of Fig. 6, example 3
The atomic force microscope modulus figure of Fig. 7, comparison example 1
Embodiment
Embodiment 1:
It is 100 parts in dry glue quality in natural emulsion, 50phr carbon black powder (N234) is joined in the aqueous solution containing 10phr ethanol, mass percentage is the carbon black slurry of 2.5%, stir 20min, natural emulsion is diluted to 40%(mass percentage, the percentage composition below without special instruction is mass percentage) after join in carbon black slurry, stir 10min at rotating speed 40m/min and rotating speed be adjusted to 300m/min and stir 40min, the rubber master batch of wadding a quilt with cotton out is taken out, dries.Above-mentioned rubber master batch is containing glue 100phr, ZnO5phr, stearic acid 2phr, anti-aging agent 1010NA1phr, accelerant CZ 1.2phr, sulphur 2phr, and refining glue, surveys vulcanization curve and Rubber processing performance, sulfuration at 143 DEG C after parking 8h, survey mechanical property.
Embodiment 2:
It is 100 parts in dry glue quality in natural emulsion, 50phr carbon black powder (N234) is added in the aqueous solution containing 50phr ethanol, mass percentage processed is the carbon black slurry of 5%, stir 20min, join in carbon black slurry after natural emulsion (wherein dry glue is 100 parts) is diluted to 30%, stir 20min at rotating speed 20m/min and rotating-speed modulation 200m/min is stirred 50min, taken out by the rubber of wadding a quilt with cotton out, all the other steps are as embodiment 1.
Embodiment 3:
It is 100 parts in dry glue quality in natural emulsion, 50phr carbon black powder (N234) is joined in the aqueous solution containing 150phr ethanol, mass percentage processed is the carbon black slurry of 7%, stir 20min, join in carbon black slurry after natural emulsion (wherein dry glue is 100 parts) is diluted to 25%, stir 30min at rotating speed 10m/min and rotating-speed modulation 300m/min is stirred 30min, taken out by the rubber of wadding a quilt with cotton out, all the other steps are as embodiment 1.
Embodiment 4:
It is 100 parts in dry glue quality in natural gum glue gel resin, 50phr carbon black powder (N234) is joined in the aqueous solution containing 50phr ethanol, mass percentage processed is the carbon black slurry of 10%, stir 20min, by natural gum glue gel resin (molecular weight, mass percentage are 5%) wherein dry glue be 100 parts, join in carbon black slurry, rotating speed 20m/min stir 20min by rotating-speed modulation 100m/min stir 60min, taken out by the rubber of wadding a quilt with cotton out, all the other steps are as embodiment 1.
Embodiment 5:
It is 100 parts in dry glue quality in natural emulsion, 50phr carbon black powder (N234) is joined in the aqueous solution containing 25phr tetrahydrofuran (THF), mass percentage processed is the carbon black slurry of 5%, stir 20min, fresh natural rubber latex (wherein dry glue is 100 parts) is joined in carbon black slurry, stir 10min at rotating speed 30m/min and rotating-speed modulation 200m/min is stirred 40min, taken out by the rubber of wadding a quilt with cotton out, all the other steps are as embodiment 1.
Comparative example 1:
By formula on two roller begins to pratise machine: natural gum (No. 1, cloud mark) 100phr, carbon black (N234) 50phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1.
Embodiment 6
It is 100 parts in dry glue quality in natural emulsion, (30phr) carbon black powder (N234) is joined in the aqueous solution containing 50phr acetone, mass percentage processed is the carbon black slurry of 5%, stir 20min, join in carbon black slurry after natural rubber latex (wherein dry glue is 100 parts) is diluted to 40%, stir 10min at rotating speed 30m/min and rotating-speed modulation 100m/min is stirred 30min, taken out by the rubber of wadding a quilt with cotton out, all the other steps are as embodiment 1.
Comparative example 2:
By formula on two roller begins to pratise machine: natural gum (No. 1, cloud mark) 100phr, carbon black (N234) 30phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1.
Embodiment 7
It is 100 parts in dry glue quality in natural emulsion, (80phr) carbon black powder (N330) is joined in the aqueous solution containing 50phr methyl alcohol, mass percentage processed is the carbon black slurry of 5%, stir 20min, join in carbon black slurry after natural rubber latex (wherein dry glue is 100 parts) is diluted to 40%, stir 10min at rotating speed 30m/min and rotating-speed modulation 100m/min is stirred 30min, taken out by the rubber of wadding a quilt with cotton out, all the other steps are as embodiment 1.
Comparative example 3:
By formula on two roller begins to pratise machine: natural gum (No. 1, cloud mark) 100phr, carbon black (N330) 80phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1.
Embodiment 8
It is 100 parts in dry glue in latex (namely following butadiene-styrene latex (1502)), (50phr) carbon black powder (N330) is joined in the aqueous solution of 50phr ethanol, mass percentage processed is the carbon black slurry slurries of 5%, stir 20min, by butadiene-styrene latex (1502) mass percentage content be 18%(wherein dry glue be 100 parts) join in carbon black slurry, stir 10min at rotating speed 30m/min and rotating-speed modulation 100m/min is stirred 30min, taken out by the rubber of wadding a quilt with cotton out, all the other steps are as embodiment 1.
Comparative example 4:
By formula on two roller begins to pratise machine: breast poly-butadiene-styrene rubber (1502) 100phr, carbon black (N330) 50phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1.
Embodiment 9
It is 100 parts in dry glue in latex (namely following butyronitrile latex), (50phr) carbon black powder (N220) is joined in the aqueous solution containing 50phr ethanol, mass percentage processed is the carbon black slurry of 5%, stir 20min, by butyronitrile latex mass percentage content be 25%(wherein dry glue be 100 parts) join in carbon black slurry, stir 10min at rotating speed 30m/min and rotating-speed modulation 100m/min is stirred 30min, taken out by the rubber of wadding a quilt with cotton out, all the other steps are as embodiment 1.
Comparative example 5:
By formula on two roller begins to pratise machine: butadiene-acrylonitrile rubber 100phr, carbon black (N220) 50phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1.
Embodiment 10
It is 100 parts in dry glue in latex (the namely following natural emulsion mixed and butadiene-styrene latex), (50phr) carbon black powder (N234) is added in the aqueous solution containing 50phr ethanol, mass percentage processed is the carbon black slurry slurries of 5%, stir 20min, the natural emulsion mixed and butadiene-styrene latex are amounted to dry glue each 50phr, the mass percentage content of mixed latex is 28% join in carbon black slurry, rotating speed 30m/min stirs 10min and rotating-speed modulation 100m/min is stirred 30min, taken out by the rubber of wadding a quilt with cotton out, all the other steps are as embodiment 1.
Comparative example 6
By formula on two roller begins to pratise machine: each 50phr of natural gum butadiene-styrene rubber, carbon black (N234) 50phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1.
Table one embodiment and the contrast of comparative example mechanical property
Claims (4)
1. prepare a processing method for high-performance carbon black rubber master batch, it is characterized in that:
Select the solution immersion carbon black powder of small molecules easy volatile solvent to prepare finely dispersed carbon black slurry, the mass percent 2.5% ~ 10% of carbon black slurry; Latex is added carbon black slurry and stir 20-60min at 100 ~ 300m/min after rotating speed 10 ~ 40m/min stirs 10 ~ 30min, latex and carbon black are wadded a quilt with cotton out, filter, dry; Described small molecules easy volatile solvent is methyl alcohol, ethanol, propyl alcohol, tetrahydrofuran (THF), acetone, butanone, or their mixture; Be 100 parts in dry glue quality in latex, the add-on of carbon black is at 30 parts ~ 80 parts; Treating compound adds 10 parts ~ 300 parts, in whole process, does not add flocculation agent.
2. a kind of processing method preparing high-performance carbon black rubber master batch according to claim 1, is characterized in that: the volatile carbon black treating compound of small molecules is ethanol.
3. a kind of processing method preparing high-performance carbon black rubber master batch according to claim 1, is characterized in that: latex is fresh natural emulsion or concentrated natural latex, butadiene-styrene latex, butyronitrile latex, neoprene latex, fourth pyrrole and butylbenzene pyrrole latex, and the mixed latex of above latex.
4. a kind of processing method preparing high-performance carbon black rubber master batch according to claim 1, is characterized in that: preparation latex mass percent concentration is 5% ~ 40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410101669.XA CN103819760B (en) | 2014-03-18 | 2014-03-18 | A kind of processing method preparing high-performance carbon black rubber master batch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410101669.XA CN103819760B (en) | 2014-03-18 | 2014-03-18 | A kind of processing method preparing high-performance carbon black rubber master batch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103819760A CN103819760A (en) | 2014-05-28 |
| CN103819760B true CN103819760B (en) | 2015-12-02 |
Family
ID=50755071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410101669.XA Active CN103819760B (en) | 2014-03-18 | 2014-03-18 | A kind of processing method preparing high-performance carbon black rubber master batch |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103819760B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018109969A1 (en) * | 2016-12-14 | 2018-06-21 | 東洋ゴム工業株式会社 | Method for producing master batch, method for producing rubber composition, and method for producing tire |
| WO2018123113A1 (en) * | 2016-12-27 | 2018-07-05 | 東洋ゴム工業株式会社 | Masterbatch manufacturing method and tire manufacturing method |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072831B (en) * | 2014-06-27 | 2016-03-09 | 青岛大学 | One is oil-filled fills carbon nanotube dual emulsion coprecipitation rubber and preparation method thereof |
| CN104211837B (en) * | 2014-07-15 | 2016-05-04 | 华南理工大学 | A kind of preparation method of carbon black extended SBR rubber master batch |
| CN105419009B (en) * | 2015-11-29 | 2019-03-01 | 北京化工大学 | A kind of method that semi-open type superheated steam spray drying process prepares high filled composite rubber master batch |
| CN107505480B (en) * | 2017-08-16 | 2020-05-08 | 四川理工学院 | Method for detecting filler dispersibility in rubber composite material |
| CN109517195B (en) * | 2017-09-18 | 2021-01-12 | 北京化工大学 | Method for preparing carbon black master batch by wet mixing |
| CN108794821A (en) * | 2018-06-07 | 2018-11-13 | 浙江环能传动科技有限公司 | A kind of method of plasticating of natural gum |
| CN112852189B (en) * | 2021-01-21 | 2022-04-05 | 山东联科科技股份有限公司 | Preparation method of carbon black |
| CN115970569B (en) * | 2023-03-17 | 2023-06-09 | 青岛黑猫新材料研究院有限公司 | System and method for processing intermediate product of carbon black |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1282510A (en) * | 1969-10-30 | 1972-07-19 | Bp Chem Int Ltd | Nitrile rubber compositions |
| CN102356120A (en) * | 2009-03-16 | 2012-02-15 | 株式会社普利司通 | Process for producing rubber-wet masterbatch, rubber composition, and tire |
| CN102816265A (en) * | 2012-07-30 | 2012-12-12 | 华南理工大学 | Hydrometallurgy method for preparing natural rubber/carbon black compound rubber |
-
2014
- 2014-03-18 CN CN201410101669.XA patent/CN103819760B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1282510A (en) * | 1969-10-30 | 1972-07-19 | Bp Chem Int Ltd | Nitrile rubber compositions |
| CN102356120A (en) * | 2009-03-16 | 2012-02-15 | 株式会社普利司通 | Process for producing rubber-wet masterbatch, rubber composition, and tire |
| CN102816265A (en) * | 2012-07-30 | 2012-12-12 | 华南理工大学 | Hydrometallurgy method for preparing natural rubber/carbon black compound rubber |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018109969A1 (en) * | 2016-12-14 | 2018-06-21 | 東洋ゴム工業株式会社 | Method for producing master batch, method for producing rubber composition, and method for producing tire |
| WO2018123113A1 (en) * | 2016-12-27 | 2018-07-05 | 東洋ゴム工業株式会社 | Masterbatch manufacturing method and tire manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103819760A (en) | 2014-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103819760B (en) | A kind of processing method preparing high-performance carbon black rubber master batch | |
| CN107457933B (en) | A kind of filler/rubber composite material preparation method | |
| EP2497798A1 (en) | Uncured rubber composition, process for producing the same, and pneumatic tire | |
| CN109517195B (en) | Method for preparing carbon black master batch by wet mixing | |
| CN103435820B (en) | Pre-treatment method of asphalt and spherical graphite negative electrode material coated by using asphalt | |
| CN105419009B (en) | A kind of method that semi-open type superheated steam spray drying process prepares high filled composite rubber master batch | |
| CN113896950B (en) | Monoatomic zinc material capable of replacing zinc oxide used in rubber field and preparation method thereof | |
| CN102786726A (en) | High performance XNBR vulcanized rubber containing graphene oxide and its preparation method | |
| CN114292450B (en) | Dry mixing method of tire rubber composition, tread composition and low-rolling-resistance high-performance tire | |
| CN104311906A (en) | Preparation method for white carbon black/NR (natural rubber) master batch for belted layer of tire | |
| CN114591545B (en) | Forming method for preparing graphene masterbatch and long-service-life heavy vehicle road wheel tire through water phase cooperative coagulation process | |
| CN104194248A (en) | Method for in-situ modification of ABS (acrylonitrile-butadiene-styrene) resin by graphene | |
| CN102020794B (en) | Nano calcium carbonate and styrene-butadiene rubber composition and preparation method thereof | |
| CN105600833B (en) | A kind of spherical mesoporous iron oxide and preparation method thereof | |
| CN104072789B (en) | A kind of method that wet method is mixing | |
| CN101885868B (en) | Method for preparing magnetic rubber from recovered rubber powder | |
| CN105218890A (en) | A kind of method preparing carbon black rubber master batch | |
| CN114407266A (en) | Preparation method of carbon black/natural latex composite material | |
| CN104356424A (en) | Preparation method of low-zinc vulcanizing activator | |
| CN108658114A (en) | A kind of preparation method of modified calcium salt | |
| CN104910646A (en) | Preparation method for wet ground heavy calcium carbonate | |
| CN105348997A (en) | Resin powder coating | |
| CN105694210B (en) | A kind of preparation method of plant nanometer fiber reinforcement non-soluble polymer composite material | |
| CN108373557A (en) | A kind of preparation method of high-performance reclaimed rubber | |
| CN102807689B (en) | Liquid-phase dispersion white carbon black latex mixture contained mine tire tread rubber compound and preparation method and application thereof |
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 |