CN1312206C - Carbon nanotube modified powder natural rubber and method for preparing same - Google Patents
Carbon nanotube modified powder natural rubber and method for preparing same Download PDFInfo
- Publication number
- CN1312206C CN1312206C CNB2005100589996A CN200510058999A CN1312206C CN 1312206 C CN1312206 C CN 1312206C CN B2005100589996 A CNB2005100589996 A CN B2005100589996A CN 200510058999 A CN200510058999 A CN 200510058999A CN 1312206 C CN1312206 C CN 1312206C
- Authority
- CN
- China
- Prior art keywords
- cnts
- natural rubber
- carbon nanotube
- modified powder
- powder natural
- 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.)
- Expired - Fee Related
Links
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 33
- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 31
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 31
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 31
- 239000000843 powder Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001694 spray drying Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229920006173 natural rubber latex Polymers 0.000 claims description 10
- 239000013055 pulp slurry Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 31
- 238000012986 modification Methods 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 7
- 239000002002 slurry Substances 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 abstract 2
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000000806 elastomer Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 150000004965 peroxy acids Chemical class 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses carbon nanotube modified powder natural rubber and a preparing method thereof, which relates to the technical field that carbon nanotubes (CNTs) are used for the modification of high molecular material. The carbon nanotube modified powder natural rubber is characterized in that the carbon nanotube modified powder natural rubber contains the CNTs, and the quality percentage of the CNTs and the rubber gum elastomer of natural latex is 1% to 50%. In the preparing method, firstly, the surfaces of the CNTs are treated, which enables the CNTs to have hydrophilicity; then, the CNTs, a dispersing agent and deionized water are mixed to obtain CNT-water slurry; the pH value of the CNT-water slurry is regulated to 9 to 12; finally, the CNT-water slurry and the natural latex are evenly mixed to obtain natural rubber liquid pulp with the CNTs. Then, modified powder natural rubber containing the CNTs is prepared by a spray drying process. The feeding quality of the modified powder natural rubber containing the CNTs is 5% to 30%, and the inlet temperature is 100 DEG C to 180 DEG C. The CNTs are evenly dispersed in the carbon nanotube modified powder natural rubber prepared by the present invention; a grain diameter of the carbon nanotube modified powder natural rubber is small; compared with traditional powdered rubber, the mechanical properties of the carbon nanotube modified powder natural rubber is remarkably enhanced.
Description
Technical field:
A kind of carbon nanotube (CNTs) modified powder natural rubber relates to CNTs is used for the polymer modification technical field.
Background technology:
CNTs is since 1991 are at first found by Japanese scholar Iijima, and because of its particular structure and excellent performance become the research focus of material science rapidly, wherein, in field of compound material, CNTs is widely used in composite modification.Yet, to compare with a large amount of research work of CNTs modified composite material, the applied research report of CNTs aspect modified rubber is seldom.People such as the surplus grain husk of Central China Normal University, Jia Zhijie have reported the research work for preparing CNTs modified EPT rubber (EPDM) with the mechanically milling method, the gained result shows that adding CNTs can improve the tensile strength of EPDM, but elongation at break then descends to some extent, simultaneously, the EPDM conductivity after the modification improves.People such as the Qiao Jin of Beijing Chemical Institute of China Petrochemical Corporation beam have invented a kind of fully vulcanized powder rubber and preparation method thereof, and utilizing particle diameter is that the rubber latex of 20~2000nm is realized through energetic ray source irradiation.
The inventor once utilized the mechanically milling method to prepare CNTs modified rubber matrix material, Performance Detection shows that CNTs shows the reinforcement effect to rubber matrix, rubber composite rebound resilience, compression fatigue and ageing-resistant performance after the modification all are better than the black-reinforced sample, but stretching and tear resistance are lower.Discover, CNTs is the agglomeration ubiquity in rubber matrix, from matrix material enhanced principle, the weighting material that requirement is used for reinforcement should fully disperse at matrix, and the high viscosity of elastic polymer matrix has improved weighting material dispersive difficulty therein greatly, and this may be to influence the major cause that CNTs modified rubber composite property improves.
Do not find as yet that so far other is about the relevant report with CNTs modified natural rubber and CNTs modified powder rubber and vulcanized rubber preparation.
Summary of the invention
The objective of the invention is to propose the modified powder natural rubber of a kind of CNTs of containing.
Powdered rubber proposed by the invention is characterised in that, contains mass percent with the dried glue of natural rubber latex and be 20%~50% carbon nanotube.
The preparation method of carbon nanotube modified powder natural rubber is characterized in that, contains following steps successively:
1) preparation contains the natural rubber pulp slurry material of carbon nanotube (CNTs).
1.1) CNTs made the surface treatment of its possess hydrophilic property and the relevant functional group of load;
1.2) preparation of carbon nano-tube suspension liquid:
Above-mentioned surface treated CNTs is mixed with dispersion agent, deionized water, obtain the CNTs-aqeous suspension, wherein the mass ratio of dispersion agent and described CNTs is 5%~20%;
1.3) regulate pH value to 9~12 of above-mentioned CNTs-aqeous suspension;
1.4) with CNTs-aqeous suspension and natural rubber latex uniform mixing after the above-mentioned adjusting pH value, obtain adding the natural rubber pulp slurry material of CNTs;
2) the natural rubber pulp slurry material with the above-mentioned CNTs of containing is a raw material, contains the modified powder natural rubber of CNTs with spray drying method for preparation, and wherein the amount of feed is 5%~30%, and inlet temperature is 100 ℃~180 ℃.
The described the 1st) step is carried out surface treatment to CNTs, is CNTs to be carried out acid boil.Described dispersion agent is Sodium dodecylbenzene sulfonate or sodium laurylsulfonate.The described the 3rd) the pH value of step joint CNTs-aqeous suspension is regulated by adding KOH or ammoniacal liquor.
Experimental results show that: the modified powder natural rubber that contains CNTs of the present invention's preparation, CNTs is homodisperse therein, the mechanical property of this powdered rubber is significantly increased.
Description of drawings
Fig. 1 is the carbon nanotube pattern (TEM) under the different states, and Fig. 1 (a) boils carbon nanotube pattern under the state, the carbon nanotube pattern that Fig. 1 (b) boils through peracid without peracid;
Fig. 2 is that adding CNTs and the powdered rubber pattern that does not add the CNTs preparation compare (SEM), and Fig. 2 (a) is the powdered rubber that does not add CNTs, and Fig. 2 (b) is the powdered rubber that adds CNTs.
Embodiment
The present invention proposes to adopt spray drying method for preparation CNTs modified powder rubber by preparation CNTs natural rubber latex suspension, in the hope of improving the dispersion of CNTs in rubber matrix, thereby opens up new approach for improving CNTs modified rubber performance of composites.Because slurry solvent flash evapn in spray-drying process makes that the good distribution state of CNTs in natural rubber latex kept, the performance of powdered rubber is improved.Prepared CNTs modified powder rubber not only can be directly used in the processing rubber goods after adding vulcanizing agent, and can be widely used in fields such as tackiness agent and composite modification.
Embodiment 1
1, at first prepare the natural rubber pulp slurry material that contains CNTs:
It is V that CNTs is placed volume ratio
Sulfuric acid: V
Nitric acidIn=3: 1 the mix acid liquor, the corresponding 10ml acid solution of 1gCNTs is boiled 30min, and washing obtains acid and boils CNTs after the oven dry.The CNTs that boils processing through peracid observes down at transmission electron microscope (TEM), compares with the CNTs that boils processing without peracid, as shown in Figure 1, as seen boils the dispersion state that processing can effectively improve CNTs through peracid.The peracid of learning from else's experience boils the CNTs30g of processing, (adding of CB is for composite reinforcing and improves isolation effect carbon black CB30g, it adds the adding that does not influence CNTs, can not influence the improved action of CNTs to the powdered rubber performance yet, also can not add CB in actual applications), Sodium dodecylbenzene sulfonate (SDAS) 3g, join with the CNTs mass ratio be in 10: 1 the deionized water, through ultra-sonic dispersion, obtain the CNTs-aqeous suspension.Adding KOH in suspension makes the suspension pH value reach 10.Get solid content and be 60% natural rubber latex 100g, this suspension is joined in the natural rubber latex, it is 10% that the adding appropriate amount of deionized water makes its total solid content, and adopt magnetic stirring apparatus through the abundant stirring more than 2 hours, it is mixed, and making CNTs content is the natural rubber pulp slurry material of 50phr (being that CNTs is 50% with natural rubber latex dry glue quality ratio).
2, spray drying method for preparation powdered rubber
The spraying drying instrument parameter is: the amount of feed 5%, 100 ℃ of inlet temperatures
Adopt 290 type spraying drying instrument of Switzerland B ü chi company to experimentize, temperature out is 80 ℃~90 ℃.Observe embodiment 1 resulting CNTs modified powder rubber pattern (Fig. 3 b) with scanning electron microscope (SEM), with the starting powder rubber that does not add CNTs (Fig. 2 a) compares, the powdered rubber good dispersion of visible CNTs modification, granularity rounding, particle diameter only are about 5 μ m.
Embodiment 2, and is identical with other condition of embodiment 1, and difference is that dispersion agent is a sodium laurylsulfonate, and the pH value is regulated and adopted ammoniacal liquor, and parameter shown in the table one.
Embodiment 3,4, and except that parameter shown in the table one, all the other conditions are identical with embodiment 1.
The different parameters contrast of embodiment 1~4 sees Table one:
Table one
Embodiment | CNTs (g) | Dispersion agent (g) | pH | The dried glue of natural rubber latex (g) | Inlet temperature ℃ | The amount of feed |
1 | 30 | 3 | 9 | 60 | 100 | 5% |
2 | 3 | 0.3 | 10.5 | 15 | 160 | 10% |
3 | 15 | 0.75 | 12 | 60 | 120 | 15% |
4 | 0.6 | 0.12 | 10 | 60 | 180 | 30% |
The powdered rubber that embodiment 2~4 prepares observation under scanning electron microscope (SEM) all has good dispersion effect, and granularity rounding, particle diameter only are about 5 μ m.
We adopt the particular manufacturing craft compacting and the sulfuration that heats up to make the vulcanized rubber that contains CNTs, and with traditional powdered rubber comparison that only contains CB, the mechanical property detected result is shown in table two respectively.
Table two
Sample | 50phr CB | 5phr CNTs | 10phr CNTs | 20phr CNTs | 25phr CNTs | 30phr CNTs | 50phr CNTs |
Tensile strength, MPa | 15.42 | 13 | 20.8 | 17.4 | 17.75 | 12.38 | 16.18 |
Elongation at break, % | 576 | 437 | 650 | 1210 | 594 | 587 | 640 |
Tear strength, KN/m | 53.9 | 63.04 | 60.9 | 57.3 | 86.5 | 67.5 | 50 |
As shown in Table 2, the prepared native rubber composite material mechanical property of the present invention is significantly increased.
Claims (4)
1, a kind of carbon nanotube modified powder natural rubber is characterized in that, contains mass percent with the dried glue of natural rubber latex and be 20%~50% carbon nanotube;
The preparation method of described carbon nanotube modified powder natural rubber, contain following steps successively:
1) preparation contains the natural rubber pulp slurry material of carbon nanotube;
1.1) CNTs is carried out surface treatment, make its possess hydrophilic property;
1.2) preparation of carbon nano-tube suspension liquid:
Above-mentioned surface treated CNTs is mixed with dispersion agent, deionized water, obtain the CNTs-aqeous suspension, wherein the mass ratio of dispersion agent and described CNTs is 5%~20%;
1.3) regulate pH value to 9~12 of above-mentioned CNTs-aqeous suspension;
1.4) with CNTs-aqeous suspension and natural rubber latex uniform mixing after the above-mentioned adjusting pH value, obtain adding the natural rubber pulp slurry material of CNTs;
2) the natural rubber pulp slurry material with the above-mentioned CNTs of containing is a raw material, contains the modified powder natural rubber of CNTs with spray drying method for preparation, and wherein the amount of feed is 5%~30%, and inlet temperature is 100 ℃~180 ℃.
2, carbon nanotube modified powder natural rubber as claimed in claim 1 is characterized in that, the described the 1st) and the step is carried out surface treatment to CNTs, is CNTs to be carried out acid boil.
3, carbon nanotube modified powder natural rubber as claimed in claim 1 is characterized in that, described dispersion agent is Sodium dodecylbenzene sulfonate or sodium laurylsulfonate.
4, carbon nanotube modified powder natural rubber as claimed in claim 1 is characterized in that, the described the 3rd) the pH value of step joint CNTs-aqeous suspension is by adding the adjusting of KOH or ammoniacal liquor.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2005100589996A CN1312206C (en) | 2005-03-29 | 2005-03-29 | Carbon nanotube modified powder natural rubber and method for preparing same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2005100589996A CN1312206C (en) | 2005-03-29 | 2005-03-29 | Carbon nanotube modified powder natural rubber and method for preparing same |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1663991A CN1663991A (en) | 2005-09-07 |
CN1312206C true CN1312206C (en) | 2007-04-25 |
Family
ID=35035319
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2005100589996A Expired - Fee Related CN1312206C (en) | 2005-03-29 | 2005-03-29 | Carbon nanotube modified powder natural rubber and method for preparing same |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1312206C (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100355826C (en) * | 2005-12-15 | 2007-12-19 | 上海交通大学 | Preparation process for improving bonding capacity of carbon nanotube with rubber molecule |
CN101418089B (en) * | 2008-12-03 | 2011-01-19 | 中国热带农业科学院农产品加工研究所 | Method for preparing natural rubber-carbon nano tube composite material by using static electricity self-assembly |
CN103160056B (en) * | 2011-12-15 | 2015-12-02 | 中国石油天然气股份有限公司 | Preparation method of high-performance butadiene-styrene-isoprene powder polymer |
CN103159963B (en) * | 2011-12-15 | 2015-05-20 | 中国石油天然气股份有限公司 | Preparation method of high-performance powdered nitrile rubber |
CN104619760B (en) | 2012-08-02 | 2016-10-26 | 阿米利尔股份公司 | Natural rubber containing nano-sized carbon |
WO2015028845A1 (en) * | 2013-08-30 | 2015-03-05 | Amril Ag | Improved natural rubber compositions |
CN105330917A (en) * | 2015-11-13 | 2016-02-17 | 吴江市风尚鞋厂 | Insulating and high-temperature-resistant sizing material for rubber shoe sole |
CN106188682B (en) * | 2016-06-20 | 2019-08-23 | 青岛科技大学 | A kind of method that the nanotube dispersion of gas phase dispersion prepares Carbon Nanotubes/natural Rubber Composites |
CN109021329A (en) * | 2018-07-06 | 2018-12-18 | 佛山皖阳生物科技有限公司 | A kind of preparation method of Heveatex composite sponge |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1410475A (en) * | 2002-03-14 | 2003-04-16 | 四川大学 | Polymer/carbon nano pipe composite powder and its solid phase shear break up preparation method |
CN1554693A (en) * | 2003-12-26 | 2004-12-15 | 江汉石油钻头股份有限公司 | Modified hydrogenated nitrile-butadiene rubber and its preparing method |
JP2005046605A (en) * | 2003-07-11 | 2005-02-24 | Mizuno Corp | Shoe |
-
2005
- 2005-03-29 CN CNB2005100589996A patent/CN1312206C/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1410475A (en) * | 2002-03-14 | 2003-04-16 | 四川大学 | Polymer/carbon nano pipe composite powder and its solid phase shear break up preparation method |
JP2005046605A (en) * | 2003-07-11 | 2005-02-24 | Mizuno Corp | Shoe |
CN1554693A (en) * | 2003-12-26 | 2004-12-15 | 江汉石油钻头股份有限公司 | Modified hydrogenated nitrile-butadiene rubber and its preparing method |
Non-Patent Citations (1)
Title |
---|
碳纳米管/天然橡胶复合材料的红外光谱和DSC分析 隋刚,梁吉,朱跃峰,周湘文,高技术通讯 2004 * |
Also Published As
Publication number | Publication date |
---|---|
CN1663991A (en) | 2005-09-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1312206C (en) | Carbon nanotube modified powder natural rubber and method for preparing same | |
CN1304473C (en) | Natural liquid rubber slurry with added carbon nanotube and its prepn process | |
CN107556527B (en) | A kind of composite nano carbon material powder and its manufacturing method | |
US9636649B2 (en) | Dispersions comprising discrete carbon nanotube fibers | |
US9371432B2 (en) | Natural rubber containing nanocarbon | |
CN107108204A (en) | Nanocomposite elastomer | |
JP6984269B2 (en) | Carbon nanotube / carbon black / rubber complex and its manufacturing method | |
CN103739903B (en) | A kind of High-conductivity carbon nanotube/rubber nanocomposite and preparation method thereof | |
CN100457812C (en) | Process for preparing attapulgite and natural rubber nano composite material | |
CN102702591A (en) | Hydrogenated nitrile rubber/carbon nanotube composite material and preparation method thereof | |
CN107955239B (en) | Hydrogenated nitrile rubber nano composite material containing graphene and preparation method thereof | |
CN110467782A (en) | A kind of carbon nanotube Plastic conductive composite material and its wet method preparation process | |
JP2019094452A (en) | High heat conductivity and high mechanical strength composite and manufacturing method therefor | |
CN108424563A (en) | The high-performance rubber composite material and preparation method of nanofiber is drawn containing Kev | |
CN103554563B (en) | Room-temperature sulfurization preparation method for carbon nanotube-filled natural rubber composite material | |
CN111690186A (en) | High-wear-resistance and impact-resistant composite rubber and preparation method thereof | |
TWI753180B (en) | A method for producing composite resin particle, resin molding, and composite resin particle | |
CN110982128B (en) | High-pressure-resistant self-lubricating sealing ring and preparation method thereof | |
EP4306574A1 (en) | Composite powder and method for manufacturing same | |
CN108411395B (en) | Conductive cellulose fiber and preparation method thereof | |
Dechojarassri et al. | Mechanical properties of natural rubber composites filled with starch sludge compared with other waste and commercial fillers | |
CN109337145A (en) | A kind of wear-resistant seal rubber | |
KR102413680B1 (en) | Manufacturing method of non-woven fabrics reinforced epoxy composites coated reduced graphene oxide-carbon nanotube | |
CN113773556A (en) | Double-component composite reinforcing agent for hydrogenated nitrile rubber and preparation method thereof | |
CN109233343A (en) | A kind of preparation method of the additive for modified rubber |
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 | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070425 Termination date: 20110329 |