CN107857907B - Rubber-plastic and multi-walled carbon nanotube composite elastic matrix and preparation method thereof - Google Patents
Rubber-plastic and multi-walled carbon nanotube composite elastic matrix and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a rubber-plastic and multi-walled carbon nanotube composite elastic matrix and a preparation method thereof, belonging to the technical field of spinning rubber ring formula design. The PVC material comprises nitrile rubber, PVC with high polymerization degree, multi-walled carbon nano tubes, a plasticizer, a stabilizer, a lubricating dispersant, an antioxidant and an anti-aging agent; the dispersion is first pre-formed and then thermally plasticated to form the composite elastomeric matrix. The rubber-plastic and multi-walled carbon nanotube composite elastic matrix is used as a main body material and applied to the formula design of a spinning rubber ring, the manufactured spinning rubber ring can meet the technical requirements of producing modern novel textile fiber yarns by an efficient process, is suitable for the production modes of compact spinning and siro spinning, and can implement the spinning processes of weight basis, large drafting and fine movement.
Description
Technical Field
The invention relates to a rubber-plastic and multi-walled carbon nanotube composite elastic matrix and a preparation method thereof, in particular to a core method for modifying, optimizing and improving the quality of a main material of a spinning rubber ring, and belongs to the technical field of formula design of spinning rubber rings.
Background
At present, the novel textile fiber shows a high-speed development trend of diversification and diversity, the shape, performance or other aspects of the fiber are mainly different from the original traditional fiber, and the novel fiber can be divided into a series of novel natural fiber, novel cellulose fiber, soybean protein fiber, water-soluble fiber, functional fiber, differential fiber, high-performance fiber, high-sensitivity fiber and the like.
The superfine denier fiber, the high modulus conductive metal fiber and other processing aids in the novel textile fiber series have corresponding special performance requirements on a spinning rubber ring drafting process, and the superfine denier fiber is easy to dissociate from a fiber bundle under the action of static electricity and adhesion force, so that the surface of the rubber ring is stuck with 'fancy clothes' to cause frequent yarn defects; the high modulus conductive metal blended fiber has large modulus, poor hand feeling, severe abrasion to the surface of a drafting rubber ring, extremely easy middle concave grooving and even cracking in the yarn guide process, and greatly shortened service life of the spinning rubber ring; various spinning processing aids are easy to migrate, adhere and swell the surface of the rubber ring, the surface of the rubber ring is continuously increased to generate adhesive tape 'blossoming', the broken ends are increased, frequent yarn defects are caused, and the rubber ring is simultaneously viscous and sluggish in operation to generate mechanical waves. The novel textile fiber mainly adopts modern high-efficient spinning technology at present, and the spinning form is for gathering spinning (closely spinning), siro spinning, and its technology embodies weight ration, big draft, fine motion, because receive the influence of above-mentioned novel textile fiber production characteristic, the spinning rubber ring of ordinary rubber and plastic system design manufacturing, the surface easily appears "flower clothing" of leading to smuggleing secretly by static and adhesion in spinning draft in-process, high shear force causes that the interior surface of guide yarn journey tears, bad phenomena such as dished wearing and tearing to arouse the loss and increases by a wide margin, spinning quality stability obviously descends, the maintenance degree of difficulty increases.
Disclosure of Invention
The invention aims to overcome the defects and provides a rubber-plastic and multi-walled carbon nanotube composite elastic matrix and a preparation method thereof.
The technical scheme of the invention is that the rubber-plastic and multi-walled carbon nanotube composite elastic matrix comprises the following components in parts by weight: based on 100 parts of nitrile rubber, 45-75 parts of high-polymerization-degree PVC, 20-30 parts of multi-walled carbon nano tubes, 18-25 parts of plasticizer, 1.5-2.5 parts of stabilizer, 2-3 parts of lubricating dispersant, 1.5 parts of antioxidant and 1 part of anti-aging agent are added.
Further, the acrylonitrile unit in the nitrile rubber accounts for 32-34 wt%, and the raw rubber Mooney viscosity ML (1+4) of the nitrile rubber is 62-68 at 100 ℃. The nitrile rubber belongs to an oil-resistant conductive high-molecular elastomer, and is particularly suitable for being used as a main material to manufacture textile rubber equipment products.
Further, the PVC model with high polymerization degree is P-2500 (the polymerization degree is 2400-2600). The PVC with high polymerization degree belongs to a thermoplastic high-molecular elastomer, and a rubber-plastic system consisting of the PVC and the nitrile rubber has excellent performances of winding resistance, aging resistance, corrosion resistance, reinforcement and wear resistance.
Furthermore, the model of the multi-wall carbon nano tube is a raw powder base model, the length range is 3-60 mu m, and the tube diameter range is 10-60 nm. The composite elastomer formed by the multi-walled carbon nano-tubes and the rubber can greatly improve the physical and chemical comprehensive indexes of the original rubber-plastic system vulcanized rubber, such as dynamic mechanical property, electric conductivity, heat conductivity, corrosion resistance, pressure resistance and the like.
Further, the plasticizer (DOP) is dioctyl phthalate. The plasticizer is a plasticizer of PVC with high polymerization degree, and the rebound resilience and the processing performance of the composite elastic matrix are improved.
Further, the stabilizer is dibutyltin laurate. The stabilizer is a thermal refining thermal degradation resistant processing aid of PVC with high polymerization degree.
Further, the lubricating dispersant is erucamide. The lubricating dispersant helps to improve the dispersion and the binding property of the multi-walled carbon nano-tube in the composite elastomer, and simultaneously can reduce the surface energy of vulcanized rubber.
Further, the antioxidant (2246-S) is 2, 2' -thiobis (4-methyl-6-tert-butylphenol).
Further, the anti-aging agent (RD) is 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer.
The antioxidant and the anti-aging agent can slow down the thermo-oxidative aging process of the composite elastomer in the processing or finished product application process.
The preparation method of the rubber-plastic and multi-walled carbon nanotube composite elastic matrix is characterized by comprising the following steps of:
(1) preparing a dispersion: firstly, weighing 45-75 parts of high-polymerization-degree PVC, 20-30 parts of multi-walled carbon nanotubes, 2-3 parts of a lubricating dispersant, 1-2 parts of an antioxidant and 0.5-1.5 parts of an anti-aging agent according to a weight ratio, putting the weighed materials into a vertical plastic stirrer, stirring for 2-4 minutes, then weighing 1.5-2.5 parts of a stabilizer and 18-25 parts of a plasticizer according to a weight ratio, adding the weighed materials into the stirrer, stirring for 4-6 minutes, controlling the discharge temperature to be 60-70 ℃, bagging after the stirring, and cooling for later use;
(2) banburying and hot plastication: weighing 100 parts of nitrile rubber at a plastication stage according to a weight ratio, putting the nitrile rubber into an internal mixer, carrying out pressurization and internal mixing for 1-2 minutes, putting the prefabricated dispersion prepared in the step (1) into the internal mixer, carrying out pressurization and internal mixing for 4-6 minutes, carrying out lifting and ram floating for 10-20 seconds twice in the middle, controlling the discharge temperature to be 170-180 ℃, and cooling a lower auxiliary machine turnover and discharge sheet for later use.
The invention has the beneficial effects that: the multi-wall carbon nanotube belongs to a novel high-strength carbon fiber material, the radial size of the multi-wall carbon nanotube is small, the outer diameter of the multi-wall carbon nanotube is generally several nanometers to dozens of nanometers, the length of the multi-wall carbon nanotube is generally in a micron order, and the length and the diameter ratio of the multi-wall carbon nanotube are very large and can reach 103-106. The composite matrix formed by the multi-walled carbon nano-tubes and the rubber and plastic can greatly improve the following properties:
(1) the rubber ring has improved dynamic bending resistance and tensile strength, good mechanical strength, toughness, elasticity, fatigue resistance and isotropy, and greatly improved comprehensive properties such as bending crack resistance, concave abrasion resistance, geometric deformation resistance and the like.
(2) The multi-walled carbon nanotube filling reinforcing agent in the composite elastic matrix has the special effects of friction increase and wear reduction, and can be directionally distributed into a staggered and connected grid structure in the finished vulcanized rubber, so that the inner surface of the rubber ring and the threads of the middle roller form 'sub-meshing' transmission, and the running stability and the wear resistance of the rubber ring are improved.
(3) The reinforcing agent filled in the multi-wall carbon nano-tube in the composite elastic matrix belongs to a superconductor or a semiconductor, and forms an electrostatic dissipation channel in a distributed grid structure, thereby being beneficial to preventing the phenomenon of 'clothes-sticking' caused by static electricity.
(4) The multi-walled carbon nanotube filling reinforcing agent in the composite elastic matrix can improve the heat conductivity coefficient of the base material, and the rubber ring has high temperature resistance, small thermal expansion coefficient and strong thermal deformation resistance in the spinning process.
(5) The multi-walled carbon nanotube filling reinforcing agent in the composite elastic matrix has a structure which is more stable than that of a high molecular material, has super-strong chemical corrosion resistance, can effectively resist the erosion of oil and chemical additives in fibers, and prevents the swelling of the inner surface and the outer surface of a rubber ring from causing the adhesion of 'flower clothes' and the occurrence of mechanical waves caused by operation viscosity.
Detailed Description
Example 1 rubber-plastic and multiwalled carbon nanotube composite elastic matrix
The weight portions are as follows: 100 parts of nitrile rubber, 45 parts of high-polymerization-degree PVC, 30 parts of multi-wall carbon nano tube (raw powder), 18 parts of plasticizer DOP, 1.5 parts of dibutyltin laurate as a stabilizer, 3 parts of erucyl as a lubricating dispersant, 2246-S1.5 parts of antioxidant and 1 parts of antioxidant RD.
(1) Preparing a dispersion: firstly, weighing high-polymerization-degree PVC, a multi-walled carbon nanotube, a lubricating dispersant, 1.5 parts of an antioxidant and 1 part of an anti-aging agent according to a weight ratio, putting the weighed materials into a vertical plastic stirrer to be stirred for 2 minutes, then weighing a stabilizer and a plasticizer according to a weight ratio, adding the weighed materials into the stirrer to be stirred for 4 minutes, controlling the discharge temperature to be 60, bagging the materials after stirring, and cooling the materials for later use;
(2) banburying and hot plastication: firstly, weighing nitrile rubber at a plastication section according to a weight ratio, putting the nitrile rubber into an internal mixer, carrying out pressurization and internal mixing for 1 minute, then putting the prefabricated dispersion prepared in the step (1) into the internal mixer, carrying out pressurization and internal mixing for 4 minutes, carrying out lifting and top plug floating for 10 seconds twice respectively in the middle, controlling the discharge temperature to be 170 ℃, and then carrying out turnover and sheet discharging on a lower auxiliary machine for cooling for later use.
Example 2 rubber-plastic and multiwalled carbon nanotube composite elastic matrix
100 parts of nitrile rubber, 60 parts of high-polymerization-degree PVC, 25 parts of multi-walled carbon nano-tube, 22 parts of plasticizer, 2 parts of stabilizer, 3 parts of lubricating dispersant, 2 parts of antioxidant and 1.5 parts of anti-aging agent.
(1) Preparing a dispersion: firstly, weighing high-polymerization-degree PVC, multi-walled carbon nanotubes, a lubricating dispersant, 1.5 parts of an antioxidant and 1 part of an anti-aging agent according to a weight ratio, putting the weighed materials into a vertical plastic stirrer to be stirred for 3 minutes, then weighing a stabilizer and a plasticizer according to a weight ratio, adding the weighed materials into the stirrer to be stirred for 5 minutes, controlling the discharge temperature to be 65 ℃, bagging after stirring, and cooling for later use;
(2) banburying and hot plastication: firstly, weighing nitrile rubber at a plastication section according to a weight ratio, putting the nitrile rubber into an internal mixer, carrying out pressurization and internal mixing for 1 minute, then putting the prefabricated dispersion prepared in the step (1) into the internal mixer, carrying out pressurization and internal mixing for 5 minutes, carrying out lifting and top plug floating for 15 seconds twice respectively in the middle, controlling the discharge temperature to be 175 ℃, and then carrying out turnover and sheet discharging on a lower auxiliary machine for cooling for later use.
Example 3 rubber-plastic and multiwalled carbon nanotube composite elastic matrix
The formula proportion is as follows in parts by weight: 100 parts of nitrile rubber, 75 parts of high-polymerization-degree PVC, 20 parts of multi-walled carbon nano-tube, 125 parts of plasticizer, 2.5 parts of stabilizer, 2 parts of lubricating dispersant, 1 part of antioxidant and 2 parts of anti-aging agent.
(1) Preparing a dispersion: firstly, weighing high-polymerization-degree PVC, a multi-walled carbon nanotube, a lubricating dispersant, 1.5 parts of an antioxidant and 1 part of an anti-aging agent according to a weight ratio, putting the weighed materials into a vertical plastic stirrer to be stirred for 4 minutes, then weighing a stabilizer and a plasticizer according to a weight ratio, adding the weighed materials into the stirrer to be stirred for 6 minutes, controlling the discharge temperature to be 70 ℃, bagging after stirring, and cooling for later use;
(2) banburying and hot plastication: firstly, weighing nitrile rubber at a plastication section according to a weight ratio, putting the nitrile rubber into an internal mixer, carrying out pressurization and internal mixing for 1 minute, then putting the prefabricated dispersion prepared in the step (1) into the internal mixer, carrying out pressurization and internal mixing for 6 minutes, carrying out lifting and top plug floating for 10 seconds twice respectively in the middle, controlling the discharge temperature to be 180 ℃, and then carrying out turnover and sheet discharging on a lower auxiliary machine for cooling for later use.
Application examples
The prepared rubber-plastic and multi-walled carbon nanotube composite elastic matrix is used as a main body material to be applied to the design of a spinning rubber ring production formula, and rubber compound manufacturing → extrusion molding → vulcanization molding → grinding → cutting → product preparation is carried out, wherein the specific formula is shown in table 1.
TABLE 1
The rubber product compounds obtained in Table 1 were subjected to test data in accordance with the test standards GB/T528-2009, GB/T531.1-2008, GB/T1689-1998, and GB/T3512-2001, and the results are shown in Table 2.
TABLE 2
Then processing the rubber-plastic compound rubber obtained in the table 1 into a spinning rubber ring, and carrying out detection test data according to detection standards of GB/T7759-1996 and GB/T1681-2009, wherein the detection results are shown in the table 3:
TABLE 3
| Serial number | Detecting items | Example 1 | Example 2 | Example 3 |
| 1 | Full circle strength | 410 | 370 | 330 |
| 2 | Coefficient of surface static friction | 0.02 | 0.028 | 0.032 |
| 3 | Spinning simulation service life (inner layer fluffing \ sky) | 208 | 187 | 156 |
And (4) analyzing results: from the experimental data in tables 2 and 3, it can be seen that the technical indexes of the rubber-plastic and multi-walled carbon nanotube composite elastic matrix applied to the spinning rubber ring formula design completely meet the performance required for spinning novel textile fiber yarns, and meanwhile, the technical bottleneck that the spinning rubber ring is produced by adopting a modern high-efficiency process to spin novel textile fiber yarns is eliminated, the comprehensive performance of the spinning process is proved to be better by on-machine spinning tests, and the service life of the rubber-plastic and multi-walled carbon nanotube composite elastic matrix can be prolonged by 1.5-2 times compared with that of a common rubber-plastic ring.
Claims (6)
1. The preparation method of the rubber-plastic and multi-walled carbon nanotube composite elastic matrix is characterized in that the formula proportion is as follows according to parts by weight: based on 100 parts of nitrile butadiene rubber, adding 45-75 parts of high-polymerization-degree PVC, 20-30 parts of multi-walled carbon nano tubes, 18-25 parts of plasticizer, 1.5-2.5 parts of stabilizer, 2-3 parts of lubricating dispersant, 1-2 parts of antioxidant and 0.5-1.5 parts of anti-aging agent;
the acrylonitrile unit in the nitrile rubber accounts for 32-34 wt%, and the raw rubber Mooney viscosity ML (1+4) of the nitrile rubber is 62-68 at 100 ℃;
the polymerization degree of the PVC with high polymerization degree is 2400-2600;
the multi-walled carbon nanotube is of a raw powder base type, the length range is 3-60 mu m, and the pipe diameter range is 10-60 nm;
the method comprises the following specific steps:
(1) preparing a dispersion: firstly, weighing 45-75 parts of high-polymerization-degree PVC, 20-30 parts of multi-walled carbon nanotubes, 2-3 parts of a lubricating dispersant, 1-2 parts of an antioxidant and 0.5-1.5 parts of an anti-aging agent according to a weight ratio, putting the weighed materials into a vertical plastic stirrer, stirring for 2-4 minutes, then weighing 1.5-2.5 parts of a stabilizer and 18-25 parts of a plasticizer according to a weight ratio, adding the weighed materials into the stirrer, stirring for 4-6 minutes, controlling the discharge temperature to be 60-70 ℃, bagging after the stirring, and cooling for later use;
(2) banburying and hot plastication: weighing 100 parts of nitrile rubber at a plastication stage according to a weight ratio, putting the nitrile rubber into an internal mixer, carrying out pressurization and internal mixing for 1-2 minutes, putting the prefabricated dispersion prepared in the step (1) into the internal mixer, carrying out pressurization and internal mixing for 4-6 minutes, carrying out lifting and ram floating for 10-20 seconds twice in the middle, controlling the discharge temperature to be 170-180 ℃, and cooling a lower auxiliary machine turnover and discharge sheet for later use.
2. The preparation method of the rubber-plastic and multi-walled carbon nanotube composite elastic matrix as claimed in claim 1, wherein the preparation method comprises the following steps: the plasticizer is dioctyl phthalate.
3. The preparation method of the rubber-plastic and multi-walled carbon nanotube composite elastic matrix as claimed in claim 1, wherein the preparation method comprises the following steps: the stabilizer is dibutyltin laurate.
4. The preparation method of the rubber-plastic and multi-walled carbon nanotube composite elastic matrix as claimed in claim 1, wherein the preparation method comprises the following steps: the lubricating dispersant is erucamide.
5. The preparation method of the rubber-plastic and multi-walled carbon nanotube composite elastic matrix as claimed in claim 1, wherein the preparation method comprises the following steps: the antioxidant is 2, 2' -thiobis (4-methyl-6-tert-butylphenol).
6. The preparation method of the rubber-plastic and multi-walled carbon nanotube composite elastic matrix as claimed in claim 1, wherein the preparation method comprises the following steps: the anti-aging agent is 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer.
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| CN102532741A (en) * | 2010-12-16 | 2012-07-04 | 中国石油化工股份有限公司 | Antistatic polyvinyl chloride composition and preparation method |
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