CN1673261A - Natural liquid rubber slurry with added carbon nanotube and its prepn process - Google Patents
Natural liquid rubber slurry with added carbon nanotube and its prepn process Download PDFInfo
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Abstract
The present invention relates to composite polymer material performance improving technology. The liquid natural rubber slurry contains natural latex and carbon nanotube (CNT) and has total solid content of natural latex and CNT in 5-30 % and weight ratio between CNT and dry natural latex of 1-50 %. The liquid natural rubber slurry is prepared through surface treatment of CNT for hydrophilicity; mixing with dispersant and deionized water to obtain water suspension of CNT; regulating the pH value of the suspension to 9-12; and finally mixing with natural latex to obtain the liquid natural rubber slurry with added CNT. The liquid natural rubber slurry with homogeneously dispersed CNT is used in preparing CNT modified rubber powder and CNT modified sulfurized rubber products with greatly raised mechanical, electrically conducting, heat conducting, antistatic and other performance.
Description
Technical field:
Natural rubber pulp slurry material that adds carbon nanotube and preparation method thereof relates to the improvement in performance of polymer composites such as rubber
Technical field.
Background technology:
CNTs (carbon nanotube) is since 1991 are at first found by Japanese scholar Iijima, because of its particular structure and excellent physicals, make its applied research aspect engineering materials become focus rapidly, wherein, in field of compound material, CNTs is widely used in composite modification, yet the applied research of CNTs aspect powdered rubber prepares after natural rubber modification and modification do not appear in the newspapers as yet.
Natural rubber pulp slurry material is one of important source material for preparing in matrix materials such as powdered rubber, as available spray-drying process natural rubber pulp slurry material is prepared into powdered rubber.Add CNTs toward natural rubber pulp slurry material, can further improve the performance of its final finished product.By retrieval, there is not to find to contain the document of natural rubber pulp slurry material and preparation method thereof the aspect of CNTS in the prior art.
Summary of the invention
The object of the present invention is to provide natural rubber pulp slurry material of a kind of interpolation carbon nanotube (CNTs) and preparation method thereof.
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 is better than conventional carbon black reinforced rubber sample, but stretching and tear resistance are relatively poor.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.Therefore, solve the scattering problem of CNTs in rubber matrix, just become the key of CNTs modified rubber Composite Preparation and performance optimization thereof.
Because natural rubber latex itself, with the mixing process of CNTs in be easy to take place the flocculation phenomenon, this is the difficult point place of the natural rubber pulp slurry material of preparation interpolation CNTs.Therefore, the present invention mainly realizes CNTs homodisperse in natural rubber latex, and solves the flocculation problems that occurs in the blend, to prepare stable CNTs/ natural rubber latex suspension.
The natural rubber pulp slurry material of interpolation carbon nanotube (CNTs) proposed by the invention, it is characterized in that, contain natural rubber latex, also contain CNTs, the total solid content of described CNTs and the dried glue of natural rubber latex is 5%～30%, and the CNTs quality is an arbitrary proportion with the ratio of natural rubber latex dry glue quality.
Prepare the method for the natural rubber pulp slurry material of above-mentioned interpolation CNTs, it is characterized in that, contain following steps successively:
1) CNTs is carried out surface treatment, makes its possess hydrophilic property:
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%;
3) pH value to 9～12 of the above-mentioned CNTs-aqeous suspension of adjusting;
4), obtain adding the natural rubber pulp slurry material of CNTs with the CNTs-aqeous suspension behind the above-mentioned adjusting pH value and many arbitrarily natural rubber latex uniform mixing.
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) pH value of step joint CNTs-aqeous suspension is regulated by adding KOH or ammoniacal liquor.
The another kind of natural rubber pulp slurry material that adds CNTs contains natural rubber latex, it is characterized in that also contain CNTs, the total solid content of described CNTs and the dried glue of natural rubber latex is 5%～30%, and the CNTs quality is 1%～50% with the ratio of natural rubber latex dry glue quality.
Prepare the method for the natural rubber pulp slurry material of above-mentioned interpolation CNTs, it is characterized in that, contain following steps successively:
1) CNTs is carried out surface treatment, makes its possess hydrophilic property:
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%;
3) pH value to 9～12 of the above-mentioned CNTs-aqeous suspension of adjusting;
4), obtain adding the natural rubber pulp slurry material of CNTs with CNTs-aqeous suspension behind the above-mentioned adjusting pH value and natural rubber latex uniform mixing.
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) pH value of step joint CNTs-aqeous suspension is regulated by adding KOH or ammoniacal liquor.
Experimental results show that: the natural rubber pulp slurry material of the interpolation carbon nanotube (CNTs) that the present invention prepares, CNTs is homodisperse therein, with its preparation CNTs modified powder rubber and further preparation add the rubber items such as sulfurized natural rubber of CNTs modification, the performance of its mechanics, conduction, heat conduction and aspect such as antistatic all improves a lot.
Description of drawings:
Carbon nanotube pattern (TEM) under Fig. 1 different states; Fig. 1 (a) boils carbon nanotube pattern under the state, the carbon nanotube pattern that Fig. 1 (b) boils through peracid without peracid;
The dispersion state (SEM) of CNTs in natural rubber in two kinds of different methods of Fig. 2; Fig. 2 (a) is the dispersion state of CNTs in natural rubber under the mechanically milling condition, and Fig. 2 (b) is the dispersion state of CNTs in natural rubber in the inventive method.
Embodiment:
CNTs/ natural rubber latex suspension is through the spray drying method for preparation powdered rubber, in this process, the liquid medium evaporation, make that the good distribution state of CNTs in natural rubber latex kept, so, observe the dispersion state of CNTs in the powdered rubber by scanning electron microscope (SEM), can be used as CNTs Characterization of Dispersed State in natural rubber latex.
The preparation steps of slurry:
1, the surface treatment of carbon nanotube:
For CNTs is disperseed in natural rubber latex preferably, need carry out surface treatment to it, wherein, it is more satisfactory treatment process that acid is boiled.CNTs area load after the processing have hydroxyl (OH), carboxyl (COOH) and carbonyl (＞functional group such as C=O) is on infrared absorption spectrum, corresponding to wavelength 1750cm
-1And 3500cm
-1Demonstrate respectively tangible carbonyl (＞C=O) and hydroxyl (OH) peak.The existence of these functional groups has improved the wetting ability of CNTs, helps the preparation of CNTs/ deionized water suspension.Simultaneously, the functional group of area load also helps strengthening the interface interaction between CNTs and the rubber matrix, thereby improves composite materials property.
2, preparation of carbon nano-tube suspension liquid
Adding dispersion agent is further to improve suspension effect and the promotion CNTs dispersive effective way of CNTs in natural rubber latex.Sodium dodecylbenzene sulfonate (SDAS) is a kind of anion surfactant commonly used, and the adding of dispersion agent is too much unfavorable to the performance of powdered rubber, and the mass ratio of dispersion agent and CNTs is 5%～20% o'clock, and the CNTs stability of suspension that obtains is good.
3, regulate the pH value of carbon pipe suspension
In the mixing process of CNTs-aqeous suspension and natural rubber latex, be easy to generate the flocculation phenomenon, its major cause is because the adding of CNTs suspension reduces the latex zeta-potential.When zeta-potential was reduced to a certain threshold value, the electrostatic repulsion forces between the latex particle was not enough to offset the magnetism between the particle, and the balance between the latex particle is broken, and latex particle collides mutually, condenses owing to thermal motion, thereby formed flocculation.For this reason, need to improve the zeta-potential of latex, add emulsifying agent and can improve zeta-potential, because SDAS is again an emulsifying agent simultaneously, so, adopt reasonable proportioning, can produce the good CNTs-water-natural rubber latex suspension of suspension.Simultaneously, also to consider the stability problem of latex,,, need in the suspension of carbon nanotube, to add ammoniacal liquor or KOH, improve more than its pH value to 9 so two aspects will be taken all factors into consideration because the pH value is a leading indicator of characterization natural latex stability.
4, carbon nano tube suspension is mixed with latex
Above-mentioned carbon nano tube suspension is slowly joined in the natural rubber latex, fully stir, obtain the slurry that carbon nanotube is evenly distributed in natural rubber latex through magnetic stirring apparatus.
Further describe the present invention in conjunction with the accompanying drawings with embodiment below, but scope of the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
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 peracid of learning from else's experience boils the CNTs30g of processing, 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).
Observing down at transmission electron microscope (TEM) through peracid CNTs that boils and the CNTs that boils processing without peracid of embodiment 1 gained as shown in Figure 1, as seen boiled the dispersion state that processing can effectively improve CNTs through peracid.With spray-drying process natural rubber pulp slurry material is further prepared powdered rubber, observe the dispersion state of CNTs in the powdered rubber with scanning electron microscope (SEM), compare with the powdered rubber for preparing with mechanical mixing method, as shown in Figure 2, as seen the powdered rubber that obtains of the method applied in the present invention, the dispersion effect of CNTs is better.
Embodiment 2
The peracid of learning from else's experience boils the CNTs3g of processing, sodium laurylsulfonate 0.3g, join with the CNTs mass ratio be in 10: 1 the deionized water, through ultra-sonic dispersion, obtain the CNTs-aqeous suspension.Adding ammoniacal liquor in suspension makes the suspension pH value reach 10.5.Get solid content and be 60% natural rubber latex 25g, this suspension is joined in the natural rubber latex, and it is 10% that the adding appropriate amount of deionized water makes its total solid content, and adopts magnetic stirring apparatus through the abundant stirring more than 2 hours, it is mixed, and making CNTs content is the natural rubber latex suspension of 20phr.Observe the powdered rubber that it prepares with SEM, CNTs dispersion state therein is better.
Embodiment 3
The peracid of learning from else's experience boils the CNTs0.6g of processing, sodium laurylsulfonate 0.12g, 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 12.Get solid content and be 60% natural rubber latex 100g, this suspension is joined in the natural rubber latex, and it is 30% that the adding appropriate amount of deionized water makes its total solid content, and adopts magnetic stirring apparatus through the abundant stirring more than 2 hours, it is mixed, and making CNTs content is the natural rubber latex suspension of 1phr.Observe the powdered rubber that it prepares with SEM, CNTs dispersion state therein is better.
Embodiment 4
The peracid of learning from else's experience boils the CNTs15g of processing, sodium laurylsulfonate 0.75g, 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 9.Get solid content and be 60% natural rubber latex 100g, this suspension is joined in the natural rubber latex, and it is 5% that the adding appropriate amount of deionized water makes its total solid content, and adopts magnetic stirring apparatus through the abundant stirring more than 2 hours, it is mixed, and making CNTs content is the natural rubber latex suspension of 25phr.Observe the powdered rubber that it prepares with SEM, CNTs dispersion state therein is better.
Step as embodiment 1 prepares the CNTs-aqeous suspension, natural rubber latex is progressively joined in this CNTs-aqeous suspension conversely, when natural latex is added to 100g, this moment, the content of CNTs reached 50phr, add appropriate amount of deionized water again and, still can obtain the natural rubber latex suspension of CNTs stable dispersion through the abundant stirring more than 2 hours.Illustrate that the CNTs that handles through this kind method can mix with natural rubber latex with the arbitrary proportion of relative broad range.
The spray-dried method of natural rubber pulp slurry material that contains CNTs that the invention described above is made can prepare the powdered rubber that contains CNTs, and its powdered rubber can be used to goods such as polymer modification and preparation vulcanized rubber.
The natural rubber latex suspension of CNTs modification is added in preparation, improve the dispersion of CNTs in rubber matrix by the liquid dispersion approach, and then adopt method such as spraying drying to prepare CNTs modified powder rubber, not only can be directly used in the processing rubber goods, and the powdered rubber that adds after the CNTs modification can be widely used in fields such as plastics, resin and other composite modification, as adopting this powdered rubber directly to prepare to add the sulfurized natural rubber of CNTs modification, improve the mechanics, conduction, heat conduction of natural rubber and the performance of aspect such as antistatic.
Claims (10)
1, a kind of natural rubber pulp slurry material that adds CNTs contains natural rubber latex, it is characterized in that, also contain CNTs, the total solid content of described CNTs and the dried glue of natural rubber latex is 5%～30%, and the CNTs quality is an arbitrary proportion with the ratio of natural rubber latex dry glue quality.
2, the method for the natural rubber pulp slurry material of preparation interpolation as claimed in claim 1 CNTs is characterized in that, contains following steps successively:
1) CNTs is carried out surface treatment, makes its possess hydrophilic property:
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%;
3) pH value to 9～12 of the above-mentioned CNTs-aqeous suspension of adjusting;
4), obtain adding the natural rubber pulp slurry material of CNTs with the CNTs-aqeous suspension behind the above-mentioned adjusting pH value and many arbitrarily natural rubber latex uniform mixing.
3, the preparation method of the natural rubber pulp slurry material of interpolation CNTs as claimed in claim 2 is characterized in that the described the 1st) step is carried out surface treatment to CNTs, is CNTs to be carried out acid boil.
4, the preparation method of the natural rubber pulp slurry material of interpolation CNTs as claimed in claim 2 is characterized in that described dispersion agent is Sodium dodecylbenzene sulfonate or sodium laurylsulfonate.
5, the preparation method of the natural rubber pulp slurry material of interpolation as claimed in claim 2 CNTs is characterized in that the described the 3rd) pH value of step joint CNTs-aqeous suspension regulates by adding KOH or ammoniacal liquor.
6, a kind of natural rubber pulp slurry material that adds CNTs contains natural rubber latex, it is characterized in that, also contain CNTs, the total solid content of described CNTs and the dried glue of natural rubber latex is 5%～30%, and the CNTs quality is 1%～50% with the ratio of natural rubber latex dry glue quality.
7, the method for the natural rubber pulp slurry material of preparation interpolation as claimed in claim 6 CNTs is characterized in that, contains following steps successively:
1) CNTs is carried out surface treatment, makes its possess hydrophilic property:
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%;
3) pH value to 9～12 of the above-mentioned CNTs-aqeous suspension of adjusting;
4), obtain adding the natural rubber pulp slurry material of CNTs with CNTs-aqeous suspension behind the above-mentioned adjusting pH value and natural rubber latex uniform mixing.
8, the preparation method of the natural rubber pulp slurry material of interpolation CNTs as claimed in claim 7 is characterized in that the described the 1st) step is carried out surface treatment to CNTs, is CNTs to be carried out acid boil.
9, the preparation method of the natural rubber pulp slurry material of interpolation CNTs as claimed in claim 7 is characterized in that described dispersion agent is Sodium dodecylbenzene sulfonate or sodium laurylsulfonate.
10, the preparation method of the natural rubber pulp slurry material of interpolation as claimed in claim 7 CNTs is characterized in that the described the 3rd) pH value of step joint CNTs-aqeous suspension regulates by adding KOH or ammoniacal liquor.
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| CN110305375A (en) * | 2019-07-11 | 2019-10-08 | 陕西延长石油(集团)有限责任公司研究院 | A kind of carbon nano-tube modification natural rubber material and preparation method thereof |
| CN114075352A (en) * | 2020-08-12 | 2022-02-22 | 苏州怒鲨智能科技有限公司 | Conductive rubber for flexible sensor and preparation method thereof |
| CN112778584A (en) * | 2021-01-28 | 2021-05-11 | 苏州第一元素纳米技术有限公司 | Rubber composite master batch and preparation method thereof |
| RU2767647C1 (en) * | 2021-03-05 | 2022-03-18 | МСД Текнолоджис С.а р.л. | Additive to rubber compositions, method of producing additive, method of producing rubber with high electrical conductivity and physical and mechanical properties and rubber |
| WO2022186728A1 (en) * | 2021-03-05 | 2022-09-09 | МСД Текнолоджис С.а р.л. | Additive for rubber compositions and method for producing same |
| CN116079958A (en) * | 2023-01-31 | 2023-05-09 | 青岛联康油脂制品有限公司 | Green tyre external spray and preparation method thereof |
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