CN1673261A - Natural liquid rubber slurry with added carbon nanotube and its prepn process - Google Patents
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Abstract
添加碳纳米管的天然橡胶液体浆料及其制备方法涉及橡胶等高分子复合材料的性能改进技术领域。该浆料含有天然胶乳，还含有CNTs，CNTs与天然胶乳干胶的总固含量为5％～30％，CNTs与天然胶乳干胶质量之比为1％～50％。制备方法为，首先对CNTs进行表面处理，使其具有亲水性：然后将其与分散剂、去离子水混合，得到CNTs－水悬浮液；调节该悬浮液的pH值到9～12；最后与天然胶乳均匀混合，得到添加CNTs的天然橡胶液体浆料。本发明制备的浆料中，CNTs在其中均匀分散，用其制备CNTs改性粉末橡胶并进一步制备添加CNTs改性的硫化天然橡胶等橡胶制品，其力学、导电、导热及抗静电等方面的性能都有很大提高。
The natural rubber liquid slurry added with carbon nanotubes and the preparation method thereof relate to the technical field of performance improvement of polymer composite materials such as rubber. The slurry contains natural rubber latex and also contains CNTs, the total solid content of CNTs and natural latex dry rubber is 5%-30%, and the mass ratio of CNTs to natural latex dry rubber is 1%-50%. The preparation method is as follows: first, the surface treatment of CNTs is carried out to make it hydrophilic; then it is mixed with a dispersant and deionized water to obtain a CNTs-water suspension; the pH value of the suspension is adjusted to 9-12; finally Mix evenly with natural rubber latex to obtain natural rubber liquid slurry with CNTs added. In the slurry prepared by the present invention, CNTs are uniformly dispersed therein, and it is used to prepare CNTs modified powder rubber and further prepare rubber products such as vulcanized natural rubber added with CNTs modified, and its mechanical, electrical, thermal and antistatic properties All have greatly improved.
Description
技术领域：Technical field:
添加碳纳米管的天然橡胶液体浆料及其制备方法涉及橡胶等高分子复合材料的性能改进Natural rubber liquid slurry added with carbon nanotubes and preparation method thereof relate to performance improvement of polymer composite materials such as rubber
技术领域。technology field.
背景技术：Background technique:
CNTs(碳纳米管)自1991年由日本学者Iijima首先发现以来，因其独特的结构和优异的物理性能，使其在工程材料方面的应用研究迅速成为热点，其中，在复合材料领域，CNTs被广泛用于复合材料改性，然而，CNTs在天然橡胶改性以及改性后粉末橡胶制备方面的应用研究则尚未见报道。Since CNTs (carbon nanotubes) were first discovered by Japanese scholar Iijima in 1991, due to their unique structure and excellent physical properties, their application research in engineering materials has quickly become a hotspot. Among them, in the field of composite materials, CNTs have been It is widely used in the modification of composite materials. However, the application research of CNTs in the modification of natural rubber and the preparation of modified powder rubber has not been reported.
天然橡胶液体浆料是制备粉末橡胶等复合材料的重要原料之一，如可用喷雾干燥法将天然橡胶液体浆料制备成粉末橡胶。往天然橡胶液体浆料加入CNTs，能进一步改进其最终制成品的性能。经检索，现有技术中没有发现含有CNTS的天然橡胶液体浆料及其制备方法方面的文献。Natural rubber liquid slurry is one of the important raw materials for preparing powder rubber and other composite materials. For example, the natural rubber liquid slurry can be prepared into powder rubber by spray drying method. Adding CNTs to natural rubber liquid slurry can further improve the properties of the final product. After searching, there is no literature on natural rubber liquid slurry containing CNTS and its preparation method found in the prior art.
发明内容Contents of the invention
本发明的目的在于提供一种添加碳纳米管(CNTs)的天然橡胶液体浆料及其制备方法。The object of the present invention is to provide a natural rubber liquid slurry added with carbon nanotubes (CNTs) and a preparation method thereof.
本发明人曾经利用机械混炼方法制备CNTs改性橡胶复合材料，性能检测表明CNTs对橡胶基体表现出补强效应，改性后的橡胶复合材料回弹性、压缩疲劳及耐老化性能均优于传统炭黑补强橡胶样品，但拉伸及撕裂性能较差。研究发现，CNTs在橡胶基体中团聚现象普遍存在，从复合材料增强的原理出发，要求用于补强的填充物应在基体中充分分散，而弹性聚合物基体的高粘滞性大大提高了填充物在其中分散的难度，这可能是影响CNTs改性橡胶复合材料性能提高的主要原因。因此，解决CNTs在橡胶基体中的分散问题，就成为CNTs改性橡胶复合材料制备及其性能优化的关键。The present inventors have used mechanical mixing method to prepare CNTs modified rubber composite material, and the performance test shows that CNTs has a reinforcing effect on the rubber matrix, and the modified rubber composite material has better resilience, compression fatigue and aging resistance than the traditional one. Carbon black reinforced the rubber sample, but the tensile and tear properties were poor. The study found that the agglomeration of CNTs in the rubber matrix is common. Starting from the principle of composite material reinforcement, it is required that the filler used for reinforcement should be fully dispersed in the matrix, and the high viscosity of the elastic polymer matrix greatly improves the filling. The difficulty of dispersing the compound in it may be the main reason affecting the performance improvement of CNTs modified rubber composites. Therefore, solving the dispersion problem of CNTs in the rubber matrix has become the key to the preparation and performance optimization of CNTs modified rubber composites.
由于天然胶乳本身的特点，在和CNTs的混合过程中很容易发生絮凝现象，这是制备添加CNTs的天然橡胶液体浆料的难点所在。因此，本发明主要实现CNTs在天然胶乳中均匀分散，并解决共混中出现的絮凝问题，以制备稳定的CNTs/天然胶乳悬浮液。Due to the characteristics of natural rubber latex itself, it is easy to flocculate during the mixing process with CNTs, which is the difficulty in preparing natural rubber liquid slurry with CNTs added. Therefore, the present invention mainly realizes the uniform dispersion of CNTs in natural latex, and solves the problem of flocculation occurring in blending, so as to prepare a stable CNTs/natural latex suspension.
本发明所提出的添加碳纳米管(CNTs)的天然橡胶液体浆料，其特征在于，含有天然胶乳，还含有CNTs，所述CNTs与天然胶乳干胶的总固含量为5％～30％，CNTs质量与天然胶乳干胶质量之比为任意比例。The natural rubber liquid slurry added with carbon nanotubes (CNTs) proposed by the present invention is characterized in that it contains natural rubber latex and also contains CNTs, and the total solid content of the CNTs and natural latex dry glue is 5% to 30%, The ratio of CNTs quality to natural rubber latex dry rubber quality is any ratio.
制备上述添加CNTs的天然橡胶液体浆料的方法，其特征在于，依次含有以下步骤：The method for preparing the above-mentioned natural rubber liquid slurry adding CNTs is characterized in that it contains the following steps in sequence:
1)对CNTs进行表面处理，使其具有亲水性：1) Surface treatment of CNTs to make them hydrophilic:
2)碳纳米管悬浮液的制备：2) Preparation of carbon nanotube suspension:
将上述经过表面处理的CNTs与分散剂、去离子水进行混合，得到CNTs-水悬浮液，其中分散剂与所述CNTs的质量比为5％～20％；Mixing the surface-treated CNTs with a dispersant and deionized water to obtain a CNTs-water suspension, wherein the mass ratio of the dispersant to the CNTs is 5% to 20%;
3)调节上述CNTs-水悬浮液的PH值到9～12；3) adjusting the pH value of the above CNTs-water suspension to 9-12;
4)将上述调节PH值后的CNTs-水悬浮液与任意多的天然胶乳均匀混合，得到添加CNTs的天然橡胶液体浆料。4) Uniformly mixing the above-mentioned CNTs-water suspension after adjusting the pH value with any amount of natural rubber latex to obtain a natural rubber liquid slurry added with CNTs.
所述第1)步对CNTs进行表面处理，是将CNTs进行酸煮。所述分散剂是十二烷基苯磺酸钠或十二烷基磺酸钠。所述第3)步调节CNTs-水悬浮液的PH值是通过加入KOH或氨水调节的。The first) step is to carry out surface treatment on CNTs, which is to boil CNTs with acid. The dispersant is sodium dodecylbenzenesulfonate or sodium dodecylsulfonate. The step 3) to adjust the pH value of the CNTs-water suspension is adjusted by adding KOH or ammonia water.
另一种添加CNTs的天然橡胶液体浆料，含有天然胶乳，其特征在于，还含有CNTs，所述CNTs与天然胶乳干胶的总固含量为5％～30％，CNTs质量与天然胶乳干胶质量之比为1％～50％。Another natural rubber liquid slurry added with CNTs contains natural rubber latex, and is characterized in that it also contains CNTs, the total solid content of the CNTs and natural latex dry rubber is 5% to 30%, and the quality of CNTs is the same as that of natural latex dry rubber. The mass ratio is 1% to 50%.
制备上述添加CNTs的天然橡胶液体浆料的方法，其特征在于，依次含有以下步骤：The method for preparing the above-mentioned natural rubber liquid slurry adding CNTs is characterized in that it contains the following steps in sequence:
1)对CNTs进行表面处理，使其具有亲水性：1) Surface treatment of CNTs to make them hydrophilic:
2)碳纳米管悬浮液的制备：2) Preparation of carbon nanotube suspension:
将上述经过表面处理的CNTs与分散剂、去离子水进行混合，得到CNTs-水悬浮液，其中分散剂与所述CNTs的质量比为5％～20％；Mixing the surface-treated CNTs with a dispersant and deionized water to obtain a CNTs-water suspension, wherein the mass ratio of the dispersant to the CNTs is 5% to 20%;
3)调节上述CNTs-水悬浮液的PH值到9～12；3) adjusting the pH value of the above CNTs-water suspension to 9-12;
4)将上述调节PH值后的CNTs-水悬浮液与天然胶乳均匀混合，得到添加CNTs的天然橡胶液体浆料。4) Uniformly mixing the above-mentioned CNTs-water suspension after adjusting the pH value with natural rubber latex to obtain a natural rubber liquid slurry added with CNTs.
所述第1)步对CNTs进行表面处理，是将CNTs进行酸煮。所述分散剂是十二烷基苯磺酸钠或十二烷基磺酸钠。所述第3)步调节CNTs-水悬浮液的PH值是通过加入KOH或氨水调节的。The first) step is to carry out surface treatment on CNTs, which is to boil CNTs with acid. The dispersant is sodium dodecylbenzenesulfonate or sodium dodecylsulfonate. The step 3) to adjust the pH value of the CNTs-water suspension is adjusted by adding KOH or ammonia water.
实验证明：本发明制备得到的添加碳纳米管(CNTs)的天然橡胶液体浆料，CNTs在其中均匀分散，用其制备CNTs改性粉末橡胶并进一步制备添加CNTs改性的硫化天然橡胶等橡胶制品，其力学、导电、导热及抗静电等方面的性能都有很大提高。The experiment proves that: the natural rubber liquid slurry added with carbon nanotubes (CNTs) prepared by the present invention is uniformly dispersed therein, and is used to prepare CNTs modified powder rubber and further prepare rubber products such as vulcanized natural rubber added with CNTs modified , its mechanical, electrical, thermal and antistatic properties have been greatly improved.
附图说明：Description of drawings:
图1不同状态下的碳纳米管形貌(TEM)；图1(a)未经过酸煮状态下的碳纳米管形貌，图1(b)经过酸煮的碳纳米管形貌；Figure 1 Morphology of carbon nanotubes in different states (TEM); Figure 1(a) Morphology of carbon nanotubes without acid cooking, Figure 1(b) Morphology of carbon nanotubes after acid cooking;
图2两种不同方法中CNTs在天然橡胶中的分散状态(SEM)；图2(a)为机械混炼条件下CNTs在天然橡胶中的分散状态，图2(b)为本发明方法中CNTs在天然橡胶中的分散状态。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 mechanical mixing condition, and Fig. 2 (b) is CNTs in the method of the present invention Dispersion state in natural rubber.
具体实施方式：Detailed ways:
CNTs/天然胶乳悬浮液经过喷雾干燥法制备粉末橡胶，在此过程中，液体介质蒸发，使得CNTs在天然胶乳中的良好分散状态得以保留，所以，通过扫描电镜(SEM)观察到粉末橡胶中CNTs的分散状态，可以作为CNTs在天然胶乳中分散状态的表征。The CNTs/natural rubber latex suspension was spray-dried to prepare powdered rubber. During this process, the liquid medium evaporated, so that the good dispersion state of CNTs in natural latex was preserved. Therefore, the CNTs in powdered rubber were observed by scanning electron microscope (SEM). The dispersion state of CNTs can be used as a characterization of the dispersion state of CNTs in natural rubber latex.
浆料的配制步骤：Preparation steps of slurry:
1、碳纳米管的表面处理：1. Surface treatment of carbon nanotubes:
为了使CNTs在天然胶乳中得到较好的分散，需要对其进行表面处理，其中，酸煮是比较理想的处理方法。处理后的CNTs表面负载有羟基(-OH)、羧基(-COOH)及羰基(＞C＝O)等官能团，在红外吸收谱上，对应于波长1750cm-1和3500cm-1分别显示出明显的羰基(＞C＝O)和羟基(-OH)峰。这些官能团的存在提高了CNTs的亲水性，有利于CNTs/去离子水悬浮液的制备。同时，表面负载的官能团也有利于增强CNTs与橡胶基体之间的界面作用，从而提高复合材料力学性能。In order to better disperse CNTs in natural rubber latex, it is necessary to carry out surface treatment, among which acid boiling is an ideal treatment method. The surface of the treated CNTs is loaded with functional groups such as hydroxyl (-OH), carboxyl ( -COOH ) and carbonyl (>C=O). Carbonyl (>C=O) and hydroxyl (-OH) peaks. The presence of these functional groups improves the hydrophilicity of CNTs, which is beneficial to the preparation of CNTs/deionized water suspensions. At the same time, the functional groups loaded on the surface are also beneficial to enhance the interfacial interaction between CNTs and the rubber matrix, thereby improving the mechanical properties of the composite.
2、碳纳米管悬浮液的制备2. Preparation of carbon nanotube suspension
加入分散剂是进一步提高CNTs在天然胶乳中的悬浮效果并且促进CNTs分散的有效办法。十二烷基苯磺酸钠(SDAS)是一种常用的阴离子表面活性剂，分散剂的加入过多对粉末橡胶的性能不利，分散剂与CNTs的质量比为5％～20％时，得到的CNTs悬浮液稳定性良好。Adding dispersant is an effective way to further improve the suspension effect of CNTs in natural rubber latex and promote the dispersion of CNTs. Sodium dodecylbenzenesulfonate (SDAS) is a commonly used anionic surfactant. Too much dispersant is unfavorable to the performance of powder rubber. When the mass ratio of dispersant to CNTs is 5% to 20%, the obtained The CNTs suspension has good stability.
3、调节碳管悬浮液的PH值3. Adjust the pH value of carbon tube suspension
在CNTs-水悬浮液与天然胶乳的混合过程中，容易产生絮凝现象，其主要原因是由于CNTs悬浮液的加入使胶乳ζ电位降低。当ζ电位降至某一临界值时，胶乳粒子之间的静电排斥力不足以抵消粒子之间的吸引力，胶乳颗粒之间的平衡被打破，胶乳粒子由于热运动而相互碰撞、凝结，从而形成絮凝。为此，需要提高胶乳的ζ电位，加入乳化剂可以提高ζ电位，因为SDAS同时又是乳化剂，所以，采用合理的配比，可以制取悬浮性良好的CNTs-水—天然胶乳悬浮液。同时，还要考虑胶乳的稳定性问题，因为pH值是表征天然胶乳稳定性的一个主要指标，所以，两个方面要综合考虑，需向碳纳米管的悬浮液中加入氨水或KOH，提高其PH值至9以上。During the mixing process of CNTs-water suspension and natural latex, flocculation is easy to occur, and the main reason is that the ζ potential of latex decreases due to the addition of CNTs suspension. When the zeta potential drops to a certain critical value, the electrostatic repulsion between the latex particles is not enough to offset the attractive force between the particles, the balance between the latex particles is broken, and the latex particles collide with each other and coagulate due to thermal motion, thus Flocculation is formed. Therefore, it is necessary to increase the zeta potential of the latex. Adding an emulsifier can increase the zeta potential. Because SDAS is also an emulsifier, a reasonable ratio can be used to prepare a CNTs-water-natural latex suspension with good suspension. At the same time, the stability of the latex should also be considered, because the pH value is a main indicator of the stability of the natural latex, so the two aspects should be considered comprehensively. It is necessary to add ammonia or KOH to the suspension of carbon nanotubes to increase its stability. PH value to above 9.
4、碳纳米管悬浮液与胶乳混合4. Carbon nanotube suspension mixed with latex
将上述碳纳米管悬浮液缓慢加入到天然胶乳中，经磁力搅拌器充分搅拌，得到碳纳米管在天然胶乳中分布均匀的浆料。Slowly add the suspension of carbon nanotubes into the natural rubber latex, and fully stir with a magnetic stirrer to obtain a slurry in which the carbon nanotubes are uniformly distributed in the natural rubber latex.
下面用实施例结合附图进一步描述本发明，但本发明的范围不受这些实施例的限制。The present invention is further described below with reference to the accompanying drawings, but the scope of the present invention is not limited by these examples.
实施例1Example 1
将CNTs置于体积比为V硫酸∶V硝酸＝3∶1的混合酸液中，1gCNTs对应10ml酸液，煮沸30min，洗涤，烘干后得到酸煮CNTs。取经过酸煮处理的CNTs30g，十二烷基苯磺酸钠(SDAS)3g，加入到与CNTs质量比为10∶1的去离子水中，经过超声分散，得到CNTs-水悬浮液。向悬浮液中加入KOH使悬浮液PH值达到10。取固含量为60％的天然胶乳100g，将此悬浮液加入到天然胶乳中，加入适量去离子水使其总固含量为10％，并采用磁力搅拌器经2小时以上的充分搅拌，使其混合均匀，制得CNTs含量为50phr(即CNTs与天然胶乳干胶质量比为50％)的天然橡胶液体浆料。Put CNTs in a mixed acid solution with a volume ratio of V sulfuric acid : V nitric acid = 3:1, 1 g of CNTs corresponds to 10 ml of acid solution, boil for 30 minutes, wash, and dry to obtain acid boiled CNTs. Take 30 g of acid boiled CNTs and 3 g of sodium dodecylbenzenesulfonate (SDAS), add them to deionized water with a mass ratio of CNTs of 10:1, and ultrasonically disperse to obtain a CNTs-water suspension. KOH was added to the suspension to bring the pH of the suspension to 10. Get solid content and be 60% natural rubber latex 100g, this suspension is joined in the natural rubber latex, add appropriate amount of deionized water to make its total solid content be 10%, and adopt magnetic stirrer through fully stirring more than 2 hours, make it Mix evenly to prepare a natural rubber liquid slurry with a CNTs content of 50 phr (that is, the mass ratio of CNTs to natural latex dry rubber is 50%).
实施例1所得的经过酸煮的CNTs与未经过酸煮处理的CNTs在透射电镜(TEM)下观察，如图1所示，可见经过酸煮处理可以有效改善CNTs的分散状态。用喷雾干燥法将天然橡胶液体浆料进一步制备得到粉末橡胶，用扫描电镜(SEM)观察到粉末橡胶中CNTs的分散状态，与用机械混炼法制备得到的粉末橡胶进行对比，如图2所示，可见本发明所采用的方法得到的粉末橡胶，CNTs的分散效果更好。The acid-cooked CNTs obtained in Example 1 and the CNTs without acid-cooking treatment were observed under a transmission electron microscope (TEM), as shown in FIG. 1 , it can be seen that the dispersion state of CNTs can be effectively improved after acid-cooking treatment. The natural rubber liquid slurry was further prepared by spray drying method to obtain powder rubber, and the dispersion state of CNTs in the powder rubber was observed by scanning electron microscope (SEM), and compared with the powder rubber prepared by mechanical mixing method, as shown in Figure 2 It can be seen that the powder rubber obtained by the method adopted in the present invention has a better dispersion effect of CNTs.
实施例2Example 2
取经过酸煮处理的CNTs3g，十二烷基磺酸钠0.3g，加入到与CNTs质量比为10∶1的去离子水中，经过超声分散，得到CNTs-水悬浮液。向悬浮液中加入氨水使悬浮液PH值达到10.5。取固含量为60％的天然胶乳25g，将此悬浮液加入到天然胶乳中，加入适量去离子水使其总固含量为10％，并采用磁力搅拌器经2小时以上的充分搅拌，使其混合均匀，制得CNTs含量为20phr的天然胶乳悬浮液。用SEM观察其制备得到的粉末橡胶，CNTs在其中的分散状态较好。Take 3 g of acid-cooked CNTs and 0.3 g of sodium dodecylsulfonate, add them into deionized water with a mass ratio of CNTs of 10:1, and disperse by ultrasonic to obtain a CNTs-water suspension. Ammonia water was added to the suspension to bring the pH value of the suspension to 10.5. Get 25g of natural latex with a solid content of 60%, add this suspension to the natural latex, add an appropriate amount of deionized water to make the total solid content 10%, and use a magnetic stirrer to fully stir for more than 2 hours to make it Mix evenly to prepare a natural rubber latex suspension with a CNTs content of 20phr. The prepared powder rubber was observed by SEM, and the dispersion state of CNTs in it was good.
实施例3Example 3
取经过酸煮处理的CNTs0.6g，十二烷基磺酸钠0.12g，加入到与CNTs质量比为10∶1的去离子水中，经过超声分散，得到CNTs-水悬浮液。向悬浮液中加入KOH使悬浮液PH值达到12。取固含量为60％的天然胶乳100g，将此悬浮液加入到天然胶乳中，加入适量去离子水使其总固含量为30％，并采用磁力搅拌器经2小时以上的充分搅拌，使其混合均匀，制得CNTs含量为1phr的天然胶乳悬浮液。用SEM观察其制备得到的粉末橡胶，CNTs在其中的分散状态较好。Take 0.6 g of acid-cooked CNTs and 0.12 g of sodium dodecylsulfonate, add them to deionized water with a mass ratio of CNTs of 10:1, and disperse by ultrasonic to obtain a CNTs-water suspension. KOH was added to the suspension to bring the pH of the suspension to 12. Get solid content and be 60% natural rubber latex 100g, this suspension is joined in the natural rubber latex, add appropriate amount of deionized water to make its total solid content be 30%, and adopt magnetic stirrer through fully stirring more than 2 hours, make it Mix evenly to prepare a natural rubber latex suspension with a CNTs content of 1phr. The prepared powder rubber was observed by SEM, and the dispersion state of CNTs in it was good.
实施例4Example 4
取经过酸煮处理的CNTs15g，十二烷基磺酸钠0.75g，加入到与CNTs质量比为10∶1的去离子水中，经过超声分散，得到CNTs-水悬浮液。向悬浮液中加入KOH使悬浮液PH值达到9。取固含量为60％的天然胶乳100g，将此悬浮液加入到天然胶乳中，加入适量去离子水使其总固含量为5％，并采用磁力搅拌器经2小时以上的充分搅拌，使其混合均匀，制得CNTs含量为25phr的天然胶乳悬浮液。用SEM观察其制备得到的粉末橡胶，CNTs在其中的分散状态较好。Take 15 g of acid-cooked CNTs and 0.75 g of sodium dodecylsulfonate, add them into deionized water with a mass ratio of CNTs of 10:1, and disperse by ultrasonic to obtain a CNTs-water suspension. KOH was added to the suspension to bring the pH of the suspension to 9. Get solid content and be 60% natural rubber latex 100g, this suspension is joined in the natural rubber latex, add appropriate amount of deionized water to make its total solid content be 5%, and adopt magnetic stirrer through fully stirring more than 2 hours, make it Mix evenly to prepare a natural rubber latex suspension with a CNTs content of 25phr. The prepared powder rubber was observed by SEM, and the dispersion state of CNTs in it was good.
实施例5Example 5
如实施例1的步骤制备得到CNTs-水悬浮液，反过来将天然胶乳逐步加入到该CNTs-水悬浮液中，当天然胶乳加入至100g时，此时CNTs的含量达到50phr，再加入适量去离子水并经过2小时以上的充分搅拌，仍可得到CNTs稳定分散的天然胶乳悬浮液。说明经过此种方法处理的CNTs可以以较宽范围的任意比例与天然胶乳混合。The CNTs-water suspension was prepared as in the steps of Example 1, and the natural rubber latex was gradually added to the CNTs-water suspension in turn. When the natural rubber latex was added to 100g, the content of CNTs reached 50phr at this time, and then an appropriate amount was added to remove Ionized water and full stirring for more than 2 hours can still obtain a natural rubber latex suspension in which CNTs are stably dispersed. It shows that CNTs treated by this method can be mixed with natural rubber latex in any ratio in a wide range.
将上述本发明制得的含CNTs的天然橡胶液体浆料经喷雾干燥法可制备含有CNTs的粉末橡胶，其粉末橡胶可用来聚合物改性以及制备硫化橡胶等制品。Powdered rubber containing CNTs can be prepared by spray drying the liquid slurry of natural rubber containing CNTs prepared in the present invention above, and the powdered rubber can be used for polymer modification and preparation of vulcanized rubber and other products.
制备添加CNTs改性的天然胶乳悬浮液，通过液体分散途径改善CNTs在橡胶基体中的分散，进而采用喷雾干燥等方法制备CNTs改性粉末橡胶，不仅可以直接用于加工橡胶制品，而且添加CNTs改性后的粉末橡胶能够广泛应用于塑料、树脂以及其它复合材料改性等领域，如可以采用这种粉末橡胶直接制备添加CNTs改性的硫化天然橡胶，提高天然橡胶的力学、导电、导热及抗静电等方面的性能。Prepare the natural rubber latex suspension modified by adding CNTs, improve the dispersion of CNTs in the rubber matrix through liquid dispersion, and then prepare CNTs modified powder rubber by spray drying and other methods. The powder rubber after curing can be widely used in the fields of modification of plastics, resins and other composite materials. For example, this powder rubber can be used to directly prepare vulcanized natural rubber modified by adding CNTs to improve the mechanical properties, electrical conductivity, thermal conductivity and resistance of natural rubber. Static properties, etc.
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