CN1415653A - Method for preparing powdered rubber with carbon black stuffing - Google Patents
Method for preparing powdered rubber with carbon black stuffing Download PDFInfo
- Publication number
- CN1415653A CN1415653A CN 02152077 CN02152077A CN1415653A CN 1415653 A CN1415653 A CN 1415653A CN 02152077 CN02152077 CN 02152077 CN 02152077 A CN02152077 A CN 02152077A CN 1415653 A CN1415653 A CN 1415653A
- Authority
- CN
- China
- Prior art keywords
- carbon black
- latex
- rubber
- filled powder
- preparation
- 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
A carbon black filled powder rubber is prepared from dry rubber, carbon black and its emulsifier, operating oil, anti oxidant, emulsifier, coagulant, and deionized water through proportioning, emulsifying carbon black, heat treating, coagulating and post-treating. Its advantages are high coating effect, high pulverizing rate (99% ore more), and high mechanical performance, flowability and storage stability of product.
Description
Technical field
The present invention relates to the preparation field of powdered rubber (Powdered Rubber), the preparation method of particularly a kind of carbon black filled powder rubber (Carbon black extended powdered rubber).
Background technology
Powdered rubber general reference particle diameter is less than 1.0mm, rubber particle with good fluidity, it is a kind of novel rubber raw materials, be used for substituting traditional niggerhead, adopt Special Equipment with inject, extrude, working method such as mold pressing or adopt existing rubber tooling to be processed into the cross-linked rubber goods with traditional working method, have the energy-and time-economizing, reduce facility investment, reduce production costs, help production process automatization control, improve mixing quality, reduce labor intensity, unusual effect such as non-environmental-pollution.The appearance of powdered rubber has been reformed traditional rubber processing with application, sets up brand-new technological process for rubber industry, can create higher economic benefit and social benefit.
Compare with traditional niggerhead, powdered rubber especially filled powder rubber has plurality of advantages; For example, the glue process of cutting that does not have piece glue with the technological process of powdered rubber processing cross-linked rubber, shorten mixing time and reduced power consumption, filler disperses more even in rubber matrix, when using some difficult mixing rubber such as chloroprene rubber, have the memory of shorter thermal history and heat still less, therefore can relax incipient scorch trend; In addition, the powdered rubber batching directly sends into forcing machine or the cross-linked rubber goods are produced in direct mold pressing, and this technological process can be exempted Banbury mixer and mill operation; Because filler is sneaked in the rubber in advance, so can eliminate flying upward of filler dust, makes surrounding environment more clean.
At present, the method for preparing powdered rubber mainly contains: mechanical crushing method, spray-drying process, cohesion coprecipitation method etc.Preceding two kinds of method equipment complexity, energy consumption is big, production cost height, and cohesion coprecipitation method processing unit is simple relatively, technological process is easy to control, and energy consumption is low, and rubber latex is easy to mix with the powder uniform filling, condenses can obtain filled powder rubber after coprecipitated.
The gordian technique for preparing powdered rubber with the cohesion coprecipitation method is a coating, and the effect of coating is the surface coverage thin film at the powdered rubber particle, thereby rubber particles is isolated, and therefore requires coating that good film-forming properties must be arranged.At first, preparing the used coating of powdered rubber with the cohesion coprecipitation method is inorganic powder such as water glass, silica, white carbon black, carbon black, lime carbonate, talcum powder etc., but isolation effect is undesirable; The coating starch xanthate of the exploitation same period has good coating buffer action owing to can crosslinked action take place to rubber particles, but the meeting in storage process of prepared powdered rubber is mouldy, variable color and aging; Developed water-soluble polymers or poly-dielectric medium coating such as polyvinyl alcohol, polyacrylic acid sodium salt, modified-cellulose etc. afterwards, but this class coating poor water resistance is incompatible with rubber matrix, thus bigger to the performance impact of powdered rubber cross-linked rubber goods; Preparing powdered rubber with macromolecule resin as coating is the new technology that development in recent years is got up, owing to good film-forming properties is arranged on the rubber particles surface and certain consistency is arranged with rubber matrix by molecular designing synthetic macromolecule resin, thereby not only rubber particles is had significant coating isolation effect, and the detrimental effect of product property is greatly reduced.
Carbon black has excellent strengthening action to rubber, is the most important reinforcing filler of rubber.Yet, carbon black has serious black pollution to the production environment and the surrounding environment of rubber mill, with the contactless contaminative of carbon black filled powder rubber of cohesion coprecipitation method preparation, therefore no black dust from flying in accumulating, the course of processing is a kind of environment-friendly rubber raw material.
When preparing carbon black filled powder rubber with macromolecule resin as coating, macromolecule resin and carbon black are isolated the coating of rubber particles synergy, so products therefrom has good flowability.But macromolecule resin has cohesive action to carbon black particle, make the part carbon black particle form particle diameter bigger be difficult to the dispersive granule, on the other hand, macromolecule resin is non-rubber material after all, the effect of the two decreases mechanical properties of vulcanizate.
Summary of the invention
The objective of the invention is to overcome have now utilizes macromolecule resin to prepare the deficiency of carbon black filled powder rubber technology as coating, a kind of powdered rubber that is suitable for preparing the carbon black filled type of four glue kinds is provided, comprises the method for powder natural rubber, powder styrene butadiene rubber, Powdered acrylonitrile-butadiene rubber, powdered polychloroprene rubber.
Purpose of the present invention is achieved through the following technical solutions: the preparation method of this carbon black filled powder rubber comprises the steps:
(1) gets the raw materials ready
Measure contained dried glue by latex: carbon black: carbon black emulsifying agent: process oil: anti-aging agent: fatty acid alkali metal salt emulsifying agent: flocculation agent: the weight ratio of deionized water is 100: 10～100: 0.5～6.0: 0～70: 0.5～3.0: 1.0～6.0: 2.0～5.0: 300～2000 proportion ingredient;
(2) sooty emulsification
The water and the carbon black emulsifying agent that add metering in the tempering tank that agitator is housed after stirring, add the carbon black of metering in stirring, continued to mix 5～30 minutes, obtain the carbon black emulsion;
(3) thermal treatment of latex
The deionized water that in latex, adds metering, the solid content of regulating latex is 5～25%, in stirring, above-mentioned carbon black emulsion is joined in the latex, heating in water bath system to 60 after mixing～95 ℃, the concentration that adds metering is 5% the fatty acid alkali metal salt emulsifying agent and the hot water suspension of anti-aging agent, if contain process oil in the prescription, adds the process oil of metering in stirring, continue to stir 10～30 minutes, constitute the powdered system;
(4) agglomeration process
Under high-speed stirring, add the flocculation agent aqueous solution of metering in the powdered system after the thermal treatment of above-mentioned process, the cohesion of system generation powdery is coprecipitated, keeps 70～90 ℃ of system temperatures, and slaking is discharge after 10～30 minutes;
(5) aftertreatment of condensation product
Condensation product is entered in industrial centrifugal machine or other dewatering units, wash with water, dewater three to four times, last centrifuge dehydration to material water ratio is 30～50%, and in the vibratory screening apparatus of the pulverizer of being with rake teeth, sieve, the wet particle product of gained is dried to moisture content below 1% with 60～130 ℃ in drying plant such as ebullated bed, pneumatic dryer, obtain the carbon black filled powder rubber that particle diameter is 0.2～1.0mm.
Described latex is natural rubber (NR) latex, styrene-butadiene rubber(SBR) (SBR) latex, paracril (NBR) latex and chloroprene rubber (CR) latex.
Described carbon black is the carbon black with reinforcement; As superelevation abrasion resistant carbon black (SAF), high wear-resistant carbon black (HAF), semi-reinforcing hydrocarbon black (SRF), extrude carbon black (FEF), intermediate super abrasion furnace black (ISAF) etc. soon.
Described process oil is rubber industry process oil commonly used or extending oil, as machine oil, Viscotrol C, aromatic hydrocarbon oil, third fractional oil, high sulfone wet goods.
Described carbon black emulsifying agent is nonionic surface active agent or aniorfic surfactant, as dodecyl Soxylat A 25-7, octadecyl Soxylat A 25-7, octyl phenyl Soxylat A 25-7, nonyl phenyl Soxylat A 25-7, polysorbas20, polysorbate60, tween 80, polyvinyl alcohol, peregal " O ", lauric acid sodium sulfate, sodium oleyl sulfate, ammonium laurate, potassium laurate etc.; What wherein effect was best is to adopt nonionic surface active agent.
Described fatty acid alkali metal salt emulsifying agent is for being dissolved in synthetic fatty acid potassium, the sodium fat synthesis of hot water below 90 ℃, as: potassium stearate, sodium stearate, potassium oleate, sodium oleate etc., mentioned emulsifier can 60～90 ℃ down with flocculation agent in calcium, magnesium, aluminum ion generate water-fast divalent metal salt on the spot, the latter plays the coating buffer action to rubber particles.
The latex solid content of the powdered system in the thermal treatment of described step (three) latex is 7～15%.
Described anti-aging agent is the general anti-aging agent of rubber, as antioxidant 4010, antioxidant 4010NA, antioxidant 264, and anti-aging agent 2264 etc.
Described flocculation agent is the mixture of aluminum chloride, aluminum nitrate, Tai-Ace S 150, calcium chloride, nitrocalcite, magnesium chloride, magnesium nitrate or above-mentioned substance and hydrochloric acid, sulfuric acid, acetate or above-mentioned substance.
The optimum drying temperature range of wet particle product is 70～120 ℃ in the aftertreatment of described step (five) condensation product.
Action principle of the present invention is: this preparation method uses the carbon black emulsifying agent to be mainly nonionic surface active agent, used coating is mainly fatty acid alkali metal salt, compare with anion surfactant, a little less than the surface adsorption effect of nonionic surface active agent to carbon black particle, used water is washed away it from powdered rubber; Carbon black has buffer action preferably to the powdered rubber particle, in the powdered system, add the small amounts of water soluble fatty acid alkali metal salt, then with the cohesion of water-soluble divalent metal salt, fatty acid alkali metal salt generate immediately insoluble divalent metal salt be covered in rubber with the surface of the macroscopic particle of carbon black formation with its isolation; Carbon black filled powder rubber particle through washing is substantially free of tensio-active agent, the content of lipid acid divalent metal salt also seldom, therefore utilize the carbon black filled powder rubber of this method preparation very pure, thereby the physical and mechanical properties that has guaranteed its cross-linked rubber is not damaged by impurity.
The present invention compared with prior art has following outstanding advantage:
1) adopt of the present inventionly when generating lipid acid divalent metal salt coating technology on the spot and preparing carbon black filled powder rubber, the coating add-on is less, and covered effect is good, and the powdered process stabilizing is reliable, easy;
2) adopt pulverizing technology of the present invention, the powder formation rate of carbon black filled powder rubber reaches more than 99%;
3) adopt the size distribution of the prepared carbon black filled powder rubber of the present invention to control, can prepare the carbon black filled powder rubber of multiple size distribution by customer requirements by regulating coherence condition;
4) adopt the prepared contactless contaminative of carbon black filled powder rubber of the present invention, good fluidity, stable storing.
5) adopt the physical and mechanical properties of the prepared carbon black filled powder rubber of the present invention good, process easyly, no carbon powder dust flies upward in the mixing process, and production environment more cleans.
Embodiment
Below by embodiment the present invention is done further concrete description, but embodiments of the present invention are not limited thereto.
Embodiment
(1) gets the raw materials ready
Get the raw materials ready by the proportioning in the table 1.
The reagent dosage of table 1 embodiment and processing condition
Annotate: the carbon black that NO.7 and NO.8 adopted be semi-reinforcing furnace black (SRF, N880)
(2) sooty emulsification
Press prescription listed in the table 1, in 100 liters of steel basins, add 50 kg water and emulsifier op-10, middling speed stirs, after treating that OP-10 all dissolves, in stirring, add carbon black, after treating that carbon black and emulsifier solution form homogeneous latex emulsion, continue to stir 10～30 minutes, make the fully emulsified carbon black emulsion that obtains of carbon black.
(3) thermal treatment of latex
Press prescription listed in the table 1, in 200 liters of steel basins, add the latex that contains 20 kilograms in dried glue, it is 20% that the adding deionized water is diluted to drc with it, in stirring, add above-mentioned carbon black emulsion, chuck is heated to 70～90 ℃, the concentration that adds metering in the stirring is 5% the fatty acid alkali metal salt and the suspension of anti-aging agent, continues to stir 10～30 minutes, constitutes the powdered system.
(4) agglomeration process
Press prescription listed in the table 1, the concentration that adds metering in above-mentioned powdered system is 10% calcium chloride water, simultaneously vigorous stirring (600～1000rpm), treat that emulsion all is condensed into particle after, reduce stirring velocity to middle stirring at low speed (300～500rpm); Slaking is discharge after 10～30 minutes, and keeping system temperature in this process is 70～90 ℃.
(5) aftertreatment of condensation product
Condensation product is entered in the industrial centrifugal machine, with tap water washing, dehydration three to four times, last centrifuge dehydration to material water ratio is 30～50%, and in band rake teeth vibratory screening apparatus, sieve, the wet particle product of gained is dried to moisture content below 1% under 70～120 ℃, obtain the carbon black filled powder rubber of suitable particle diameter, its size distribution is as shown in table 2, and physical and mechanical properties is as shown in table 3; By table 2 as seen, can prepare the powdered rubber that particle diameter meets industrial requirements by the present invention, by table 3 as seen, the physical and mechanical properties of above-mentioned powdered rubber is good.
The size distribution of table 2 carbon black filled powder rubber
Sequence number NO.1 NO.2 NO.3 NO.4 NO.5 NO.6 NO.7 NO.8 rubber kind NR NR SBR SBR NBR NBR CR CR≤0.45mm, (%) 26.2 46.3 99.2 95.9 66.7 53.6 65.2 55.1≤0.9mm, (%) 99.6 100 99.7 99.5 100 100 100 100＞0.9mm, (%) 0.4 0.0 0.3 0.5 0000
The physical and mechanical properties of table 3 carbon black filled powder rubber
Sequence number NO.1 NO.2 NO.3 NO.4 NO.5 NO.6 NO.7 NO.8 rubber kind NR NR SBR SBR NBR NBR CR CR vulkameter t
10, min
4.0 10.2 10.4 6.0 6.5 8.5 9.0 4.1 (150 ℃) vulkameter t
90, min
20.2 23.2 23.6 17.0 17.5 25.2 25.6 20.1 (150 ℃) tensile strength, MPa 25.6 23.2 24.1 20.6 28.5 26.0 15.8 15.3 tensile yield, % 640 580 540 490 410 350 480 460100% stress at definite elongations
3.3 3.8 2.8 3.5 3.6 6.4 3.1 3.5MPa300% stress at definite elongations,
11.3 12.3 11.1 13.2 16.1 21.9 11.5 12.0MPa hardness (Shao A), spend 63 71 67 74 72.8 75.0 59 62 setafter breaks, % 28.0 30.0 16.0 25.0 12.0 16.0 16.0 20.0 tear strengths, N/m 91.4 87.8 40.9 43.2 40.0 36.0 46.3 47.6 annotates:
1. the sulfurizing formula of carbon black filled type powder natural rubber: rubber (not containing carbon black) 100, carbon black
(HAF, N330) variable, zinc oxide 5, stearic acid 2, sulphur 2.25, accelerator NS
0.7。
2. the sulfurizing formula of carbon black filled type powder styrene butadiene rubber: rubber (not containing carbon black) 100, carbon black
(HAF, N330) variable, zinc oxide 3, stearic acid 1, sulphur 1.75, accelerator NS
1.0。
3. the sulfurizing formula of carbon black filled type Powdered acrylonitrile-butadiene rubber: rubber (not containing carbon black) 100, carbon black
(HAF, N330) variable, zinc oxide 4, stearic acid 1.5, sulphur 1.75, promotor
DM1.5, promotor T.T0.2.
4. the sulfurizing formula of carbon black filled type powdered polychloroprene rubber: rubber (not containing carbon black) 100, carbon black
(SAF, N880) variable, zinc oxide 5, magnesium oxide 4, stearic acid 0.5.
Claims (10)
1, a kind of preparation method of carbon black filled powder rubber is characterized in that comprising the steps:
(1) gets the raw materials ready
Measure contained dried glue by latex: carbon black: carbon black emulsifying agent: process oil: anti-aging agent: fatty acid alkali metal salt emulsifying agent: flocculation agent: the weight ratio of deionized water is 100: 10～100: 0.5～6.0: 0～70: 0.5～3.0: 1.0～6.0: 2.0～5.0: 300～2000 proportion ingredient;
(2) sooty emulsification
The water and the carbon black emulsifying agent that add metering in the tempering tank that agitator is housed after stirring, add the carbon black of metering in stirring, continued to mix 5～30 minutes, obtain the carbon black emulsion;
(3) thermal treatment of latex
The deionized water that in latex, adds metering, the solid content of regulating latex is 5～25%, in stirring, above-mentioned carbon black emulsion is joined in the latex, heating in water bath system to 60 after mixing～95 ℃, the concentration that adds metering is 5% the fatty acid alkali metal salt emulsifying agent and the hot water suspension of anti-aging agent, if contain process oil in the prescription, adds the process oil of metering in stirring, continue to stir 10～30 minutes, constitute the powdered system;
(4) agglomeration process
Under high-speed stirring, add the flocculation agent aqueous solution of metering in the powdered system after the thermal treatment of above-mentioned process, the cohesion of system generation powdery is coprecipitated, keeps 70～90 ℃ of system temperatures, and slaking is discharge after 10～30 minutes;
(5) aftertreatment of condensation product
Condensation product is entered in industrial centrifugal machine or other dewatering units, wash with water, dewater three to four times, last centrifuge dehydration to material water ratio is 30～50%, and in the vibratory screening apparatus of the pulverizer of being with rake teeth, sieve, the wet particle product of gained is dried to moisture content below 1% with 60～130 ℃ in drying plant such as ebullated bed, pneumatic dryer, obtain the carbon black filled powder rubber that particle diameter is 0.2～1.0mm.
2, the preparation method of carbon black filled powder rubber according to claim 1 is characterized in that: described latex is natural rubber latex, styrene butadiene rubber latex, paracril latex and chloroprene rubber latex.
3, the preparation method of carbon black filled powder rubber according to claim 1 is characterized in that: described carbon black is superelevation abrasion resistant carbon black, high wear-resistant carbon black, semi-reinforcing hydrocarbon black, extrudes carbon black, intermediate super abrasion furnace black soon.
4, the preparation method of carbon black filled powder rubber according to claim 1 is characterized in that: described process oil is machine oil, Viscotrol C, aromatic hydrocarbon oil, third fractional oil, high sulfone oil.
5, the preparation method of carbon black filled powder rubber according to claim 1 is characterized in that: described carbon black emulsifying agent is nonionic surface active agent or aniorfic surfactant.
6, the preparation method of carbon black filled powder rubber according to claim 1 is characterized in that: described fatty acid alkali metal salt emulsifying agent is for being dissolved in synthetic fatty acid potassium, the sodium fat synthesis of hot water below 90 ℃.
7, the preparation method of carbon black filled powder rubber according to claim 1 is characterized in that: the latex solid content of the powdered system in the thermal treatment of described step (three) latex is 7～15%.
8, the preparation method of carbon black filled powder rubber according to claim 1 is characterized in that: described anti-aging agent is the general anti-aging agent of rubber.
9, the preparation method of carbon black filled powder rubber according to claim 1 is characterized in that: described flocculation agent is the mixture of aluminum chloride, aluminum nitrate, Tai-Ace S 150, calcium chloride, nitrocalcite, magnesium chloride, magnesium nitrate or above-mentioned substance and hydrochloric acid, sulfuric acid, acetate or above-mentioned substance.
10, the preparation method of carbon black filled powder rubber according to claim 1 is characterized in that: the optimum drying temperature range of wet particle product is 70～120 ℃ in the aftertreatment of described step (five) condensation product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021520771A CN1168770C (en) | 2002-11-29 | 2002-11-29 | Method for preparing powdered rubber with carbon black stuffing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021520771A CN1168770C (en) | 2002-11-29 | 2002-11-29 | Method for preparing powdered rubber with carbon black stuffing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1415653A true CN1415653A (en) | 2003-05-07 |
| CN1168770C CN1168770C (en) | 2004-09-29 |
Family
ID=4752101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021520771A Expired - Lifetime CN1168770C (en) | 2002-11-29 | 2002-11-29 | Method for preparing powdered rubber with carbon black stuffing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1168770C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300223C (en) * | 2004-06-02 | 2007-02-14 | 中国石油天然气股份有限公司 | Method for making powdered rubber |
| CN101268137B (en) * | 2005-09-21 | 2011-07-13 | 出光兴产株式会社 | Process oil and rubber composition |
| CN102816265A (en) * | 2012-07-30 | 2012-12-12 | 华南理工大学 | Hydrometallurgy method for preparing natural rubber/carbon black compound rubber |
| CN102884111A (en) * | 2009-12-03 | 2013-01-16 | 米其林集团总公司 | Filler blending for rubber formulations |
| CN104211837A (en) * | 2014-07-15 | 2014-12-17 | 华南理工大学 | Preparation method of carbon-black-containing butadiene styrene rubber master batch |
| CN106065152A (en) * | 2016-08-23 | 2016-11-02 | 汪静 | Hot high pressure elasto-plasticity insulating materials and preparation method thereof |
| CN106397994A (en) * | 2016-08-23 | 2017-02-15 | 中广核三角洲（苏州）新材料研发有限公司 | Process for preparing pressure resistant radiation resistant elastomer material |
| CN106432922A (en) * | 2016-08-23 | 2017-02-22 | 中广核三角洲（苏州）新材料研发有限公司 | Thermoplastic high-voltage-withstanding cable material |
| CN106589755A (en) * | 2016-08-23 | 2017-04-26 | 中广核三角洲（苏州）新材料研发有限公司 | High voltage resistant thermoplastic elastomer material and preparation method thereof |
-
2002
- 2002-11-29 CN CNB021520771A patent/CN1168770C/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300223C (en) * | 2004-06-02 | 2007-02-14 | 中国石油天然气股份有限公司 | Method for making powdered rubber |
| CN101268137B (en) * | 2005-09-21 | 2011-07-13 | 出光兴产株式会社 | Process oil and rubber composition |
| CN102884111A (en) * | 2009-12-03 | 2013-01-16 | 米其林集团总公司 | Filler blending for rubber formulations |
| CN102884111B (en) * | 2009-12-03 | 2014-09-24 | 米其林集团总公司 | Filler blending for rubber formulations |
| CN102816265A (en) * | 2012-07-30 | 2012-12-12 | 华南理工大学 | Hydrometallurgy method for preparing natural rubber/carbon black compound rubber |
| CN104211837A (en) * | 2014-07-15 | 2014-12-17 | 华南理工大学 | Preparation method of carbon-black-containing butadiene styrene rubber master batch |
| 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 |
| CN106065152A (en) * | 2016-08-23 | 2016-11-02 | 汪静 | Hot high pressure elasto-plasticity insulating materials and preparation method thereof |
| CN106397994A (en) * | 2016-08-23 | 2017-02-15 | 中广核三角洲（苏州）新材料研发有限公司 | Process for preparing pressure resistant radiation resistant elastomer material |
| CN106432922A (en) * | 2016-08-23 | 2017-02-22 | 中广核三角洲（苏州）新材料研发有限公司 | Thermoplastic high-voltage-withstanding cable material |
| CN106589755A (en) * | 2016-08-23 | 2017-04-26 | 中广核三角洲（苏州）新材料研发有限公司 | High voltage resistant thermoplastic elastomer material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1168770C (en) | 2004-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102718995B (en) | Industrial lignin reinforcing rubber and preparation method thereof | |
| CN100513430C (en) | Preparation method of core-shell type emulsion particle emulsion for enhancing rubber | |
| CN101314675B (en) | Industry xylogen reinforced and filled coblended elastomer material, and preparation method thereof | |
| CN101456961B (en) | Method for preparing reactive nano calcium carbonate-native rubber composite material | |
| CN1865306A (en) | Low content nitrile cross-linked powdery acrylonitrile butadiene preparation method | |
| CN102775654A (en) | Preparation method for liquid phase stirring and mixing of white carbon black and natural rubber | |
| JPS5850257B2 (en) | Method for producing non-viscous flowable powdery com-base compound containing filler | |
| CN1168770C (en) | Method for preparing powdered rubber with carbon black stuffing | |
| CN101735466A (en) | Method for preparing rubber composite by high-pressure mixing equipment and application thereof | |
| CN1206268C (en) | Method for preparing powdered rubber in stuffing type with extra fine calcium carbonate | |
| Huabcharoen et al. | Purification and characterization of silica from sugarcane bagasse ash as a reinforcing filler in natural rubber composites | |
| CN106752102A (en) | A kind of preparation method of the high-dispersion nano calcium carbonate for being applied to nylon engineering plastic | |
| CN105566692B (en) | A kind of native rubber composite material and preparation method thereof | |
| JP2004536956A (en) | Method for recycling scrap-derived rubber | |
| US20170121511A1 (en) | A process to prepare high-quality natural rubber silica masterbatch by liquid phase mixing | |
| CN102020794B (en) | Nano calcium carbonate and styrene-butadiene rubber composition and preparation method thereof | |
| CN108299657B (en) | Preparation method and application of high-dispersion modified lignin | |
| WO2016014037A1 (en) | A process to prepare high-quality natural rubber-silica masterbatch by liquid phase mixing | |
| WO2011038578A1 (en) | Preparation method of complex composition for rubber products and product obtained therefrom | |
| CN106317456B (en) | A method of rubber master batches are prepared using the calcium sulfate of lignin dispersion | |
| CN102775650A (en) | Tread rubber sizing material containing liquid phase dispersion white carbon black latex mixture and preparation method and application thereof | |
| CN104211837A (en) | Preparation method of carbon-black-containing butadiene styrene rubber master batch | |
| CN1268694C (en) | Environmental protection type carbon black and its preparing method | |
| CN109749168A (en) | A kind of nano zine oxide/rubber composite material and preparation method | |
| CN113861526A (en) | High-wear-resistance low-heat-generation carbon black master batch and preparation method 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 | ||
| ASS | Succession or assignment of patent right |
Owner name: SHUANGQIAN GROUP CO., LTD. Free format text: FORMER OWNER: SOUTH CHINA UNIVERSITY OF TECHNOLOGY Effective date: 20080822 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20080822 Address after: Study on Shanghai Minhang District city Double Coin Holding Ltd tire Jianchuan Road No. 2613 Patentee after: DOUBLE COIN HOLDINGS Ltd. Address before: Guangdong city of Guangzhou province Tianhe District Wushan Patentee before: South China University of Technology |
|
| CX01 | Expiry of patent term |
Granted publication date: 20040929 |
|
| CX01 | Expiry of patent term |