CN112341680A - Method for preparing anti-aging nitrile rubber from modified carbon nano tubes - Google Patents
Method for preparing anti-aging nitrile rubber from modified carbon nano tubes Download PDFInfo
- Publication number
- CN112341680A CN112341680A CN202011467793.XA CN202011467793A CN112341680A CN 112341680 A CN112341680 A CN 112341680A CN 202011467793 A CN202011467793 A CN 202011467793A CN 112341680 A CN112341680 A CN 112341680A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- nano tube
- aging
- nitrile rubber
- modified carbon
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application provides a method for preparing anti-aging nitrile rubber by using modified carbon nanotubes, belonging to the field of high polymer materials and material preparation. According to the method for preparing the anti-aging nitrile rubber by using the modified carbon nano tube, firstly, after the carbon nano tube is treated by mixed acid, the carbon nano tube is modified by zinc nitrate hexahydrate and sodium borohydride, and nano zinc oxide is grafted on the carbon nano tube to obtain the modified carbon nano tube filler. Then, the nitrile rubber co-mixed rubber with high strength, good aging resistance and good comprehensive performance is prepared by mixing and vulcanizing the modified filler, nitrile rubber, ethylene propylene diene monomer, sulfur, an auxiliary crosslinking agent, an accelerator, an anti-aging agent, carbon black and other auxiliary agents.
Description
Technical Field
The application relates to the field of high polymer materials and material preparation, in particular to a method for preparing anti-aging nitrile rubber by using modified carbon nanotubes.
Background
Nitrile rubber (NBR) is an unsaturated polar rubber obtained by random copolymer of butadiene and acrylonitrile, and has excellent oil resistance and wear resistance. Ethylene Propylene Diene Monomer (EPDM) is a nonpolar rubber with saturated main chain, and has excellent high temperature resistance, ozone aging resistance and electric insulation performance. The high temperature resistance of NBR can be improved by using both NBR and EPDM.
The NBR and EPDM rubbers have a large difference in polarity and saturation, and have many problems in combination, such as poor co-vulcanization of the two rubbers, over-vulcanization of one phase and under-vulcanization of the other phase during vulcanization, resulting in poor physical and mechanical properties of the vulcanizate.
Carbon Nanotubes (CNTs) are carbon materials with extremely high physical and mechanical properties, and the physical and mechanical properties of rubber materials can be improved by adding a small amount of Carbon Nanotubes (CNTs). The CNTs have extremely large length-diameter ratio, have the effect of sewing NBR and EPDM, and play a role in forced compatibilization. However, the CNTs have few surface active groups, when the CNTs are added into a rubber material, strong interaction cannot be established between the CNTs and a material matrix, the CNTs are easy to extract when stressed, and the CNTs cannot bear external force borne by the material; and the surface energy of the CNTs is extremely high, if the CNTs are added into a rubber material only by a simple mode, the agglomeration phenomenon is extremely easy to generate, the size of the agglomerated carbon nano tube is increased, the carbon nano tube can not play a role in reinforcement in a stress process, but can be easily used as a stress concentration point to damage an original filler network to become a defect, and the mechanical property of the material is reduced.
Zinc oxide (ZnO) is an important activator in the rubber vulcanization process, and the vulcanization-activation effect of the zinc oxide (ZnO) is related to the cross-linked network of the vulcanized rubber. Not only can be used as a vulcanization accelerator, but also has certain reinforcing effect on rubber. However, due to the characteristics of high surface energy and growth along a specific crystal plane, nano ZnO is extremely easy to agglomerate, and the industrial application of nano ZnO in rubber composite materials is seriously hindered.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for modifying carbon nanotubes to solve the technical problem of poor dispersibility of the existing carbon nanotubes so as to obtain the nitrile rubber blend rubber with good aging resistance and high mechanical strength.
In order to achieve the above object, the technical solution of the present invention is as follows:
acidifying the carbon nano tube to prepare a carboxylated carbon nano tube: mixing 3g of carbon nano tube with 90ml of concentrated sulfuric acid and 30ml of concentrated nitric acid, performing ultrasonic dispersion for 2 hours, refluxing the obtained carbon nano tube suspension for 7 hours at 50 ℃, performing suction filtration and washing by adopting PVDF (polyvinylidene fluoride), and drying for 24 hours to obtain a carboxylated carbon nano tube;
dissolving 6g of zinc nitrate hexahydrate in 600ml of deionized water, dissolving a carboxylated carbon nanotube in a 10mg/ml zinc nitrate solution, ultrasonically dispersing for 1h, stirring for 6h at room temperature, adding 0.354g of sodium borohydride, stirring for 1h at room temperature, filtering, washing and drying for 24h to obtain a modified carbon nanotube grafted with nano zinc oxide;
and banburying and vulcanizing the modified carbon nano tube, the nitrile rubber and the ethylene propylene diene monomer to prepare the high-strength anti-aging nitrile rubber co-mixed rubber.
The nitrile rubber co-mixed rubber prepared by the method not only can obtain good mechanical property and heat resistance, but also can improve the compatibility of nitrile rubber and ethylene propylene diene monomer, and simultaneously improves the dispersibility of carbon nano tubes and nano zinc oxide in rubber materials.
And (3) banburying the carbon nano tube grafted with the nano zinc oxide with the nitrile rubber and the ethylene propylene rubber through mixed acid treatment and vulcanization to obtain the nitrile rubber/ethylene propylene diene monomer blended rubber. Especially, the carbon nano tube grafted with the nano zinc oxide can not only improve the dispersibility of the carbon nano tube and the nano zinc oxide, but also enable the hybrid material to have the superior performances of the carbon nano tube and the nano zinc oxide.
The unique structure of carbon nanotubes dictates that it possess many specific physical and chemical properties. The covalent bond of C ═ C constituting the carbon nanotube is the most stable chemical bond in nature, so that the carbon nanotube has very excellent mechanical properties. Since carbon atoms constituting the carbon nanotube are bonded to each other by a sigma bond, it is presumed that the carbon nanotube has very high axial strength, elastic modulus and toughness as soon as it is produced. At present, the modulus calculated by using an idealized model is generally used as the theoretical modulus value of the carbon nano tube, and the value is about 1-5TPa and about 5 times of that of a steel material; according to the external force value of the carbon nanotube to be bent, which is calculated by Lieber et al through an atomic force microscope, the tensile strength of an ideal multi-wall carbon nanotube can be roughly calculated to reach 250GPa, the tensile strength of the multi-wall carbon nanotube is continuously increased along with the reduction of the diameter of the multi-wall carbon nanotube, theoretically, the tensile strength of a single-wall carbon nanotube is about 1TPa, the tensile strength is one hundred times of that of a steel material, and meanwhile, the carbon nanotube only has the density equivalent to one sixth of that of the steel material. Meanwhile, the carbon nano tube has a very large length-diameter ratio, has a 'sewing' effect on the blending glue, and plays a role in forced compatibilization.
In rubber, zinc oxide may be present primarily as a vulcanization activator, and may sometimes be added to the rubber as a rubber filler to increase the stress at elongation, hardness, and thermal conductivity of the compound. Compared with the prior art, the nano zinc oxide has the characteristics of high reaction activity, large specific surface area, small particle size and the like. Research shows that the nanometer zinc oxide particle can produce combination reaction with rubber molecule, i.e. grafting between nanometer particle and rubber molecule. Therefore, the comprehensive performance of the rubber is also improved to a great extent, mainly comprising the wear resistance, the tearing strength and the like of the rubber, and the performance of the final finished product is also improved correspondingly. The use of the nano zinc oxide can improve the processing safety of the rubber material to a great extent, improve the performances of the rubber material to a certain extent, such as hot air aging property, mechanical property and adhesive property of a framework material, and obviously reduce the production cost. Relevant researches show that the mechanical properties such as tensile stress and tensile strength of the composite material are obviously improved along with the increase of the addition amount of the nano zinc oxide, and when the addition amount exceeds a certain amount, the comprehensive properties of the composite material begin to be reduced.
The carbon nano tube is acidified by concentrated sulfuric acid and concentrated nitric acid in a proper proportion, carboxyl oxygen-containing groups can be introduced to the surface of the carbon nano tube, and the interaction between the carbon nano tube and a rubber matrix can be improved to improve the dispersibility of the carbon nano tube in rubber and the interfacial force between the carbon nano tube and the rubber matrix. Meanwhile, the carbon nano tube subjected to acidification treatment can cause defects on the surface of the carbon nano tube, and is beneficial to loading other substances on the surface of the carbon nano tube.
6g of zinc nitrate hexahydrate and 0.354g of sodium borohydride are mixed with the carboxylated carbon nano tube, and the secondary modification is continuously carried out, so that the nano zinc oxide has the excellent performance of nano zinc oxide.
According to the application, the carbon nano tube is grafted with the nano zinc oxide, so that the hybrid material overcomes the defect of a single material, and has excellent performances of the two. After being blended with the nitrile rubber and the ethylene propylene diene monomer, the mechanical property of the blended rubber is improved, and the blended rubber has excellent heat resistance and other properties, can adapt to specific use environment conditions, and has wide market prospect and application.
Detailed Description
Examples
The embodiment provides a method for preparing nitrile rubber blending rubber by using modified carbon nanotubes, which comprises the following steps:
(1) mixing 3g of carbon nano tube with 90ml of concentrated sulfuric acid and 30ml of concentrated nitric acid, performing ultrasonic dispersion for 2 hours, refluxing the obtained carbon nano tube suspension for 7 hours at 50 ℃, performing suction filtration and washing by adopting PVDF (polyvinylidene fluoride), and drying for 24 hours to obtain a carboxylated carbon nano tube;
(2) dissolving 6g of zinc nitrate hexahydrate in 600ml of deionized water, dissolving a carboxylated carbon nanotube in a 10mg/ml zinc nitrate solution, ultrasonically dispersing for 1h, stirring for 6h at room temperature, adding 0.354g of sodium borohydride, stirring for 1h at room temperature, filtering, washing and drying for 24h to obtain a modified carbon nanotube grafted with nano zinc oxide;
(3) mixing nitrile rubber, ethylene propylene diene monomer and modified carbon nano tube according to the weight ratio of 70: 30: 5 and other auxiliary agents are subjected to blending and banburying in an internal mixer at the temperature of 60 ℃, discharging is carried out after torque balance, and after the mixture is completely cooled, the mixture is fed into an open mill and thinly passed for 15 times for sheet discharging;
(4) vulcanizing the material in the step (3) at the temperature of 170 ℃, wherein the vulcanization time is positive vulcanization time Tc90 + 5 min.
The physical properties of the nitrile rubber/ethylene propylene diene monomer blended rubber prepared from the modified carbon nanotube and the nitrile rubber/ethylene propylene diene monomer blended rubber prepared from the unmodified carbon nanotube are shown in the following table.
As can be seen from the table, the nitrile rubber blend rubber prepared by the modified carbon nano tube has better mechanical property and aging resistance.
Claims (4)
1. The method for preparing the anti-aging nitrile rubber by using the modified carbon nano tube is characterized by comprising the following steps of:
the carbon nano tube is treated by mixed acid to prepare a carboxylated carbon nano tube; stirring the carboxylated carbon nanotube and zinc nitrate hexahydrate for 6 hours at room temperature, adding sodium borohydride, stirring for 1 hour at room temperature, filtering, washing and drying to obtain a modified carbon nanotube grafted with nano zinc oxide;
nitrile butadiene rubber, ethylene propylene diene monomer, modified carbon nano tubes, sulfur, an auxiliary crosslinking agent accelerator, an anti-aging agent, carbon black and other auxiliary agents are mixed and vulcanized to prepare the nitrile butadiene rubber compound with high strength, good aging resistance and good comprehensive performance.
2. The method for preparing the aging-resistant nitrile rubber from the modified carbon nanotubes as claimed in claim 1, wherein the preparation method of the carboxylated carbon nanotubes comprises the following steps: adding 3g of carbon nano tube into a mixed acid solution prepared from 90ml of concentrated sulfuric acid and 30ml of concentrated nitric acid, performing ultrasonic dispersion for 2h, refluxing the obtained carbon nano tube suspension for 7h at 50 ℃, performing suction filtration and washing by adopting PVDF, and drying for 24h to obtain the carboxylated carbon nano tube.
3. The method for preparing the aging-resistant nitrile rubber from the modified carbon nanotubes according to claim 1, wherein the method for preparing the modified carbon nanotubes grafted with the nano zinc oxide comprises the following steps: dissolving 6g of zinc nitrate hexahydrate in 600ml of deionized water, dissolving the carboxylated carbon nanotube in 10mg/ml of zinc nitrate solution, ultrasonically dispersing for 1h, stirring for 6h at room temperature, adding 354mg of sodium borohydride, stirring for 1h at room temperature, filtering, washing, drying for 24h, and obtaining the modified carbon nanotube grafted with nano zinc oxide.
4. The method for preparing the aging-resistant nitrile rubber by using the modified carbon nanotubes as claimed in claim 1, wherein the banburying temperature is 60 ℃, the vulcanization temperature is 170-175 ℃, and the pressure is 10-12 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011467793.XA CN112341680A (en) | 2020-12-14 | 2020-12-14 | Method for preparing anti-aging nitrile rubber from modified carbon nano tubes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011467793.XA CN112341680A (en) | 2020-12-14 | 2020-12-14 | Method for preparing anti-aging nitrile rubber from modified carbon nano tubes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112341680A true CN112341680A (en) | 2021-02-09 |
Family
ID=74428185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011467793.XA Pending CN112341680A (en) | 2020-12-14 | 2020-12-14 | Method for preparing anti-aging nitrile rubber from modified carbon nano tubes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112341680A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789302A (en) * | 2005-12-28 | 2006-06-21 | 华东理工大学 | In-situ grafted black carbon, its preparation method and reinforced rubber containing the same |
| CN1891632A (en) * | 2005-07-04 | 2007-01-10 | 同济大学 | Method for preparing nano zinc oxide powder |
| CN103694505A (en) * | 2013-12-24 | 2014-04-02 | 苏州华东橡胶工业有限公司 | Compound carbon nanotube and rubber material and preparation method thereof |
| CN104059257A (en) * | 2014-06-20 | 2014-09-24 | 安徽嘉木橡塑工业有限公司 | Abrasion-resistance oil-resistance rubber composite material |
| CN106009131A (en) * | 2016-06-14 | 2016-10-12 | 航天材料及工艺研究所 | Preparing method for antioxidant-modified carbon nano tube/hydrogenated butadiene-acrylonitrile rubber |
| CN107673398A (en) * | 2017-10-11 | 2018-02-09 | 北京振兴华龙制冷设备有限责任公司 | A kind of preparation method of Nanometer-sized Rods ZnO and its application for preparing ventilating duct for air-conditioner |
| US20180086901A1 (en) * | 2016-09-23 | 2018-03-29 | Baker Hughes, A Ge Company, Llc | Wear resistant and high temperature resistant elastomer nanocomposites |
| CN109181113A (en) * | 2018-10-09 | 2019-01-11 | 合肥凯大新型材料科技有限公司 | A kind of filler improving rubber stability |
-
2020
- 2020-12-14 CN CN202011467793.XA patent/CN112341680A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1891632A (en) * | 2005-07-04 | 2007-01-10 | 同济大学 | Method for preparing nano zinc oxide powder |
| CN1789302A (en) * | 2005-12-28 | 2006-06-21 | 华东理工大学 | In-situ grafted black carbon, its preparation method and reinforced rubber containing the same |
| CN103694505A (en) * | 2013-12-24 | 2014-04-02 | 苏州华东橡胶工业有限公司 | Compound carbon nanotube and rubber material and preparation method thereof |
| CN104059257A (en) * | 2014-06-20 | 2014-09-24 | 安徽嘉木橡塑工业有限公司 | Abrasion-resistance oil-resistance rubber composite material |
| CN106009131A (en) * | 2016-06-14 | 2016-10-12 | 航天材料及工艺研究所 | Preparing method for antioxidant-modified carbon nano tube/hydrogenated butadiene-acrylonitrile rubber |
| US20180086901A1 (en) * | 2016-09-23 | 2018-03-29 | Baker Hughes, A Ge Company, Llc | Wear resistant and high temperature resistant elastomer nanocomposites |
| CN107673398A (en) * | 2017-10-11 | 2018-02-09 | 北京振兴华龙制冷设备有限责任公司 | A kind of preparation method of Nanometer-sized Rods ZnO and its application for preparing ventilating duct for air-conditioner |
| CN109181113A (en) * | 2018-10-09 | 2019-01-11 | 合肥凯大新型材料科技有限公司 | A kind of filler improving rubber stability |
Non-Patent Citations (2)
| Title |
|---|
| 四川省纳米技术协会: "《纳米材料技术研发与应用》", 29 February 2012, 电子科技大学出版社 * |
| 朱路平等: ""多壁碳纳米管负载ZnO纳米复合材料的制备及其光催化性能研究"", 《上海第二工业大学学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9636649B2 (en) | Dispersions comprising discrete carbon nanotube fibers | |
| CN102702591B (en) | Hydrogenated nitrile rubber/carbon nanotube composite material and preparation method thereof | |
| Liu et al. | Preparation of rubber/graphene oxide composites with in-situ interfacial design | |
| CN102634106B (en) | Preparation method of graphene oxide nanobelt/polar rubber composite material | |
| CN107955239B (en) | Hydrogenated nitrile rubber nano composite material containing graphene and preparation method thereof | |
| CN108610511A (en) | A kind of functionalization two-dimensional layer transition metal carbide material f-MXene and preparation method thereof and the application in rubber | |
| CN103694505A (en) | Compound carbon nanotube and rubber material and preparation method thereof | |
| KR101748142B1 (en) | Latex composition, production method therefor, composite material and conductive compact | |
| CN104558708A (en) | Multifunctional vulcanized rubber containing polyvinylpyrrolidone-modified graphene oxide and preparation method of multifunctional vulcanized rubber | |
| CN104893042A (en) | Rubber vulcanized rubber containing ionic liquid modified graphene oxide and preparation method of vulcanized rubber | |
| CN102924763B (en) | Preparation method of high-modulus low-heat carbon nano tube/ rubber composite material | |
| Jia et al. | Advances in rubber/halloysite nanotubes nanocomposites | |
| CN103012819B (en) | Method for preparing acetylacetone polyvinyl alcohol/graphene nanocomposite | |
| CN109796790A (en) | Modified MXenes of a kind of ion insertion agent and preparation method thereof and the application in rubber | |
| CN112341680A (en) | Method for preparing anti-aging nitrile rubber from modified carbon nano tubes | |
| CN106117949A (en) | High-density polyethylene resin based nano composite material and preparation method thereof | |
| CN109206677A (en) | A kind of dissaving polymer modified carbon black surface and its application in rubber processing | |
| CN106543510B (en) | A kind of high-damping rubber material and preparation method thereof | |
| CN113773556B (en) | Double-component composite reinforcing agent for hydrogenated nitrile rubber and preparation method thereof | |
| CN109762221B (en) | Graphene oxide-loaded halloysite modified styrene butadiene rubber and preparation method thereof | |
| CN114957901A (en) | Modified polytetrafluoroethylene resin and preparation method thereof | |
| CN104861219A (en) | Rubber composite material and preparation method thereof | |
| CN110734586B (en) | Method for preparing fluorine-containing nitrile rubber from modified fluorinated graphene | |
| CN1775839A (en) | Method for preparing carbon nano tube/rubber nano composite matcrial by non-acidation treatment | |
| CN114230863B (en) | Graphene and carbon black compound reinforced heat conduction filler and application thereof in preparation of high-strength high-elasticity heat conduction styrene butadiene rubber composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210209 |