CN109608669B - Carbon nano tube reinforced polypropylene composite material and preparation method thereof - Google Patents
Carbon nano tube reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon nano tube reinforced polypropylene composite material and a preparation method thereof, wherein the method comprises the following steps: placing the carbon nano tube array and the polypropylene resin M1 in a protective gas atmosphere for ultraviolet light treatment, so that the polypropylene and the carbon nano tube array generate graft polymerization reaction to obtain a modified carbon nano tube; and (3) placing the modified carbon nano tube and polypropylene resin M2 in a protective gas atmosphere for melting and mixing to prepare the carbon nano tube reinforced polypropylene composite material. The invention solves the problem of poor mechanical property of the polypropylene composite material in the prior art.
Description
Technical Field
The invention relates to the technical field of polypropylene resin, in particular to a carbon nano tube reinforced polypropylene composite material and a preparation method thereof.
Background
Polypropylene-based resins are easily processed and molded, have a high weight to mechanical property ratio, and are often used in various articles for daily use and industrial parts. Polypropylene resins are not satisfactory in mechanical strength and heat resistance, and in polypropylene resins used for industrial parts, inorganic fibers such as talc, mica powder, and glass fibers are often added to enhance mechanical properties, but the effects are not satisfactory.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a carbon nanotube reinforced polypropylene composite material and a preparation method thereof, and aims to solve the problem of poor mechanical properties of the polypropylene composite material in the prior art.
The technical scheme of the invention is as follows:
a preparation method of a carbon nanotube reinforced polypropylene composite material comprises the following steps:
placing the carbon nano tube array and the polypropylene resin M1 in a protective gas atmosphere for ultraviolet light treatment, so that the polypropylene and the carbon nano tube array generate graft polymerization reaction to obtain a modified carbon nano tube;
and (3) placing the modified carbon nano tube and polypropylene resin M2 in a protective gas atmosphere for melting and mixing to prepare the carbon nano tube reinforced polypropylene composite material.
The preparation method of the carbon nanotube reinforced polypropylene composite material comprises the step of treating with ultraviolet light at a wavelength of 216 nm.
The preparation method of the carbon nano tube reinforced polypropylene composite material comprises the step of controlling protective gas to continuously flow during ultraviolet light treatment, and arranging the polypropylene resin M1 at the position of an upper air inlet.
The preparation method of the carbon nano tube reinforced polypropylene composite material comprises the step of preparing a protective gas, wherein the protective gas is nitrogen or inert gas.
The preparation method of the carbon nanotube reinforced polypropylene composite material comprises the following steps of preparing a polypropylene resin M1 which is an unmodified polypropylene resin, and preparing a polypropylene resin M2 which is a polypropylene resin modified by unsaturated carboxylic acid or derivatives thereof.
The preparation method of the carbon nanotube reinforced polypropylene composite material comprises the step of converting the acid content in the polypropylene resin M2 into maleic anhydride and then accounting for 0.004-0.05% of the total mass of the acid modified polypropylene resin M2.
The preparation method of the carbon nanotube reinforced polypropylene composite material comprises the following steps of mixing the modified carbon nanotube and acid modified polypropylene resin according to a ratio of 25-50: 50-75 mass ratio, and melting and mixing.
The preparation method of the carbon nanotube reinforced polypropylene composite material comprises the following steps of (1) preparing a polypropylene resin, wherein the polypropylene resin is a polypropylene polymer, an ethylene/propylene copolymer or a propylene/alpha olefin copolymer;
the unsaturated carboxylic acid comprises one or more of maleic acid, fumaric acid, itaconic acid, acrylic acid and methacrylic acid;
the derivative of the unsaturated carboxylic acid comprises one or more of anhydride, unsaturated carboxylic acid ester, unsaturated carboxylic acid amide and metal salt of the unsaturated carboxylic acid.
The preparation method of the carbon nanotube reinforced polypropylene composite material comprises the following steps of modifying the carbon nanotube to have an average length of 0.8-8 mm and a diameter of 10-50 nm.
The preparation method of the carbon nanotube reinforced polypropylene composite material comprises the step of mixing at the temperature of 250-300 ℃.
A carbon nanotube-reinforced polypropylene composite material, which is produced by the production method described above.
Has the advantages that: according to the invention, the polypropylene and the carbon nano tube are subjected to graft polymerization reaction through ultraviolet irradiation treatment in the protective gas, so that polypropylene molecules are grafted on the surface of the carbon nano tube to form the modified carbon nano tube, the modified carbon nano tube and the polypropylene are mixed and melted and mixed to prepare the carbon nano tube reinforced polypropylene composite material, the existence of the polypropylene molecules on the surface of the modified carbon nano tube can overcome the interface strength between the carbon nano tube and the polypropylene resin, so that the modified carbon nano tube and the polypropylene resin have good compatibility and mechanical transfer performance, and the added modified carbon nano tube can increase the mechanical strength of the polypropylene resin, thereby enhancing the overall mechanical performance of the material.
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FIG. 1 is a schematic flow chart of a preferred embodiment of the method for preparing a carbon nanotube-reinforced polypropylene composite according to the present invention.
Detailed Description
The present invention provides a carbon nanotube reinforced polypropylene composite material and a method for preparing the same, and the present invention will be described in further detail below in order to make the objects, technical solutions, and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The preparation method of the carbon nanotube reinforced polypropylene composite material disclosed by the invention is shown in figure 1 and comprises the following steps:
s1, placing the carbon nanotube array and the polypropylene resin M1 in a protective gas atmosphere for ultraviolet light treatment, so that the polypropylene and the carbon nanotube array are subjected to graft polymerization reaction to obtain modified carbon nanotubes;
s2, placing the modified carbon nano tube and the polypropylene resin M2 in a protective gas atmosphere for melting and mixing to obtain the carbon nano tube reinforced polypropylene composite material.
The carbon nanotube is a one-dimensional nano material with a special structure, the radial dimension of the carbon nanotube is in a nanometer level, the axial dimension of the carbon nanotube is in a micrometer level, and two ends of the carbon nanotube are basically sealed. The carbon nano tube mainly comprises a plurality of layers to dozens of layers of coaxial circular tubes formed by hexagonally arranged carbon atoms, has the characteristics of keeping fixed distance between layers, light weight, perfect connection of a hexagonal structure and the like, ensures that the manufacturing process and the cost of the carbon nano tube are far superior to those of carbon fiber, and simultaneously has mechanical property and performance on composite materials superior to those of the carbon fiber and lower mixing ratio. However, since the surface of the carbon nanotube is too smooth, the mechanical transmission and compatibility between the carbon nanotube and the polypropylene resin are not good, so that the interfacial strength between the carbon nanotube and the polypropylene resin is too high, and if the carbon nanotube and the polypropylene resin are directly compression molded, the compression molded product has high tensile strength but low impact strength. Therefore, in the present invention, the carbon nanotubes need to be modified in step S1.
In the step S1, the carbon nanotube array and the polypropylene resin M1 are provided, then the carbon nanotube array and the polypropylene resin M1 are respectively laid flat and placed side by side in a protective gas atmosphere, then ultraviolet light treatment is performed, under the irradiation effect of ultraviolet light, the thermal effect of a reaction system is favorably provided, so that the system is in a state that the temperature is raised to the state that the polypropylene polymer forms gas, and the system moves to the surface of the carbon nanotube array under the action of protective gas flow to perform graft polymerization reaction with the carbon nanotube array, meanwhile, the ultraviolet light irradiation can open the C = C double bond on the surface of the carbon nanotube to generate a dangling bond, and the polypropylene polymer is partially broken to form a free radical, and after the free radical and the surface of the carbon nanotube are suspended in a bonding manner, the bonding can be performed, so that the polypropylene polymer is further grafted to the surface of the carbon nanotube, obtaining a modified carbon nano tube which is activated by ultraviolet irradiation and is beneficial to being combined with the polypropylene polymer; meanwhile, a layer of polypropylene molecular structure is grafted on the surface of the modified carbon nanotube, so that more binding sites are provided for further binding with polypropylene molecules, and more polypropylene molecules can be bound.
Wherein the polypropylene resin M1 is an unmodified polypropylene resin, and comprises a polypropylene single polymer, an ethylene/propylene copolymer, a propylene/alpha olefin copolymer and the like. The Melt Flow Rate (MFR) of the unmodified polypropylene-based resin M1 is preferably 5 to 70g/10min, more preferably 30 to 60g/10min, and when the MFR is not less than the lower limit, moldability is good, and when the MFR is not more than the upper limit, impact strength is high. Wherein MFR is measured under a load of 2.16kg at 230 ℃ in accordance with JIS K7210.
Preferably, the carbon nanotube array and the polypropylene resin powder M1 are respectively laid flat and placed in a protective gas atmosphere to perform ultraviolet light treatment, so that the ultraviolet light uniformly activates the polypropylene resin.
The protective gas in the step S1 is nitrogen or inert gas, and when ultraviolet light treatment is performed, the protective gas is controlled to continuously flow, and the polypropylene resin is arranged at the air inlet, and the continuously flowing protective gas can accelerate the polypropylene resin to move to the surface of the carbon nanotube array and the carbon nanotube array, so that the polypropylene resin and the carbon nanotube array undergo graft polymerization.
Preferably, the wavelength of the ultraviolet light treatment in step S1 is 216nm, which is too long to effectively activate the carbon nanotubes and the polypropylene resin, and too short to effectively activate the carbon nanotubes, the structure of the carbon nanotube array itself is easily damaged, and the carbon nanotubes are damaged.
Wherein the power of the ultraviolet light treatment is 40-50 mW, and the time is 40-60 mins. Preferably, the ultraviolet light treatment has a power of 45mW and a time of 50mins, and an excessively long treatment time may cause degradation of the polypropylene-based resin.
The average length of the modified carbon nanotubes in the step S1 is 0.8-8 mm, because the carbon nanotubes have extremely high mechanical properties, the mechanical strength of the carbon nanotubes can be better transmitted only when the carbon nanotubes have a sufficiently long length, so that the overall strength of the composite material is enhanced, and the appearance of the final product is also better, but when the average length of the modified carbon nanotubes is too long, the dispersibility of the modified carbon nanotubes is poor. Preferably, the average length of the carbon nanotube array is 1mm to 6mm, and more preferably 1.2mm to 5 mm.
The diameter of the carbon nanotube is 10 to 50nm, and more preferably within 12 to 20 nm. Within the range, the carbon nano tube can be ensured to have higher length-diameter ratio, so that the surface area of the carbon nano tube is larger, and the interface strength between the whole carbon nano tube and the resin material is increased.
In the step S1, the carbon nanotube array is a multi-walled nanotube array, the average length is 0.8-10 mm, and the diameter of the carbon nanotube is 12-15 nm. Wherein the preparation of the carbon nanotube array comprises the following steps: depositing a cobalt-nickel alloy catalyst layer with the thickness of 20-50 nm on a substrate, placing the substrate in a chemical vapor deposition reaction furnace, introducing protective gas (such as hydrogen), heating to 750-900 ℃, introducing carbon source gas, controlling the flow to be 1-2L/min, and reacting for 20-60 min, thereby generating a carbon nano tube array on the substrate. Wherein the carbon source gas comprises 25-40% of ethylene, 10-15% of hexane and the balance of nitrogen by volume.
The specific steps of step S1 are:
placing a first substrate with a carbon nanotube array and a second substrate evenly and flatly paved with unmodified polypropylene resin powder in parallel in a reaction chamber with a high-strength ultraviolet lamp, arranging the edge of the carbon nanotube array to be in contact with the edge of an unmodified polypropylene resin powder layer, and arranging the unmodified polypropylene resin powder layer to be positioned at an air inlet of the reaction chamber; the air inlet and the air outlet of the reaction cavity are closed, and the reaction cavity is vacuumized to reduce the air pressure in the reaction cavity to 10-6Introducing pure nitrogen into the reaction chamber through the air inlet below Torr until the normal atmospheric pressure is reached, opening the air outlet, and continuously introducing nitrogen to keep the flow of the gas in the chamber, wherein the flow rate is 2L/min; opening high intensity purpleAnd (3) an external lamp, wherein the irradiation power is 45mW, the wavelength of ultraviolet light is 216nm, the distance between an ultraviolet light source and the first substrate and the distance between the ultraviolet light source and the second substrate are 3mm, and the irradiation is maintained for 50min to obtain the modified carbon nano tube with the polypropylene molecules grafted on the surface.
Preferably, before step S2, the method further includes the steps of: the modified carbon nano tube is spun into carbon nano tube fiber with the diameter of 6-20 mu m so as to enhance the overall mechanical property of the carbon nano tube. The method comprises the following specific steps: fixing the substrate with the generated carbon nanotube array, clamping the carbon nanotube array by a spinning tool for spinning to prepare carbon nanotube fibers with the average diameter of 6-20 microns; and cutting the carbon nanotube fiber into carbon nanotube short fibers with different lengths by a cutting tool. The number average fiber length of the short fibers is preferably in the range of 2.7 to 8.9 mm. When the number average fiber length is below 2.7mm, no obvious effect is achieved on the improvement of the mechanical strength of the whole composite material; when the number average fiber length is 8.9mm or more, the dispersibility of the short fibers in the matrix is lowered and even the falling-off occurs when the composite material is produced.
In the step S2, the modified carbon nanotubes and the polypropylene resin M2 are melted in a protective gas atmosphere and mixed at a temperature of 250 to 300 ℃, and polypropylene molecules are grafted on the surfaces of the modified carbon nanotubes and are activated by ultraviolet light, so that the modified carbon nanotubes and the polypropylene resin M2 can be bonded together to form the carbon nanotube reinforced polypropylene composite material with stable structure and excellent mechanical properties. The protective gas is nitrogen or inert gas.
Preferably, the polypropylene resin M2 is a polypropylene resin modified with an unsaturated carboxylic acid or a derivative thereof, and the amount of the acid is 0.004 to 0.050% by weight based on the total weight of the polypropylene resin in terms of anhydrous maleic anhydride, and the presence of the unsaturated carboxylic acid can provide more strong binding sites to firmly bind the polypropylene molecules in the polypropylene resin M2 with the polypropylene molecules in the modified carbon nanotubes and the carbon nanotubes. When the acid amount of the polypropylene-based resin M2 is too low, a sufficient amount of unsaturated carboxyl groups cannot be provided, whereas when the acid amount is too high, the impact strength of the polypropylene-based molecule itself in the polypropylene-based resin M2 is affected. The amount of the acid in the polypropylene resin M2 is preferably 0.005 to 0.025%. Correspondingly, the modified carbon nano tube and the acid modified polypropylene resin are mixed according to the weight ratio of 25-50: and mixing and melting the raw materials in a mass ratio of 50-75, and mixing, thereby obtaining the modified material with ideal mechanical properties and better appearance. Namely, the mass ratio of the modified carbon nanotube to the acid-modified polypropylene resin is preferably 25 to 50: 55-70, most preferably 25-50: 57-68. When the added amount of the polypropylene-based resin M2 is within the above range, the yield of the whole product is high.
The polypropylene resin in the polypropylene resin M2 includes a polypropylene homopolymer, an ethylene/propylene copolymer, a propylene/α -olefin copolymer, and the like, and the polypropylene resin M2 includes a polymer obtained by graft-copolymerizing a polypropylene resin with an unsaturated carboxylic acid or a derivative thereof, a polymer obtained by random-copolymerizing propylene with an unsaturated carboxylic acid or a derivative thereof, a polymer obtained by block-copolymerizing propylene with an unsaturated carboxylic acid or a derivative thereof, or a polymer obtained by graft-copolymerizing the random copolymer or the block copolymer with an unsaturated carboxylic acid or a derivative thereof. The unsaturated carboxylic acid includes maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, and the like. The derivative of the unsaturated carboxylic acid includes an acid anhydride of the unsaturated carboxylic acid (e.g., anhydrous maleic acid, anhydrous itaconic acid, etc.), an unsaturated carboxylic acid ester (e.g., methyl acrylate, methyl methacrylate, etc.), an unsaturated carboxylic acid amide (e.g., maleic acid diamide, itaconic acid diamide, acrylic acid amide, methacrylic acid amide, etc.), a metal salt of the unsaturated carboxylic acid (e.g., sodium methacrylate, etc.), and the like.
Among the above unsaturated carboxylic acids or derivatives thereof, acrylic acid, methacrylic acid, and maleic anhydride are preferable.
Preferably, a polymer obtained by graft copolymerization of a polypropylene-based resin and maleic anhydride is M2, or a copolymer obtained by copolymerization of propylene and acrylic acid, methacrylic acid or maleic anhydride is M2.
While the acid content of the polypropylene resin M2 is controlled within the above range, the acid-modified polypropylene resin having an acid content of 0.004 to 0.050% may be used as it is as the polypropylene resin M2 for reaction with the modified carbon nanotubes, or the acid-modified polypropylene resin (M2-1) and the unmodified polypropylene resin (M2-2) may be used in a mixture of a predetermined amount by mass ratio of 0.1 to 4:50 to 75, wherein the acid content of the acid-modified polypropylene resin (M2-1) is preferably 0.4 to 8% of the total mass of the acid-modified polypropylene resin (M2-1) in terms of maleic anhydride. When the amount of the acid is within the above range, the interfacial strength between the acid-modified polypropylene-based resin (M2-1) and the carbon nanotube fiber is high, so that the tensile strength of the final press-molded product is improved. As the unmodified polypropylene-based resin (M2-2), any of the various polypropylene-based resins specified for the acid-modified polypropylene-based resin (M2-1) can be used. Among these, block copolymers of ethylene/propylene and individual polymers of polypropylene are more preferable.
Preferably, before the mixing, an additive such AS an antioxidant, a fluorescent brightener, a pigment, a fuel, carbon black, a filler, a releasing agent, an ultraviolet absorber, an antistatic agent, rubber, a softener, a wetting agent (liquid paraffin, epoxidized soybean oil, etc.), a flame retardant, an organic metal salt, and the like, and an anti-dripping polytetrafluoroethylene resin, or a resin such AS impact-resistant polystyrene, ABS, AES, AAS, AS, acryl, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyarylate, a polysulfone-based resin, and a polyphenylene sulfide resin may be further added.
Based on the method, the invention also provides a carbon nanotube reinforced polypropylene composite material, which is prepared by the preparation method.
The present invention will be described in detail below with reference to examples.
The testing and characterization method comprises the following steps:
A. tensile test
The experiment was carried out according to ISO 527 standard using a dumbbell-shaped test piece 10mm wide, 4mm thick and 80mm long parallel portions.
B. Cantilever impact test
The experiment was performed on a specimen cut with a scratch according to ISO 179 standard.
C. Specific gravity measurement
The determination was carried out according to ISO 1183 standard using the Archimedes method.
D. Bending test
A3-point bending test was carried out using a short strip specimen having a width of 10mm, a thickness of 4mm and a length of 80mm in accordance with ISO 178.
Raw material
M2-1: acid-modified Polypropylene resin (Sanyo chemical, Youmex1001, acid content 2.3%)
M2-2: unmodified Polypropylene-based resin (product of Japan Polypropylene Corporation), propylene alone polymer, MFR 40g/10 min.
Example 1
(1) Preparing a carbon nanotube array: depositing a cobalt-nickel alloy catalyst layer with the thickness of 20nm on a first substrate, placing the first substrate in a chemical vapor deposition reaction furnace, introducing hydrogen protective gas, heating to 800 ℃, introducing carbon source gas (wherein the volume of the carbon source gas comprises 30% of ethylene, 15% of hexane and the balance of nitrogen), controlling the flow at 1.5L/min, and reacting for 40min, thereby generating a carbon nanotube array with the average length of 0.8-10 mm on the first substrate;
(2) preparing modified carbon nanotubes: placing a first substrate with a carbon nanotube array and a second substrate evenly and flatly paved with unmodified polypropylene resin powder in parallel in a reaction chamber with a high-strength ultraviolet lamp, arranging the edge of the carbon nanotube array to be in contact with the edge of an unmodified polypropylene resin powder layer, and arranging the unmodified polypropylene resin powder layer to be positioned at an air inlet of the reaction chamber; the air inlet and the air outlet of the reaction cavity are closed, and the reaction cavity is vacuumized to reduce the air pressure in the reaction cavity to 10-6Introducing pure nitrogen into the reaction chamber through the air inlet below Torr until the normal atmospheric pressure is reached, opening the air outlet, and continuously introducing nitrogen to keep the flow of the gas in the chamber, wherein the flow rate is 2L/min; opening a high-intensity ultraviolet lamp with irradiation power of 45mW, ultraviolet wavelength of 216nm, ultraviolet source distance of 3mm from the first substrate and the second substrate, and maintaining irradiation for 50min to obtain polymer grafted on the surfaceModified carbon nanotubes of propylene molecules;
(3) carbon nanotube-reinforced polypropylene-based composite material: 0.45 part of acid modified polypropylene resin (M2-1) and 69.55 parts of unmodified polypropylene resin (M2-2) are uniformly mixed by mass under the protective gas environment of nitrogen to prepare polypropylene resin M2, the mixture is heated to 280 ℃ to be melted, 30 parts of modified carbon nano tubes are added at the temperature, the mixture is stirred for 1.5 hours at the speed of 120rpm, and the composite material (X-1) is obtained after standing and cooling.
Example 2
(1) Preparing a carbon nanotube array: reference example 1;
(2) preparing modified carbon nanotubes: reference example 1;
(3) carbon nanotube-reinforced polypropylene-based composite material: 0.65 part by mass of an acid-modified polypropylene resin (M2-1) and 69.35 parts by mass of an unmodified polypropylene resin (M2-2) were uniformly mixed in an atmosphere of a nitrogen-containing protective gas, and then, a polypropylene resin M2 was heated to 280 ℃ to melt, 30 parts by mass of a modified carbon nanotube was added while maintaining the temperature, and the mixture was stirred at 120rpm for 1.5 hours, left to stand and cooled to obtain a composite material (X-2).
Example 3
(1) Preparing a carbon nanotube array: reference example 1;
(2) preparing modified carbon nanotubes: reference example 1;
(3) carbon nanotube-reinforced polypropylene-based composite material: under a nitrogen protective gas atmosphere, 70 parts by mass of an unmodified polypropylene resin (M2-2) was directly heated to 280 ℃ as a polypropylene resin M2 to melt, 30 parts by mass of a modified carbon nanotube was added while maintaining the temperature, and the mixture was stirred at 120rpm for 1.5 hours, and then allowed to stand and cool to obtain a composite material (X-3).
Example 4
(1) Preparing a carbon nanotube array: reference example 1;
(2) preparing modified carbon nanotubes: reference example 1;
(3) carbon nanotube-reinforced polypropylene-based composite material: in a nitrogen atmosphere, 1.4 parts by mass of an acid-modified polypropylene resin (M2-1) and 68.6 parts by mass of an unmodified polypropylene resin (M2-2) were uniformly mixed to prepare a polypropylene resin M2, and the mixture was heated to 280 ℃ to melt, 30 parts by mass of a modified carbon nanotube was added while maintaining the temperature, stirred at 120rpm for 1.5 hours, and allowed to stand to cool to obtain a composite material (X-4).
The product (X-1), the product (X-2), the product (X-3) and the product (X-4) were subjected to extrusion molding in an environment of a cylinder temperature of 230 ℃ and a mold temperature of 80 ℃ and then subjected to a tensile test, a cantilever impact test, a specific gravity measurement and a bending test, respectively, and the results are shown in Table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Composite material | X-1 | X-2 | X-3 | X-4 |
| Weight ratio of the polypropylene-based resin (M2) | 70 | 70 | 70 | 70 |
| Weight ratio of modified carbon nanotube fiber | 30 | 30 | 30 | 30 |
| (M2) acid amount% | 0.014 | 0.022 | 0.000 | 0.045 |
| Average length (mm) of modified carbon nanotube fiber | 3.5 | 3.5 | 3.5 | 3.5 |
| The weight ratio of (M2-1) in M2% | 6.4 | 9.3 | 0.0 | 2.0 |
| The weight ratio of (M2-2) in M2% | 93.6 | 90.7 | 100.0 | 98.0 |
| Tensile strength GPa | 0.75 | 1.18 | 0.45 | 1.12 |
| Cantilever impact Strength kJ/m2 | 88 | 80 | 92 | 61 |
| Specific gravity of | 1.10 | 1.10 | 1.08 | 1.09 |
| Bending strength MPa | 432 | 478 | 383 | 627 |
As can be seen from the above table, the tensile strength and impact strength of the resulting products are well balanced using the protocols of example 1 and example 2. In contrast, in example 3, since the acid amount of the polypropylene-based resin M2 was less than the optimum range of example, the tensile strength of the resulting product was low; in example 4, since the acid content of the polypropylene-based resin M2 was higher than the optimum range in the examples, the impact strength of the resulting product was low.
In summary, according to the preparation method of the carbon nanotube reinforced polypropylene composite material provided by the present invention, ultraviolet irradiation treatment is performed in protective gas to perform a graft polymerization reaction between polypropylene and a carbon nanotube, so as to graft polypropylene molecules on the surface of the carbon nanotube to form a modified carbon nanotube, the modified carbon nanotube and polypropylene are mixed and melted and mixed to prepare the carbon nanotube reinforced polypropylene composite material, the presence of the polypropylene molecules on the surface of the modified carbon nanotube can overcome the interface strength between the carbon nanotube and the polypropylene resin, so that the modified carbon nanotube and the polypropylene resin have good compatibility and mechanical transfer performance, and the added modified carbon nanotube can increase the mechanical strength of the polypropylene resin, thereby enhancing the mechanical properties of the whole material.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a carbon nanotube reinforced polypropylene composite material is characterized by comprising the following steps:
placing the carbon nano tube array and the polypropylene resin M1 in a protective gas atmosphere for ultraviolet light treatment, so that the polypropylene and the carbon nano tube array generate graft polymerization reaction to obtain a modified carbon nano tube;
placing the modified carbon nano tube and polypropylene resin M2 in a protective gas atmosphere for melting and mixing to prepare a carbon nano tube reinforced polypropylene composite material;
the polypropylene resin M1 is an unmodified polypropylene resin, and the polypropylene resin M2 is a polypropylene resin modified by unsaturated carboxylic acid or derivatives thereof;
the amount of acid in the polypropylene resin M2 is 0.004 to 0.05% by mass of the acid-modified polypropylene resin M2 in terms of maleic anhydride.
2. The method for producing a carbon nanotube-reinforced polypropylene-based composite material according to claim 1, wherein the ultraviolet light treatment has a wavelength of 216 nm.
3. The method for producing a carbon nanotube-reinforced polypropylene-based composite material according to claim 1, wherein the flow of the protective gas is controlled during the ultraviolet light treatment, and the polypropylene-based resin M1 is provided at an upper tuyere position.
4. The method for producing a carbon nanotube-reinforced polypropylene-based composite material according to claim 1, wherein the modified carbon nanotubes and the acid-modified polypropylene-based resin are mixed in an amount of 25 to 50: 50-75 mass ratio, and melting and mixing.
5. The method for producing a carbon nanotube-reinforced polypropylene-based composite material according to claim 1, wherein the polypropylene-based resin is a polypropylene polymer, an ethylene/propylene copolymer or a propylene/α -olefin copolymer;
the unsaturated carboxylic acid comprises one or more of maleic acid, fumaric acid, itaconic acid, acrylic acid and methacrylic acid;
the derivative of the unsaturated carboxylic acid comprises one or more of anhydride, unsaturated carboxylic acid ester, unsaturated carboxylic acid amide and metal salt of the unsaturated carboxylic acid.
6. The method for producing a carbon nanotube-reinforced polypropylene-based composite material according to claim 1, wherein the modified carbon nanotubes have an average length of 0.8 to 8mm and a diameter of 10 to 50 nm.
7. The method for producing a carbon nanotube-reinforced polypropylene-based composite material according to claim 1, wherein the kneading temperature is 250 to 300 ℃.
8. A carbon nanotube-reinforced polypropylene-based composite material produced by the production method according to any one of claims 1 to 7.
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| CN107304266A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | For the polypropylene composite materials powder of selective laser sintering and its preparation |
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| KR101102848B1 (en) * | 2009-08-11 | 2012-01-05 | (주)세명아이엔씨 | Polypropylene-graft-maleic anhydride/Carbon Nanotube Nanocomposites with Excellent Thermal Stability and Electrical Conductivity |
| CA2801617C (en) * | 2010-06-11 | 2018-05-29 | National Research Council Of Canada | Modified carbon nanotubes and their compatibility |
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| CN1654528A (en) * | 2005-01-27 | 2005-08-17 | 中国石油化工股份有限公司 | Carbon nanotube/polypropylene composite materials and process for preparing same |
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