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
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- 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
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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.
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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 |
| CN103159963B (en) * | 2011-12-15 | 2015-05-20 | 中国石油天然气股份有限公司 | Preparation method of powdered acrylonitrile-butadiene rubber with high performance |
| CN103160056B (en) * | 2011-12-15 | 2015-12-02 | 中国石油天然气股份有限公司 | A kind of preparation method of high performance butadiene-styrene-ispowder powder polymer |
| EA201590308A1 (en) | 2012-08-02 | 2015-05-29 | Амрил Аг | NATURAL RUBBER CONTAINING NANOCARBON |
| JP2016536415A (en) * | 2013-08-30 | 2016-11-24 | アムリル・アクチェンゲゼルシャフトＡｍｒｉｌ Ａｇ | Improved natural rubber composition |
| 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 |
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| 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 |
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| 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)
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| 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 * |
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