CN109337138B - Magnetic rubber composite material with anisotropy and preparation method thereof - Google Patents
Magnetic rubber composite material with anisotropy and preparation method thereof Download PDFInfo
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- CN109337138B CN109337138B CN201811003689.8A CN201811003689A CN109337138B CN 109337138 B CN109337138 B CN 109337138B CN 201811003689 A CN201811003689 A CN 201811003689A CN 109337138 B CN109337138 B CN 109337138B
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Abstract
The invention discloses an anisotropic magnetic rubber composite material and a preparation method thereof, wherein the anisotropic magnetic rubber composite material comprises, by weight, 100 parts of a rubber matrix, 3-30 parts of CNs @ Fe 3 O 4 hybrid particle dispersion liquid, 1-3 parts of sulfur, 0.5-5 parts of zinc oxide, 0.5-3 parts of stearic acid and 0.5-3 parts of an accelerator.
Description
Technical Field
The present invention relates to a functional rubber material, more specifically to a magnetic rubber composite material having anisotropic behavior; belongs to the technical field of rubber composite materials.
Background
The properties of rubber composites depend on the properties of the matrix, the filler, and the microstructure of the composite from which they are composed. The filler in the anisotropic rubber composite material is oriented along a certain direction, so that the macroscopic properties of the anisotropic rubber composite material, such as heat conduction, electric conduction, mechanics and the like, also show a certain anisotropy, and the anisotropic rubber composite material has potential application value in the occasions with oriented deformation characteristics, such as bending, oriented stretching and the like.
As a rigid nanofiller with a large aspect ratio, nanocrystalline cellulose (NCC) has a series of performance characteristics such as wide source, reproducibility, degradability, low density, and the like, and is particularly concerned by people. Because of its excellent mechanical properties, NCC is widely used as a reinforcing filler in various rubbers. However, the reinforcing effect is closely related to the structure and self-assembly behavior of the composite material in the matrix, besides the high strength of the composite material. Since NCC has a large aspect ratio, it exhibits a significantly different elastic modulus in the length (110-220GPa) and diameter (2-50GPa) directions. This property gives NCC a unique advantage in reinforced rubber: the orientation arrangement of NCC along the length direction is realized in the processing process, and the composite material with excellent mechanical property and anisotropy is obtained. Although the NCC reinforced rubber has been reported in the related art, the rubber is all prepared into the isotropic rubber composite material, and the anisotropic rubber composite material prepared by utilizing the characteristic of high length-diameter ratio is not seen in the prior art.
Ferroferric oxide (Fe 3 O 4) is used as a magnetic material and is commonly used for preparing magnetic rubber, but the mechanical property of the prepared magnetic rubber is limited due to the smooth surface and the weak interface interaction between the ferroferric oxide and a rubber molecular chain.
Disclosure of Invention
aiming at the defects of the existing rubber composite material, the invention provides a magnetic rubber composite material with excellent mechanical property, magnetism, lower density and anisotropy and a preparation method thereof.
The invention discovers that NCC has excellent reinforcing effect on rubber, and simultaneously, because of the characteristics of high specific surface area and nano rod shape of NCC and the large amount of hydroxyl on the surface of NCC, the NCC is favorable for adsorbing Fe 3 O 4 to load on the surface of the NCC, thereby constructing magnetic nano particles with high length-diameter ratio, and the magnetic rubber composite material with anisotropy can be prepared by utilizing the orientation arrangement of magnetic powder inducing NCC under the action of a weak magnetic field, the NCC and Fe 3 O 4 have better matching action, the mechanical property of the prepared composite material in the parallel orientation direction is obviously better than that of the composite material in the vertical orientation direction and non-orientation direction, and the higher mechanical property can be realized by adding less filler, thereby being favorable for reducing the filler consumption and reducing the density of the material.
The purpose of the invention is realized by the following technical scheme:
The magnetic rubber composite material with anisotropy comprises the following raw materials in parts by weight:
The NCC @ Fe 3 O 4 hybrid particle dispersion liquid is prepared by the following steps of adding Fe 2+ and Fe 3+ into an NCC water dispersion liquid, uniformly mixing, removing air, adjusting the pH value to 9-11, controlling the temperature to be 50-80 ℃, reacting for 20-40 min, and washing a product after reaction to obtain the NCC @ Fe 3 O 4 hybrid particle dispersion liquid, wherein the mass ratio of NCC to Fe 3 O 4 in the NCC @ Fe 3 O 4 hybrid particle dispersion liquid is 1: 2-4: 1;
the preparation method comprises the steps of mixing the obtained NCC @ Fe 3 O 4 hybrid particle dispersion liquid with latex or rubber solution, adding sulfur, zinc oxide, stearic acid and an accelerator, uniformly mixing, pouring into a mold placed in an external magnetic field, inducing the NCC @ Fe 3 O 4 hybrid particles in the solution to be arranged in parallel in the direction of the magnetic field through the magnetic field, and carrying out vulcanization molding.
To further achieve the object of the present invention, preferably, the rubber is one or more of natural rubber, epoxidized natural rubber, styrene-butadiene rubber, nitrile rubber and ethylene-propylene rubber.
Preferably, the accelerator is one or a mixture of more of benzothiazole disulfide, N-cyclohexyl-2-benzothiazole sulfonamide, N-tertiary butyl-2-benzothiazole sulfonamide, N-oxydiethylene-2-benzothiazole sulfonamide, tetramethyl thiuram disulfide and N, N-dicyclohexyl-2-benzothiazole sulfonamide.
Preferably, the NCC is a rod-shaped product which is extracted from microcrystalline cellulose, cotton, sisal, flax, paper, crop straws and tunicates by a sulfuric acid hydrolysis method, has the diameter of 10-20 nm and the length of 200 nm-2 mu m.
preferably, the mass concentration of NCC in the NCC aqueous dispersion is 0.1-1.0%.
Preferably, the Fe 3 O 4 is spherical particles with the diameter of 20-30 nm, which are synthesized by adopting a solution containing Fe 2+ and Fe 3+ through a coprecipitation method.
Preferably, the pH value is adjusted to 9-11 by adding ammonia water.
preferably, the washing product is washed by using absolute ethyl alcohol and deionized water alternately for 3-6 times.
The preparation method of the magnetic rubber composite material with anisotropy comprises the following steps:
1) Preparing a NCC @ Fe 3 O 4 hybrid particle dispersion liquid;
2) Mixing the obtained NCC @ Fe 3 O 4 hybrid particle dispersion liquid with latex or rubber solution, adding sulfur, zinc oxide, stearic acid and an accelerator, uniformly mixing, pouring into a mold placed in an external magnetic field, inducing the NCC @ Fe 3 O 4 hybrid particles in the solution to be aligned in parallel along the direction of the magnetic field by the magnetic field, continuously applying the magnetic field in the solvent volatilization process, fixing the orientation state, controlling the magnetic field strength to be 50 mT-500 mT, and controlling the distance between a magnetic field generator and the mold to be 10-40 mm until the solvent is completely volatilized to obtain anisotropic rubber/NCC @ Fe 3 O 4 rubber compound;
3) And (3) paving the rubber/NCC @ Fe 3 O 4 mixed rubber obtained in the step 2) in a hot-press forming die according to the orientation direction, and carrying out vulcanization forming to obtain the anisotropic magnetic rubber composite material.
Preferably, the material of the mould is polytetrafluoroethylene; the solvent is volatilized for 2-3 days at 40-60 ℃.
The anisotropic rubber composite material disclosed by the invention has the realization principle of anisotropy, namely, NCC with a high length-diameter ratio is used as a template, Fe 3 O 4 magnetic nanoparticles are generated in situ on the surface of the NCC as a template to construct NCC @ Fe 3 O 4 hybrid particle dispersion liquid, the orientation arrangement of hybrid particles in a matrix is realized under the action of an external magnetic field by utilizing the magnetism of Fe 3 O 4, and the orientation state is fixed in the solvent volatilization process, so that the anisotropic magnetic rubber composite material is prepared.
Compared with the prior art, the invention has the following advantages and beneficial effects:
The improved technology integrates the characteristics of high reinforcement of NCC on rubber and orientation arrangement of magnetic powder under the action of a magnetic field, and the provided anisotropic magnetic rubber composite material has obvious mechanical property anisotropy and higher magnetism, is beneficial to reducing the using amount of fillers, reducing the energy consumption of the material in the processing process, reducing the density of the material, and meeting the use requirements of light weight and occasions with directional deformation characteristics. In particular, the tensile strength parallel to the orientation direction is up to 34.7MPa, the degree of orientation is up to 1.38, i.e.the tensile strength parallel to the orientation direction is 38% higher than the tensile strength perpendicular to the orientation direction, when the amount of filler is the same. The magnetic induction intensity is 22.9emu/g at most.
Detailed Description
For a better understanding of the present invention, the present invention is further illustrated by the following examples, but the embodiments of the present invention are not limited thereto.
Example 1
Adding 0.87g of FeCl 2.4H 2 O and 2.33g of FeCl 3.6H 2 O into 1g of NCC (t-NCC) dispersion liquid with the concentration of 0.5 percent extracted from ascidians, uniformly mixing, pouring the obtained mixed liquid into a three-neck flask placed in a water bath at 70 ℃, continuously stirring, introducing nitrogen for 20min, dropwise adding ammonia water to adjust the pH of the mixed liquid to 10, continuously reacting for 30min, washing the reaction product for 4 times by using deionized water and ethanol alternately, and finally obtaining NCC Fe 3 O 4 hybrid particle dispersion liquid with the mass ratio of NCC to Fe 3 O 4 being 1: 1.
According to the weight parts, 5 parts of NCC @ Fe 3 O 4 hybrid particle dispersion liquid is slowly added into natural rubber latex containing 100 parts of dry rubber, then ethanol dispersion liquid containing 2 parts of sulfur, 5 parts of zinc oxide, 3 parts of stearic acid and 1.5 parts of benzothiazole disulfide is added into the mixed liquid to be uniformly mixed, the concentration of the rubber in the mixed liquid is adjusted to be 20% through rotary evaporation, then the mixed liquid is poured into a rectangular polytetrafluoroethylene mold with magnets arranged in parallel at two sides, the magnetic field strength is 100mT, the distance between the magnets and the edge of the mold is 25mm, the solvent is volatilized at 50 ℃, the NCC @ Fe 3 O 4 hybrid particles are induced to be oriented and arranged along the NCC length direction (magnetic field action direction), the magnetic field is continuously applied in the solvent volatilization process, the solvent is completely volatilized after 48 hours, the orientation state is fixed, then the mixed rubber is obtained through demolding, after the mixed rubber is placed for 6 hours at room temperature, and then the mixed rubber is subjected to hot vulcanization molding at 143 ℃, and the anisotropic rubber composite material.
Example 2
Adding 0.87g of FeCl 2.4H 2 O and 2.33g of FeCl 3.6H 2 O into 2g of NCC (t-NCC) dispersion liquid with the concentration of 0.5 percent extracted from sea squirts, uniformly mixing, pouring the obtained mixed liquid into a three-neck flask placed in a water bath with the temperature of 80 ℃, continuously stirring, introducing nitrogen for 20min, dropwise adding ammonia water to adjust the pH of the mixed liquid to be 10, continuously reacting for 30min, finishing, alternately washing the reaction product for 4 times by using deionized water and ethanol, and finally obtaining the hybrid particle dispersion liquid with the mass ratio of NCC to Fe 3 O 4 of 2: 1.
According to the weight portion, a dispersion liquid containing 10 portions of NCC @ Fe 3 O 4 is slowly added into nitrile rubber latex containing 100 portions of dry rubber, then an ethanol dispersion liquid containing 1.5 portions of sulfur, 5 portions of zinc oxide, 1 portion of stearic acid and 1 portion of N-cyclohexyl-2-benzothiazole sulfenamide is added into a mixed liquid to be uniformly mixed, the concentration of the rubber in the mixed liquid is adjusted to be 20% through rotary evaporation, then the mixture is poured into a rectangular polytetrafluoroethylene mold with magnets arranged in parallel at two sides, the magnetic field intensity is 150mT, the distance between the magnets and the edges of the mold is 25mm, the solvent is volatilized and hybrid particles are induced to be oriented and arranged along the length direction of the NCC (the action direction of the magnetic field) at 50 ℃, the magnetic field is continuously applied in the volatilization process of the solvent, the solvent is completely volatilized after 50 hours, the orientation state is fixed, then the mixed rubber is obtained through demolding, the mixed rubber is placed at room temperature for 6 hours and then is subjected to hot vulcanization molding at 150 ℃, and the oriented anisotropic.
Example 3
adding 0.22g of FeCl 2.4H 2 O and 0.58g of FeCl 3.6H 2 O into 1g of NCC (c-NCC) dispersion liquid with the concentration of 0.5 percent extracted from cotton, uniformly mixing, pouring the obtained mixed liquid into a three-neck flask placed in a water bath at 60 ℃, continuously stirring, introducing nitrogen for 20min, dropwise adding ammonia water to adjust the pH of the mixed liquid to be 11, continuously reacting for 20min, washing the reaction product for 4 times by using deionized water and ethanol, and finally obtaining the hybrid particle dispersion liquid with the mass ratio of NCC to Fe 3 O 4 being 4: 1.
According to the weight portion, a dispersion liquid containing 20 portions of NCC @ Fe 3 O 4 is slowly added into epoxidized natural rubber latex containing 100 portions of dry rubber, then an ethanol dispersion liquid containing 3 portions of sulfur, 3 portions of zinc oxide, 2 portions of stearic acid and 1 portion of N-tert-butyl-2-benzothiazole sulfenamide is added into a mixed liquid to be uniformly mixed, the concentration of the rubber in the mixed liquid is adjusted to be 20% through rotary evaporation, then the mixed liquid is poured into a rectangular polytetrafluoroethylene mold with magnets arranged in parallel at two sides, the magnetic field intensity is 200mT, the distance between the magnets and the edges of the mold is 20mm, the solvent is volatilized and hybrid particles are induced to be oriented and arranged along the length direction of the NCC (the action direction of the magnetic field) at 50 ℃, the magnetic field is continuously applied in the volatilization process of the solvent, the solvent is completely volatilized after 55 hours, the orientation state is fixed, then the mixed rubber is obtained through demolding, after standing for 6 hours at room temperature, and then the thermal vulcanization molding is carried out at 145 ℃, and the.
Example 4
1.74g of FeCl 2.4H 2 O and 4.65g of FeCl 3.6H 2 O are added into 1g of NCC (t-NCC) dispersion liquid with the concentration of 0.5 percent extracted from sea squirts and are uniformly mixed, then the obtained mixed liquid is poured into a three-neck flask placed in a water bath with the temperature of 70 ℃ and is continuously stirred, ammonia water is added dropwise after nitrogen is introduced for 20min to adjust the pH of the mixed liquid to be 9, the reaction is continuously carried out for 40min and is finished, the reaction product is alternately washed by deionized water and ethanol for 4 times, and finally the hybrid particle dispersion liquid with the mass ratio of 1:2 of NCC and Fe 3 O 4 is obtained.
According to the weight portion, a dispersion liquid containing 10 portions of NCC @ Fe 3 O 4 is slowly added into styrene-butadiene rubber latex containing 100 portions of dry rubber, then an ethanol dispersion liquid containing 1 portion of sulfur, 3 portions of zinc oxide, 2 portions of stearic acid, 1.5 portions of benzothiazole disulfide and 0.5 portion of N-cyclohexyl-2-benzothiazole sulfenamide is added into the mixed liquid to be uniformly mixed, the concentration of the rubber in the mixed liquid is adjusted to be 20% through rotary evaporation, then the mixed liquid is poured into a rectangular polytetrafluoroethylene die with magnets arranged in parallel at two sides, the magnetic field strength is 50mT, the distance between the magnets and the edge of the die is 25mm, the solvent is volatilized and the hybrid particles are induced to be aligned along the length direction (magnetic field action direction) of the NCC under the condition at 50 ℃, the magnetic field is continuously applied in the solvent volatilization process, the solvent is completely volatilized after 48 hours, the oriented state is fixed, then the mixed rubber is obtained through demolding, the standing is kept for 6 hours at room temperature, and then the hot vulcanization molding is carried out at 160 ℃, and the.
example 5
0.44g of FeCl 2 & 4H 2 O and 1.16g of FeCl 3 & 6H 2 O are added into 1g of NCC (m-NCC) dispersion liquid with the concentration of 0.5 percent extracted from microcrystalline cellulose and are uniformly mixed, then the obtained mixed liquid is poured into a three-neck flask placed in a water bath with the temperature of 65 ℃ and is continuously stirred, ammonia water is added dropwise after nitrogen is introduced for 20min to adjust the pH value of the mixed liquid to be 10, the reaction is continuously carried out for 30min and then is finished, the reaction product is alternately washed by deionized water and ethanol for 4 times, and finally the hybrid particle dispersion liquid with the mass ratio of NCC to Fe 3 O 4 of 2:1 is obtained.
according to the weight portion, a dispersion liquid containing 20 portions of NCC @ Fe 3 O 4 is slowly added into natural rubber latex containing 100 portions of dry rubber, then an ethanol dispersion liquid containing 1.5 portions of sulfur, 5 portions of zinc oxide, 1 portion of stearic acid, 1.5 portions of benzothiazole disulfide and 0.3 portion of tetramethylthiuram disulfide is added into the mixed liquid to be uniformly mixed, the concentration of the rubber in the mixed liquid is adjusted to be 20% through rotary evaporation, then the mixed liquid is poured into a rectangular polytetrafluoroethylene die with magnets arranged in parallel at two sides, the magnetic field intensity is 200mT, the distance between the magnets and the edge of the die is 30mm, the solvent is volatilized at 40 ℃, hybrid particles are induced to be oriented and arranged along the length direction (magnetic field action direction), the magnetic field is continuously applied in the solvent volatilization process, the solvent is completely volatilized after 60 hours, the oriented state is fixed, then the mixed rubber is obtained through demoulding, the mixed rubber is placed in a drying box at 50 ℃ to further remove residual solvent, and is placed for 6 hours at room temperature and then is subjected to hot vulcanization forming at 145 ℃, and the anisotropic rubber composite material with the magnetic.
Example 6
Adding 0.87g of FeCl 2.4H 2 O and 2.33g of FeCl 3.6H 2 O into 1g of NCC (c-NCC) dispersion liquid with the concentration of 0.5 percent extracted from cotton, uniformly mixing, pouring the obtained mixed liquid into a three-neck flask placed in a water bath at 65 ℃, continuously stirring, introducing nitrogen for 20min, dropwise adding ammonia water to adjust the pH of the mixed liquid to 10, continuously reacting for 30min, finishing, alternately washing the reaction product for 4 times by using deionized water and ethanol, and finally obtaining the hybrid particle dispersion liquid with the mass ratio of NCC to Fe 3 O 4 of 2: 1.
according to the weight portion, a dispersion liquid containing 30 portions of NCC @ Fe 3 O 4 is slowly added into natural rubber latex containing 100 portions of dry rubber, then an ethanol dispersion liquid containing 3 portions of sulfur, 5 portions of zinc oxide, 1 portion of stearic acid, 1.5 portions of benzothiazole disulfide and 0.5 portion of N-oxydiethylene-2-benzothiazole sulfenamide is added into the mixed liquid to be uniformly mixed, the concentration of the rubber in the mixed liquid is adjusted to be 20% through rotary evaporation, then the mixed liquid is poured into a rectangular polytetrafluoroethylene die with magnets arranged in parallel at two sides, the magnetic field strength is 300mT, the distance between the magnets and the edge of the die is 30mm, the solvent is volatilized and the hybrid particles are induced to be aligned along the length direction (magnetic field action direction) of the NCC under the condition at 60 ℃, the magnetic field is continuously applied during the volatilization of the solvent, the solvent is completely volatilized after 40 hours, the oriented state is fixed, then the mixed rubber is obtained through demoulding, the standing is kept for 6 hours at room temperature, and then the hot vulcanization forming is carried out at 150 ℃, and.
Comparative example 1
Adding 0.87g of FeCl 2 & 4H 2 O and 2.33g of FeCl 3 & 6H 2 O into 2g of NCC (m-NCC) dispersion liquid with the concentration of 0.5 percent extracted from microcrystalline cellulose, uniformly mixing, pouring the obtained mixed liquid into a three-neck flask placed in a water bath with the temperature of 80 ℃, continuously stirring, introducing nitrogen for 20min, dropwise adding ammonia water to adjust the pH value of the mixed liquid to be 10, continuously reacting for 30min, finishing, alternately washing the reaction product for 4 times by using deionized water and ethanol, and finally obtaining the hybrid particle dispersion liquid with the mass ratio of NCC to Fe 3 O 4 being 2: 1.
According to the weight portion, the dispersion liquid containing 20 portions of NCC @ Fe 3 O 4 is slowly added into natural rubber latex containing 100 portions of dry rubber, then the ethanol dispersion liquid containing 1.5 portions of sulfur, 5 portions of zinc oxide, 1 portion of stearic acid, 1.5 portions of benzothiazole disulfide and 0.6 portion of N-cyclohexyl-2-benzothiazole sulfenamide is added into the mixed liquid to be uniformly mixed, then the mixed liquid is poured into a polytetrafluoroethylene mould to be molded, the solvent is volatilized at 50 ℃, the solvent is completely volatilized after 48 hours, then the mixed rubber is obtained after demoulding, after the mixed rubber is placed for 6 hours at room temperature, the heat vulcanization molding is carried out at 150 ℃, and the isotropic rubber composite material (shown in table 1) is obtained.
Comparative example 2
Adding 0.87g of FeCl 2.4H 2 O and 2.33g of FeCl 3.6H 2 O into 100ml of deionized water, uniformly mixing, pouring the obtained mixed solution into a three-neck flask placed in a water bath at 70 ℃, continuously stirring, introducing nitrogen for 20min, dropwise adding ammonia water to adjust the pH of the mixed solution to 10, continuing to react for 30min, finishing the reaction, alternately washing the reaction product for 4 times by using deionized water and ethanol, and finally obtaining Fe 3 O 4 dispersion.
According to the mass parts, 10 parts of Fe 3 O 4 dispersion liquid is slowly added into nitrile rubber latex containing 100 parts of crude rubber, then ethanol dispersion liquid containing 1.5 parts of sulfur, 5 parts of zinc oxide, 1 part of stearic acid and 1 part of N-cyclohexyl-2-benzothiazole sulfonamide is added into the mixed liquid and uniformly mixed, then the mixed liquid is poured into a polytetrafluoroethylene mold for casting molding, the solvent is completely volatilized after drying for 48 hours at 50 ℃, the mixed rubber is obtained after demolding, and after standing for 6 hours at room temperature, the magnetic rubber composite material without NCC is obtained by hot vulcanization molding at 150 ℃ (see Table 1).
In contrast, comparative example 1, in which no external magnetic field was applied during the solvent evaporation, resulted in an isotropic composite material, and comparative example 2, in which only Fe 3 O 4 magnetic particles were added, had limited performance because of no reinforcement of the rubber by NCC.
TABLE 1 comparison of the Properties of the anisotropic magnetic rubber composites according to the invention with those of the comparative examples
In table 1, the degree of orientation (η) is defined as the ratio of the tensile strength in the parallel orientation direction (TS ∥) to the tensile strength in the perpendicular orientation direction (TS ⊥), and the greater the value of η, the greater the degree of orientation:
Tensile strength includes parallel and perpendicular directions. The magnetic property of the sample is tested at room temperature by adopting a Vibration Sample Magnetometer (VSM) of a PPMS-9 type comprehensive physical property measuring system of the American Quantum Design company, and the testing range is-20.0 kOe.
As can be seen from Table 1, by the comparative examples and comparative examples 1, the composite materials with obviously different tensile strengths in the parallel orientation direction and the perpendicular orientation direction can be obtained by applying the external magnetic field, and show obvious anisotropic behavior, so that the technology provided by the invention can induce the orientation arrangement of NCC @ Fe 3 O 4 hybrid particles, and has better application value in the fields of bending deformation, oriented stretching and the like.
It can be seen from comparing example 2 with comparative example 2 that, with the same addition of 10 parts of filler, the single Fe 3 O 4 can not have a good reinforcing effect on rubber due to the smooth surface and the weak interaction with the rubber molecular chain, the tensile strength of the prepared composite material is only about 17.5MPa (comparative example 2), while the mechanical properties of the prepared composite material can be significantly improved by loading Fe 3 O 4 on the NCC surface with high reinforcing property and magnetically inducing orientation arrangement of hybrid particles, the tensile strength in the parallel direction is as high as 23.8MPa (example 2), the lifting range is as high as 36% as compared with comparative example 2, and further, the magnetic field strength and the distance between the magnet and the die edge have a significant influence on the orientation degree of the hybrid particles in the prepared composite material by comparing the orientation degrees of the examples.
The technology provided by the invention can fully utilize the characteristic that the strength of the NCC in the axial direction is obviously superior to that in the radial direction, and more fully play the reinforcing effect of the NCC on rubber. At lower filler levels (there is some comparison to show why they are small), even more than isotropic materials can achieve the effect of requiring higher filler levels. Comparing example 2 with comparative example 1, it can be seen that the tensile strength of the material prepared with only 10 parts of hybrid particles in the parallel direction reached 23.8MPa, which is higher than the tensile strength (22.5MPa) of the isotropic composite material prepared with 20 parts of hybrid particles in comparative example 1. The technology provided by the invention is beneficial to reducing the using amount of the filler, reducing the energy consumption of the material in the processing process, reducing the density of the material and meeting the light-weight use requirement. Meanwhile, the rubber composite material prepared by the invention also has certain magnetism, and the application range of the rubber composite material can be further expanded.
The present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (10)
1. The magnetic rubber composite material with anisotropy is characterized by comprising the following raw materials in parts by weight:
The NCC @ Fe 3 O 4 hybrid particle dispersion liquid is prepared by the following steps of adding Fe 2+ and Fe 3+ into an NCC water dispersion liquid, uniformly mixing, removing air, adjusting the pH value to 9-11, controlling the temperature to be 50-80 ℃, reacting for 20-40 min, and washing a product after reaction to obtain the NCC @ Fe 3 O 4 hybrid particle dispersion liquid, wherein the mass ratio of NCC to Fe 3 O 4 in the NCC @ Fe 3 O 4 hybrid particle dispersion liquid is 1: 2-4: 1;
the preparation method comprises the steps of mixing the obtained NCC @ Fe 3 O 4 hybrid particle dispersion liquid with latex or rubber solution, adding sulfur, zinc oxide, stearic acid and an accelerator, uniformly mixing, pouring into a mold placed in an external magnetic field, inducing the NCC @ Fe 3 O 4 hybrid particles in the solution to be arranged in parallel in the direction of the magnetic field through the magnetic field, and carrying out vulcanization molding.
2. The anisotropic magnetic rubber composite of claim 1, wherein the rubber is a mixture of one or more of natural rubber, epoxidized natural rubber, styrene-butadiene rubber, nitrile rubber, and ethylene-propylene rubber.
3. The anisotropic magnetic rubber composite of claim 1, wherein the accelerator is one or more of benzothiazole disulfide, N-cyclohexyl-2-benzothiazolesulfenamide, N-t-butyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, tetramethylthiuram disulfide, N-dicyclohexyl-2-benzothiazolesulfenamide.
4. The anisotropic magnetic rubber composite material of claim 1, wherein the NCC is a rod-like product extracted from microcrystalline cellulose, cotton, sisal, flax, paper, crop straw and tunicate by sulfuric acid hydrolysis, and having a diameter of 10-20 nm and a length of 200 nm-2 μm.
5. The anisotropic magnetic rubber composite of claim 4, wherein the aqueous NCC dispersion has a mass concentration of NCC of 0.1-1.0%.
6. The anisotropic magnetic rubber composite material of claim 1, wherein the Fe 3 O 4 is spherical particles with a diameter of 20-30 nm synthesized by a coprecipitation method using a solution containing Fe 2+ and Fe 3+.
7. The anisotropic magnetic rubber composite material of claim 1, wherein the pH is adjusted to 9-11 by adding ammonia water.
8. the anisotropic magnetic rubber composite material of claim 1, wherein the washed product is washed with absolute ethyl alcohol and deionized water alternately for 3-6 times.
9. The method for preparing a magnetic rubber composite material having anisotropy according to claim 1, characterized by comprising the steps of:
1) Preparing a NCC @ Fe 3 O 4 hybrid particle dispersion liquid;
2) Mixing the obtained NCC @ Fe 3 O 4 hybrid particle dispersion liquid with latex or rubber solution, adding sulfur, zinc oxide, stearic acid and an accelerator, uniformly mixing, pouring into a mold placed in an external magnetic field, inducing the NCC @ Fe 3 O 4 hybrid particles in the solution to be aligned in parallel along the direction of the magnetic field by the magnetic field, continuously applying the magnetic field in the solvent volatilization process, fixing the orientation state, controlling the magnetic field strength to be 50 mT-500 mT, and controlling the distance between a magnetic field generator and the mold to be 10-40 mm until the solvent is completely volatilized to obtain anisotropic rubber/NCC @ Fe 3 O 4 rubber compound;
3) And (3) paving the rubber/NCC @ Fe 3 O 4 mixed rubber obtained in the step 2) in a hot-press forming die according to the orientation direction, and carrying out vulcanization forming to obtain the anisotropic magnetic rubber composite material.
10. the method for preparing the anisotropic magnetic rubber composite material of claim 9, wherein the material of the mold is polytetrafluoroethylene; the solvent is volatilized for 2-3 days at 40-60 ℃.
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| CN112574574A (en) * | 2020-12-07 | 2021-03-30 | 上海阿莱德实业股份有限公司 | Silica gel-based carbon material oriented heat-conducting interface material and electromagnetic preparation method thereof |
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