CN101955593A - Method for improving surface hydrophilicity of waste rubber powder - Google Patents
Method for improving surface hydrophilicity of waste rubber powder Download PDFInfo
- Publication number
- CN101955593A CN101955593A CN 201010167618 CN201010167618A CN101955593A CN 101955593 A CN101955593 A CN 101955593A CN 201010167618 CN201010167618 CN 201010167618 CN 201010167618 A CN201010167618 A CN 201010167618A CN 101955593 A CN101955593 A CN 101955593A
- Authority
- CN
- China
- Prior art keywords
- rubber powder
- waste rubber
- waste
- plasma
- modification
- 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.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 92
- 239000005060 rubber Substances 0.000 title claims abstract description 91
- 239000000843 powder Substances 0.000 title claims abstract description 89
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims description 21
- 238000012986 modification Methods 0.000 claims description 21
- 239000010920 waste tyre Substances 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 230000006872 improvement Effects 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 229920002449 FKM Polymers 0.000 claims 1
- 239000003570 air Substances 0.000 claims 1
- 229920002521 macromolecule Polymers 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 238000009832 plasma treatment Methods 0.000 abstract description 22
- 239000003960 organic solvent Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Images
Landscapes
- Processing Of Solid Wastes (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
本发明公开了一种改善废旧橡胶粉表面亲水性的方法，其特点是将废旧橡胶粉10-100z重量份置于等离子体处理装置中，在室温、大气压的开放环境下，将等离子体喷射到废旧橡胶粉表面，使废旧橡胶粉在等离子体氛围中运动处理，处理废旧橡胶粉的功率为10W-5000W，时间为2.0s-300s。经上述等离子体处理后的废旧橡胶粉表面极性增加，表面氧元素和氮元素增加，表面的亲水性得到显著改善。该方法为一步法，改善了废旧橡胶粉的表面性能、结构和形态，提高了在聚合物中的掺入量。具有工艺简单、可控性强、操作简便和高效的优点。无需有机溶剂，对环境友好。
The invention discloses a method for improving the surface hydrophilicity of waste rubber powder, which is characterized in that 10-100 z weight parts of waste rubber powder are placed in a plasma treatment device, and the plasma is sprayed in an open environment at room temperature and atmospheric pressure To the surface of the waste rubber powder, the waste rubber powder is processed in the plasma atmosphere, the power of the waste rubber powder is 10W-5000W, and the time is 2.0s-300s. The polarity of the surface of the waste rubber powder after the plasma treatment is increased, the oxygen and nitrogen elements on the surface are increased, and the hydrophilicity of the surface is significantly improved. The method is a one-step method, which improves the surface performance, structure and shape of the waste rubber powder, and increases the mixing amount in the polymer. It has the advantages of simple process, strong controllability, convenient operation and high efficiency. No need for organic solvents, friendly to the environment.
Description
技术领域technical field
本发明涉及一种改善废旧橡胶粉表面亲水性的方法，属于废旧橡胶粉表面改性领域。The invention relates to a method for improving the surface hydrophilicity of waste rubber powder, belonging to the field of surface modification of waste rubber powder.
背景技术Background technique
随着汽车工业的迅猛发展，世界的废旧轮胎的积压量已达30亿条，并且以每年10亿条的量迅速增加，因此废旧轮胎的处理问题也变得日益严峻。废旧轮胎也被称为“黑色污染”。填埋和燃烧等方法因为占用资源和二次污染已被逐渐淘汰，除了翻新和原形利用外，大多数废旧轮胎被制成胶粉。废旧轮胎胶粉是由废旧橡胶轮胎经去除钢丝、帘子线后经粉碎后得到的具有一定粒度的橡胶颗粒，是一种由天然橡胶、顺丁橡胶、补强剂(炭黑)、润滑剂、硫及硫化促进剂等多种材料组成的含交联结构的混合物，已用于沥青改性、防水卷材、橡胶砖和轮胎填充物等领域。With the rapid development of the automobile industry, the backlog of waste tires in the world has reached 3 billion, and is increasing rapidly by 1 billion per year. Therefore, the problem of waste tire disposal has become increasingly serious. Waste tires are also known as "black pollution". Methods such as landfilling and burning have been gradually eliminated due to resource occupation and secondary pollution. In addition to retreading and original shape utilization, most waste tires are made into rubber powder. Waste tire rubber powder is a rubber particle with a certain particle size obtained by crushing waste rubber tires after removing steel wires and cords. It is a kind of natural rubber, butadiene rubber, reinforcing agent (carbon black), lubricant, A mixture containing cross-linked structure composed of various materials such as sulfur and vulcanization accelerators, has been used in fields such as asphalt modification, waterproof membranes, rubber bricks and tire fillers.
近年来，随着高分子复合材料的发展和胶粉生产技术的改进，胶粉尤其是改性胶粉在高分子复合材料中的应用发展很快。将废旧橡胶粉通过改性可应用于橡胶、塑料和建筑材料中，不仅可以降低材料的生产成本，还能提高材料的某些物理化学性能，如在橡胶中提高耐屈挠性、改善加工性能；在塑料中掺用可以增韧塑料；在建筑材料中可提高减震、缓冲性能等。据介绍，未经改性的胶粉(精细胶粉)在胶料中的掺用量一般在10％以下，而经过改性处理，掺用量可提高到25％-50％，在塑料中的掺用量则更大，可达100％，胶粉与其他聚合物(如热塑性塑料、橡胶等)的表面结合力更强，力学性能更好，胶粉的表面改性对拓展胶粉的应用、提高其附加值具有重要实用价值。In recent years, with the development of polymer composite materials and the improvement of rubber powder production technology, the application of rubber powder, especially modified rubber powder, in polymer composite materials has developed rapidly. The waste rubber powder can be applied to rubber, plastics and building materials through modification, which can not only reduce the production cost of materials, but also improve some physical and chemical properties of materials, such as improving flex resistance and processing performance in rubber ; When used in plastics, it can toughen plastics; in building materials, it can improve shock absorption and cushioning properties. According to reports, the amount of unmodified rubber powder (fine rubber powder) in the rubber is generally below 10%, and after modification, the amount can be increased to 25%-50%. The dosage is larger, up to 100%. The surface bonding force between the rubber powder and other polymers (such as thermoplastics, rubber, etc.) is stronger, and the mechanical properties are better. Its added value has important practical value.
由于废旧橡胶粉仍然具有交联网状结构，其表面呈惰性，这也是橡胶粉回收利用的一大难题。它很难与主体材料产生良好的界面相容性，根据应用需要可以有目的地改变胶粉表面的物理化学性质，如表面结构和官能团、表面能、表面润湿性和表面吸附性等，以满足现代新材料、新工艺和新技术发展的需要。目前，废旧胶粉改性的主要方法有物理法、化学法、机械法和生物法等。其中尤其以物理方法效率高、污染小而受到推崇。但利用室温、常压介质阻挡等离子体对废旧橡胶粉表面处理的改性技术还未见有报道。Since waste rubber powder still has a cross-linked network structure, its surface is inert, which is also a major problem in the recycling of rubber powder. It is difficult to produce good interfacial compatibility with the host material, and the physical and chemical properties of the surface of the rubber powder, such as surface structure and functional groups, surface energy, surface wettability and surface adsorption, can be purposefully changed according to the application needs, so as to Meet the needs of modern new materials, new technology and new technology development. At present, the main methods of modification of waste rubber powder are physical method, chemical method, mechanical method and biological method. Among them, the physical method is highly praised for its high efficiency and low pollution. However, there is no report on the modification technology of the surface treatment of waste rubber powder by using room temperature and normal pressure dielectric barrier plasma.
发明内容Contents of the invention
本发明的目的是针对现有技术的不足而提供的一种改善废旧橡胶粉表面亲水性的方法，其特点是在室温、大气压的开放条件下，采用等离子体处理废旧橡胶粉获得表面改性的废旧橡胶粉。The purpose of the present invention is to provide a method for improving the surface hydrophilicity of waste rubber powder in view of the deficiencies in the prior art, which is characterized in that the waste rubber powder is treated with plasma to obtain surface modification under the open conditions of room temperature and atmospheric pressure. waste rubber powder.
本发明的目的由以下技术措施实现，其中所述原料的份数除特殊说明外，均为重量份数。The object of the present invention is achieved by the following technical measures, wherein the parts of the raw materials are parts by weight unless otherwise specified.
改善废旧橡胶粉表面亲水性的方法包括以下步骤：The method for improving the surface hydrophilicity of waste rubber powder comprises the following steps:
将废旧橡胶粉10-100份置于等离子体处理装置中，在室温、大气压的开放环境下，将等离子体喷射到废旧橡胶粉表面，使废旧橡胶粉在等离子体氛围中运动处理，处理废旧橡胶粉的功率为10W-5000W，时间为2.0s-300s，生成废旧橡胶粉等离子体改性粉体。Put 10-100 parts of waste rubber powder in a plasma treatment device, spray plasma onto the surface of waste rubber powder in an open environment at room temperature and atmospheric pressure, and make the waste rubber powder move in the plasma atmosphere to process waste rubber The power of the powder is 10W-5000W, and the time is 2.0s-300s to generate plasma-modified powder of waste rubber powder.
废旧橡胶粉为废旧轮胎胶粉、废旧氟橡胶胶粉或废旧防潮垫橡胶粉。The waste rubber powder is waste tire rubber powder, waste fluorine rubber powder or waste moisture-proof pad rubber powder.
等离子体为氮气、空气和功能性气体中的至少一种，其中氮气的纯度为99.99％，氮气与空气的气体摩尔比为0.1-1，功能性气体与氮气或空气的摩尔比为0.001-0.3，同时流经等离子体形成区形成等离子体氛围。The plasma is at least one of nitrogen, air and functional gas, wherein the purity of nitrogen is 99.99%, the gas molar ratio of nitrogen to air is 0.1-1, and the molar ratio of functional gas to nitrogen or air is 0.001-0.3 , while flowing through the plasma formation area to form a plasma atmosphere.
功能性气体为氧气、二氧化硫、硅氧烷气体及丙烯酸、甲基丙烯酸、丙烯酸甲酯和甲基丙烯酸甲酯蒸汽中的至少一种。The functional gas is at least one of oxygen, sulfur dioxide, siloxane gas, and vapors of acrylic acid, methacrylic acid, methyl acrylate and methyl methacrylate.
按上述方法制备得到的表面亲水性改善的废旧橡胶粉。The waste rubber powder with improved surface hydrophilicity prepared by the above method.
表面亲水性改善的废旧橡胶粉用于热塑性高分子材料的改性、高分子弹性体复合材料的改性。The waste rubber powder with improved surface hydrophilicity is used for the modification of thermoplastic polymer materials and the modification of polymer elastomer composite materials.
性能测试Performance Testing
1.废旧轮胎胶粉在等离子体处理前后亲水性的变化1. Changes in hydrophilicity of waste tire rubber powder before and after plasma treatment
由图2可知，废旧轮胎胶粉在未经等离子体处理前具有疏水性，胶粉完全浮于水的表面；经过等离子体处理后具有很强的亲水性，均匀地悬浮在水中。It can be seen from Figure 2 that waste tire rubber powder is hydrophobic before plasma treatment, and the rubber powder completely floats on the surface of water; after plasma treatment, it has strong hydrophilicity and is evenly suspended in water.
2.废旧轮胎胶粉水接触角变化情况2. Changes in water contact angle of waste tire rubber powder
测试结果表明当等离子体处理时间为120s时，只需30W的功率，废旧轮胎胶粉的水接触角就由未处理的124.7°降为39.4°，再增加功率到40W，水接触角为零，表明此时废旧轮胎胶粉已由疏水性转变为亲水性，详见表1所示。The test results show that when the plasma treatment time is 120s, only 30W of power is needed, and the water contact angle of waste tire rubber powder is reduced from 124.7° to 39.4°, and the water contact angle is zero when the power is increased to 40W. It shows that the waste tire rubber powder has changed from hydrophobicity to hydrophilicity at this time, as shown in Table 1 for details.
3.废旧轮胎胶粉水接触角随等离子体处理时间的变化情况3. Variation of water contact angle of waste tire rubber powder with plasma treatment time
实验结果表明，当等离子体处理功率为80W时，处理时间仅为10s，废旧轮胎胶粉的水接触角就由124.7°降为0°，表明等离子体处理在适当的功率条件下，其处理效率很高，详见表2所示。The experimental results show that when the plasma treatment power is 80W, the treatment time is only 10s, and the water contact angle of the waste tire rubber powder is reduced from 124.7° to 0°, which shows that the treatment efficiency of the plasma treatment is high under the appropriate power condition. Very high, see Table 2 for details.
4.等离子体处理前后胶粉表面元素的X光电子能谱分析4. X-ray photoelectron spectroscopy analysis of rubber powder surface elements before and after plasma treatment
由表3数据得知胶粉表面氧元素含量由等离子体处理前的8.12％增加至12.54％，氮元素含量由0.63％增加至1.2％。本发明得到的胶粉表面含氧基团和含氮基团均较处理前有一定程度增加，分析结果表明等离子体处理可获得表面官能化的具有化学活性的胶粉。From the data in Table 3, it can be seen that the oxygen content on the surface of rubber powder increased from 8.12% before plasma treatment to 12.54%, and the nitrogen content increased from 0.63% to 1.2%. Oxygen-containing groups and nitrogen-containing groups on the surface of the rubber powder obtained by the present invention are increased to a certain extent compared with those before treatment, and the analysis results show that the surface functionalized rubber powder with chemical activity can be obtained by plasma treatment.
5.等离子体表面改性废旧橡胶粉对复合材料力学性能的影响。5. Effect of plasma surface modification of waste rubber powder on the mechanical properties of composite materials.
测试结果表明，经等离子体表面改性后的GTR能使复合材料的力学性能得到显著改善，当废旧轮胎胶粉(GTR)替代丁苯橡胶(NBR)20重量份时，未经改性的GTR/NBR复合材料的拉伸强度为2.4MPa，经本发明改性的GTR/NBR复合材料的拉伸强度3.4MPa，提高了约42％；撕裂强度由未改性前的15.0KN/m提高至19.1KN/m；100％定伸应力由1.7MPa提高至1.9MPa，详见图3、图4和图5所示。这是由于经表面改性后，GTR表面呈亲水性，其与NBR基体的相容性得以改善，改善了复合材料的综合力学性能。未改性的GTR由于其表面的非极性特征，导致GTR在极性聚合物NBR基体中难以分散，所制备的复合材料力学性能差。The test results show that the mechanical properties of the composite material can be significantly improved by the plasma surface modified GTR. The tensile strength of the /NBR composite material is 2.4MPa, and the tensile strength of the GTR/NBR composite material modified by the present invention is 3.4MPa, which has increased by about 42%; the tear strength is improved by 15.0KN/m before the modification to 19.1KN/m; 100% modulus stress increased from 1.7MPa to 1.9MPa, as shown in Figure 3, Figure 4 and Figure 5 for details. This is because after surface modification, the surface of GTR is hydrophilic, and its compatibility with NBR matrix is improved, which improves the comprehensive mechanical properties of the composite material. Due to the non-polar characteristics of the surface of unmodified GTR, it is difficult to disperse GTR in the polar polymer NBR matrix, and the mechanical properties of the prepared composite are poor.
本发明具有如下优点：The present invention has the following advantages:
(1)工艺流程短、工艺简单、可控性强、无需后处理、自动化程度高、能耗低、无污染、易实现连续化操作。(1) Short process flow, simple process, strong controllability, no need for post-processing, high degree of automation, low energy consumption, no pollution, and easy to realize continuous operation.
(2)废旧橡胶粉表面产生同性相斥效果，有效防止粉体在共混物基体中团聚，获得废旧橡胶粉尺寸分布均匀的聚合物复合材料。(2) The same-sex repulsion effect is generated on the surface of waste rubber powder, which effectively prevents the powder from agglomerating in the blend matrix, and obtains a polymer composite material with uniform size distribution of waste rubber powder.
(3)废旧橡胶粉胶粉内部的弹性结构不会改变，其颗粒分布均匀、分布范围窄、与相应的高分子复合后的综合性能优异。(3) The elastic structure inside the waste rubber powder will not change, and its particle distribution is uniform, the distribution range is narrow, and the comprehensive performance after compounding with the corresponding polymer is excellent.
(4)本发明采用介质阻挡等离子体放电对废旧橡胶粉进行表面改性，效率高，速度快，有利于工业化生产，为废橡胶粉的高值化利用提供了新的技术路线。(4) The present invention uses dielectric barrier plasma discharge to modify the surface of waste rubber powder, which has high efficiency and high speed, is conducive to industrial production, and provides a new technical route for high-value utilization of waste rubber powder.
附图说明Description of drawings
图1为废旧橡胶粉改性用低温等离子体发生装置结构示意图Figure 1 is a schematic diagram of the structure of a low-temperature plasma generator for the modification of waste rubber powder
1.电极，2.等离子体发生器，3.废旧橡胶粉，4 220V电压，5变压器，6等离子体电源。1. Electrode, 2. Plasma generator, 3. Waste rubber powder, 4 220V voltage, 5 Transformer, 6 Plasma power supply.
图2为常压室温等离子体处理前后废旧橡胶粉在水中悬浮实验对比Figure 2 is a comparison of the suspension experiments of waste rubber powder in water before and after atmospheric pressure and room temperature plasma treatment
A原GTR B等离子体改性GTRA original GTR B plasma modified GTR
图3为室温、大气压下等离子体改性对GTR/NBR复合材料拉伸强度的影响Figure 3 shows the effect of plasma modification on the tensile strength of GTR/NBR composites at room temperature and atmospheric pressure
图4为室温、大气压下等离子体改性对GTR/NBR复合材料撕裂强度的影响Figure 4 shows the effect of plasma modification on the tear strength of GTR/NBR composites at room temperature and atmospheric pressure
图5为室温、大气压下等离子体改性对GTR/NBR复合材料100％定伸应力的影响Figure 5 shows the effect of plasma modification on the 100% modulus stress of GTR/NBR composites at room temperature and atmospheric pressure
具体实施方式Detailed ways
下面通过实施例对本发明进行具体的描述，有必要在此指出的是以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容作出一些非本质的改进和调整。The present invention is specifically described below through the examples, it is necessary to point out that the following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the protection scope of the present invention, those skilled in the art can according to above-mentioned this The content of the invention makes some non-essential improvements and adjustments.
实施例1Example 1
将废旧轮胎胶粉10份置于等离子体处理装置中。如图1所示(或加装等离子体传输装置，实现连续生产)，该容器或载体置于室温、大气压等离子体喷射装置的下方，距上方石英片距离为2mm，废旧橡胶粉平铺于下方直径为70mm的石英玻璃器皿中，胶粉的平铺平均厚度约为1mm。开启等离子体设备，在室温、空气气氛中进行等离子体处理，处理时间为300s，功率为10W。Put 10 parts of waste tire rubber powder in a plasma treatment device. As shown in Figure 1 (or add a plasma transmission device to realize continuous production), the container or carrier is placed under the room temperature and atmospheric pressure plasma spray device, and the distance from the upper quartz plate is 2mm, and the waste rubber powder is laid on the bottom In a quartz glass vessel with a diameter of 70mm, the average thickness of the rubber powder is about 1mm. The plasma equipment was turned on, and the plasma treatment was performed at room temperature and in an air atmosphere. The treatment time was 300s, and the power was 10W.
实施例2Example 2
将废旧氟橡胶粉100份置于等离子体处理专用设备中。如图1所示(或加装等离子体传输装置，实现连续生产)，该容器或载体置于室温、大气压等离子体喷射装置的下方，距上方石英片距离为2mm，废旧橡胶粉平铺于下方直径为70mm的石英玻璃器皿中，胶粉的平铺平均厚度为1mm。开启等离子体设备，在室温、氮气气氛中进行等离子体处理，处理时间为2s，功率为5000W。Place 100 parts of waste fluororubber powder in special equipment for plasma treatment. As shown in Figure 1 (or add a plasma transmission device to realize continuous production), the container or carrier is placed under the room temperature and atmospheric pressure plasma spray device, and the distance from the upper quartz plate is 2mm, and the waste rubber powder is laid on the bottom In a quartz glass vessel with a diameter of 70mm, the average thickness of the rubber powder is 1mm. The plasma equipment was turned on, and plasma treatment was performed at room temperature in a nitrogen atmosphere, the treatment time was 2s, and the power was 5000W.
实施例3Example 3
将废旧防潮垫胶粉60份置于等离子体处理专用设备中。如图1所示，该容器或载体置于常压、室温等离子体喷射装置的下方，距上方石英片距离为2mm，废旧橡胶粉平铺于下方直径为70mm的石英玻璃器皿中，胶粉的平铺平均厚度为1mm。开启等离子体设备，在空气与氮气的摩尔比为1，丙烯酸蒸汽与氮气摩尔比为0.1的气氛中进行等离子体处理，处理时间为120s，功率为80W。Put 60 parts of the waste moisture-proof pad rubber powder in the special equipment for plasma treatment. As shown in Figure 1, the container or carrier is placed under the normal pressure and room temperature plasma spraying device, and the distance from the upper quartz plate is 2mm. The average thickness of the tiles is 1 mm. The plasma equipment was turned on, and plasma treatment was performed in an atmosphere with a molar ratio of air to nitrogen of 1 and a molar ratio of acrylic acid vapor to nitrogen of 0.1, with a treatment time of 120 s and a power of 80 W.
表1废旧橡胶粉水接触角随等离子体处理功率的变化(废旧轮胎胶粉，处理时间为120s)Table 1 Variation of water contact angle of waste rubber powder with plasma treatment power (waste tire rubber powder, treatment time is 120s)
表2废旧橡胶粉水接触角随等离子体处理时间的变化Table 2 Variation of water contact angle of waste rubber powder with plasma treatment time
表3等离子体改性前后废轮胎胶粉的表面光电子能谱元素分析Table 3 Surface photoelectron spectroscopy elemental analysis of waste tire rubber powder before and after plasma modification
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010167618 CN101955593A (en) | 2010-05-11 | 2010-05-11 | Method for improving surface hydrophilicity of waste rubber powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010167618 CN101955593A (en) | 2010-05-11 | 2010-05-11 | Method for improving surface hydrophilicity of waste rubber powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101955593A true CN101955593A (en) | 2011-01-26 |
Family
ID=43483202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010167618 Pending CN101955593A (en) | 2010-05-11 | 2010-05-11 | Method for improving surface hydrophilicity of waste rubber powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101955593A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305197A (en) * | 2013-06-08 | 2013-09-18 | 西南石油大学 | Cement paste toughening agent and application of cement paste toughening agent in preparation of cementing flexible cement paste |
| CN104311865A (en) * | 2014-10-13 | 2015-01-28 | 重庆交通大学 | Rubber surface modification method |
| CN106079012A (en) * | 2016-06-21 | 2016-11-09 | 南京林业大学 | A kind of method utilizing steam dielectric barrier discharge plasma to strengthen agricultural crop straw glue performance |
| CN108822734A (en) * | 2018-06-22 | 2018-11-16 | 安徽快来防水防腐有限公司 | A kind of high temperature resistant, the preparation method of the SBS of resistance to ultralow temperature modified asphalt waterproof coiled material |
| CN109121277A (en) * | 2018-08-23 | 2019-01-01 | 国网天津市电力公司电力科学研究院 | A kind of dielectric barrier discharge system and method improving rubber surface hydrophilicity |
| CN109503865A (en) * | 2018-12-18 | 2019-03-22 | 广西远景资源再生有限公司 | A kind of technique that rubber powder surface is modified |
| CN111621058A (en) * | 2020-05-15 | 2020-09-04 | 大连理工大学 | Method and device for regenerating waste rubber by low-temperature plasma desulfurization |
| CN112830723A (en) * | 2021-02-26 | 2021-05-25 | 西南石油大学 | A high-temperature elastic-ductile cement slurry system for shale oil and gas wells |
| CN113461866A (en) * | 2021-07-28 | 2021-10-01 | 四川大学 | Hydrophilic waste rubber powder, high-strength composite hydrogel and preparation method and application thereof |
| CN114350003A (en) * | 2022-01-18 | 2022-04-15 | 库博标准投资有限公司 | Method for changing surface activity of rubber material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858091A (en) * | 2006-04-25 | 2006-11-08 | 扬州大学 | Method for treating fluoro rubber by vacuum radio frequency plasma polarization |
-
2010
- 2010-05-11 CN CN 201010167618 patent/CN101955593A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858091A (en) * | 2006-04-25 | 2006-11-08 | 扬州大学 | Method for treating fluoro rubber by vacuum radio frequency plasma polarization |
Non-Patent Citations (1)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库工程科技I辑》 20080515 童薇 常压空气介质阻挡等离子体改性氟橡胶表面的研究 第4-26页 1-6 , 第5期 2 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305197A (en) * | 2013-06-08 | 2013-09-18 | 西南石油大学 | Cement paste toughening agent and application of cement paste toughening agent in preparation of cementing flexible cement paste |
| CN103305197B (en) * | 2013-06-08 | 2015-06-10 | 西南石油大学 | Cement paste toughening agent and application of cement paste toughening agent in preparation of cementing flexible cement paste |
| CN104311865A (en) * | 2014-10-13 | 2015-01-28 | 重庆交通大学 | Rubber surface modification method |
| CN104311865B (en) * | 2014-10-13 | 2017-04-05 | 重庆交通大学 | A kind of rubber surface method of modifying |
| CN106079012A (en) * | 2016-06-21 | 2016-11-09 | 南京林业大学 | A kind of method utilizing steam dielectric barrier discharge plasma to strengthen agricultural crop straw glue performance |
| CN108822734A (en) * | 2018-06-22 | 2018-11-16 | 安徽快来防水防腐有限公司 | A kind of high temperature resistant, the preparation method of the SBS of resistance to ultralow temperature modified asphalt waterproof coiled material |
| CN109121277A (en) * | 2018-08-23 | 2019-01-01 | 国网天津市电力公司电力科学研究院 | A kind of dielectric barrier discharge system and method improving rubber surface hydrophilicity |
| CN109503865A (en) * | 2018-12-18 | 2019-03-22 | 广西远景资源再生有限公司 | A kind of technique that rubber powder surface is modified |
| CN111621058A (en) * | 2020-05-15 | 2020-09-04 | 大连理工大学 | Method and device for regenerating waste rubber by low-temperature plasma desulfurization |
| CN112830723A (en) * | 2021-02-26 | 2021-05-25 | 西南石油大学 | A high-temperature elastic-ductile cement slurry system for shale oil and gas wells |
| CN113461866A (en) * | 2021-07-28 | 2021-10-01 | 四川大学 | Hydrophilic waste rubber powder, high-strength composite hydrogel and preparation method and application thereof |
| CN114350003A (en) * | 2022-01-18 | 2022-04-15 | 库博标准投资有限公司 | Method for changing surface activity of rubber material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101955593A (en) | Method for improving surface hydrophilicity of waste rubber powder | |
| CN103030828B (en) | A kind of preparation method of rubber-based composite material with superhydrophobic surface | |
| CN104324524B (en) | A kind of preparation method of superhydrophobic superlipophilic ultralight sponge | |
| CN105037865B (en) | A kind of modified waste rubber powder and preparation method and application | |
| CN102226034B (en) | Preparation method of glass-fiber-reinforced epoxy resin composite material modified by circuit board recovered powder and nanoparticles | |
| CN102584886A (en) | Silane coupling agent and preparation method thereof | |
| CN105670040A (en) | Loaded rubber anti-aging agent and preparation method and application thereof | |
| JP5757582B2 (en) | Desulfurization of rubber and other elastomers | |
| CN103497437B (en) | Light high-strength brominated butyl rubber airtight material and preparation method and application thereof | |
| JP5809783B2 (en) | Resin composition for gasket, method for producing the same, and gasket for secondary battery | |
| CN108641150A (en) | A kind of repeatable processing rubber material and preparation method thereof | |
| CN108262332A (en) | A kind of nuisanceless recovery method of photovoltaic module | |
| Dutta et al. | Graphene and graphene-based nanomaterials for biological and environmental applications for sustainability | |
| CN103265828A (en) | Solid phase grafting modification method of regeneration pyrolysis carbon black | |
| Whba et al. | Intrinsic challenges and strategic approaches for enhancing the potential of natural rubber and its derivatives: A review | |
| CN103897217B (en) | A kind of electron beam irradiation modified white carbon black improves the method for black filled rubber performance | |
| CN105694239B (en) | Waste printed circuit board nonmetal powder/ethylene propylene diene monomer composite material and preparation method thereof | |
| Liu et al. | Rapid Preparation Triggered by Visible Light for Tough Hydrogel Sensors with Low Hysteresis and High Elasticity: Mechanism, Use and Recycle‐by‐Design | |
| CN115368649B (en) | Anti-skid rubber sole and preparation method thereof | |
| CN1847315A (en) | Polyarylene sulfide resin composition and molded article therefrom | |
| CN106565961B (en) | Polypropylene lithium ion battery separator intensity strengthening agent and utilize battery diaphragm prepared by it | |
| Cheng et al. | Radiation processing for modification of polymers. | |
| CN100577746C (en) | A modification method for high-structure superconducting carbon black BP2000 | |
| CN104356420A (en) | Method for grafting polyethylene film with acrylic acid under initiating action of air plasma under atmospheric pressure | |
| CN101665599A (en) | High-strength environmentally-friendly rubber powder rubber plate 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 | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20110126 |