CN110467761B - Lignin compounded magnetic thermoplastic elastomer and preparation method thereof - Google Patents
Lignin compounded magnetic thermoplastic elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lignin compounded magnetic thermoplastic elastomer and a preparation method thereof, and the preparation method comprises the following steps: (1) putting lignin in a solvent, and carrying out ultrasonic filtration to obtain a filtrate; (2) dissolving ferric salt and ferrous salt in water, stirring, dropwise adding ammonia water into the mixture until black flocculate appears, and stirring to obtain reaction liquid; (3) when the temperature is reduced, dropwise adding the filtrate, stirring, aging, centrifuging to obtain a solid product, and washing the solid product to be neutral to obtain lignin-ferroferric oxide nanoparticles; (4) plasticating rubber, dissolving the rubber in a solvent, adding nano particles into the solvent, and stirring to obtain a suspension; volatilizing the solvent and drying; (5) and (4) mixing the materials obtained in the step (4), discharging, thinly passing, and performing hot press molding to obtain the material. The invention adopts a solution method, and no vulcanizing agent is added in the process, so that the reinforcing effect and the magnetic property of the composite material can be effectively improved, and the composite material can be molded again.
Description
Technical Field
The invention belongs to the technical field of preparation of functional materials, particularly relates to a preparation method of a magnetic thermoplastic elastomer, and particularly relates to a lignin-compounded magnetic thermoplastic elastomer and a preparation method thereof.
Background
The thermoplastic elastomer is also called as artificial rubber, and has the physical and mechanical properties of high elasticity and the like of the traditional vulcanized rubber and the processing property of thermoplastic plastics.
Magnetic materials are a general term for materials that can react in some way to a magnetic field, and are generally classified into soft magnetic materials and hard magnetic materials according to the difficulty of magnetization, and ferroferric oxide is widely used as the most common magnetic substance in magnetic materials. The composite material prepared by the magnetic powder and the thermoplastic elastomer is called as the magnetic thermoplastic elastomer, and the magnetic thermoplastic elastomer has wide application and has mature or potential application value in a plurality of fields such as refrigerator sealing strips, electromagnetic shielding devices, medical instruments and the like.
Lignin is the second largest biomass resource in the world next to cellulose, but is used as a waste in the biorefinery industry and the paper industry for a long time, so that the recycling rate is low, and serious environmental pollution is caused. The lignin structure contains a large number of phenolic hydroxyl groups. Resulting in large intermolecular forces, easy agglomeration into large particles, and difficulty in dispersion.
In the prior art, elastomer materials are mostly prepared by a dry method, so that various problems that magnetic particles are difficult to be well dispersed in a matrix material, the toughness of the elastomer is poor when the addition amount of the magnetic particles is high, and the like are faced.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art and provides a lignin compounded magnetic thermoplastic elastomer and a preparation method of the thermoplastic elastomer.
In order to solve the technical problem, the invention discloses a preparation method of a lignin compounded magnetic thermoplastic elastomer, which comprises the following steps:
(1) putting lignin in a solvent, performing ultrasonic treatment and filtering to obtain a filtrate;
(2) dissolving ferric salt and ferrous salt in water, heating and stirring, dropwise adding ammonia water into the mixture until black flocculate appears, maintaining the pH value to be above 10, and continuously stirring to obtain reaction liquid;
(3) after the temperature of the reaction liquid obtained in the step (2) is reduced, dropwise adding the filtrate obtained in the step (1), stirring, cooling at room temperature, aging, centrifuging to obtain a solid product and a filtrate, washing the solid product to be neutral to obtain lignin-ferroferric oxide nanoparticles, and measuring the solid content of the lignin-ferroferric oxide nanoparticles;
(4) plasticating rubber, placing the rubber into a solvent, adding the lignin-ferroferric oxide nano particles obtained in the step (3) after dissolving, and stirring to obtain a suspension; volatilizing the solvent in the suspension, and drying;
(5) and (4) adding the material obtained in the step (4) into an internal mixer for mixing, discharging, performing thin-pass through by using an open mill, and performing hot-press molding by using a flat vulcanizing machine to obtain the lignin composite magnetic thermoplastic elastomer.
In the step (1), the lignin is any one or combination of more of herbaceous lignin, hardwood lignin, softwood lignin and lignin modified by the lignin; the solvent is tetrahydrofuran.
In the step (1), the dosage of each lignin is 50-200 g, and the dosage of the tetrahydrofuran solvent is 200-1000 mL; the frequency of the ultrasonic wave is 20 KHz-130 KHz, and the time is 1-30 min.
In the step (2), the ferric salt is any one or combination of ferric chloride and ferric sulfate; the ferrous salt is any one or the combination of ferrous chloride and ferrous sulfate.
In the step (2), ferric salt and ferrous salt with the mass ratio of ferric ion to ferrous ion of 2:1 are dissolved in water, and the amount of water is controlled to ensure that the mass concentration of ferric ion is 0.05-0.15 mol/L; stirring at 50-80 ℃ and 200-1000 rpm for 5-20 min under the protection of nitrogen; dropwise adding 5-25 wt% ammonia water at a rate of 5-15 mL/min until black flocculate appears, maintaining the pH value at above 10, and continuously stirring at 200-1000 rpm for 1-5 h to obtain a reaction solution.
Among them, the concentration of the aqueous ammonia is preferably 25 wt%.
In the step (3), when the temperature of the reaction liquid obtained in the step (2) is reduced to below 50 ℃, dropwise adding the filtrate obtained in the step (1) at a rate of 1.5-35 mL/min, wherein the volume ratio of the filtrate to the reaction liquid is 1: 8-1: 120; stirring at 200-1000 rpm for 0.5-2 h, cooling and aging at room temperature for 1-2 h, centrifuging at 2000-10000 rpm for 5-30 min to obtain a solid product and a filtrate, washing the solid product to be neutral with water to obtain lignin-ferroferric oxide nanoparticles, and further detecting the solid content of the lignin-ferroferric oxide nanoparticles.
In the step (4), the rubber is any one or combination of more of nitrile rubber, carboxyl nitrile rubber, chlorinated butyl rubber and brominated butyl rubber; the solvent is tetrahydrofuran.
In the step (4), plasticating the rubber for 1-10 min at room temperature, and placing the rubber in a solvent, wherein the mass volume ratio of the rubber to the solvent is 0.1-0.02 g/L; after dissolving, adding the lignin-ferroferric oxide nanoparticles obtained in the step (3) into the solution, wherein the mass ratio of the rubber to the lignin-ferroferric oxide nanoparticles is 5: 1-1: 5; stirring at 200-1000 rpm for 0.5-2 h to obtain a suspension, placing the suspension in a fume hood to volatilize the solvent, and drying.
Wherein the mass of the ferroferric oxide nanoparticles is the mass of solids in the lignin-ferroferric oxide nanoparticles prepared in the step (3), namely the mass of the solids is multiplied by the mass of the product obtained in the step (3).
In the step (5), the mixing temperature is 80-180 ℃ and the mixing time is 5-20 min; the open milling and thin passing times are 5-20 times; the temperature of the plate vulcanizing machine is 120-250 ℃; the hot-press forming time is 5-30 min.
The lignin composite magnetic thermoplastic elastomer prepared by the method.
According to the invention, lignin and magnetic particles are introduced as mutual dispersants on the basis of the prior art, the composite magnetic particles are prepared in situ, and the thermoplastic elastomer is prepared by a solution method, so that the dispersibility of the magnetic particles in a matrix material can be greatly improved; in addition, the lignin is used as a high polymer with good plasticity, and is different from traditional magnetic particles such as inorganic rigid particles, and the lignin magnetic particles can greatly improve the toughness of the elastomer material. The technology has obvious advantages compared with the prior art in combination.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. according to the invention, lignin is introduced in the process of preparing the magnetic nanoparticles, and the lignin-ferroferric oxide magnetic particles are synthesized in situ by utilizing the chelation between the lignin and metal elements, so that the agglomeration of the lignin is weakened, and the ferroferric oxide is easily dispersed into a nano scale.
2. The method adopts a solution method when preparing the composite material, so that the step of drying magnetic particles after centrifugation is omitted, and compared with the method for preparing the magnetic thermoplastic elastomer by a dry method in the prior art, the solution method is more favorable for nano-scale dispersion of magnetic nano particles and lignin in a material matrix, thereby improving the reinforcing effect of the composite material, and ensuring that the material has good magnetic property and reinforcing effect.
3. The lignin compounded magnetic thermoplastic elastomer prepared by the invention has excellent mechanical property and remarkably improved magnetic property, and can be widely applied to the application fields of household appliances, electronic products, automobile parts and the like which have high requirements on mechanical property and magnetic property.
4. In the invention, no vulcanizing agent is added in the process of preparing the elastomer, so molecular chains are not crosslinked, and the obtained elastomer can be molded again.
Drawings
FIG. 1 is an infrared spectrum of the lignin-ferroferric oxide nanoparticles of example 1.
FIG. 2 is a transmission electron microscope image of the lignin-ferroferric oxide nanoparticles of example 1.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
Example 1: a lignin composite magnetic thermoplastic elastomer and a preparation method thereof are disclosed:
(1) dissolving 110g of lignin in 500mL of tetrahydrofuran solvent, carrying out 40KHz ultrasonic treatment for 10min, and filtering to remove undissolved lignin to obtain filtrate;
(2) 260g of FeCl3·6H2O and 96g FeCl2·4H2Dissolving O in 12L of water, heating to 65 ℃, stirring for 10min under the protection of nitrogen, dropwise adding 25% wt of concentrated ammonia water at the speed of 10mL/min until black flocculate appears, maintaining the pH value to be above 10, and continuously stirring for 2 h; wherein the stirring speed is 500 rpm;
(3) when the temperature of the reaction liquid is reduced to 50 ℃, dropwise adding the filtrate obtained in the step (1) at the speed of 10mL/min, continuously stirring at 500rpm/min for 30min, cooling and aging at room temperature for 1h, centrifuging at 4000rpmn for 10min, separating a product, washing the solid to be neutral by water, and preparing the lignin-ferroferric oxide nano particle, wherein the solid content is 39% by measuring;
(4) plasticating the carboxylated nitrile rubber for 5min at normal temperature, weighing 40g of the carboxylated nitrile rubber, placing the weighed carboxylated nitrile rubber into 400mL of tetrahydrofuran solvent, dissolving the weighed carboxylated nitrile rubber overnight, adding 51.3g (with the solid content of 20g) of the product obtained in the step (3), mechanically stirring the mixture at 500rpm for 1h, placing the obtained suspension into a fume hood, volatilizing the tetrahydrofuran solvent, and then placing the suspension into an oven for complete drying;
(5) and (3) adding the material obtained in the step (4) into an internal mixer, mixing for 30min at 120 ℃, thinly passing through an open mill for 20 times of sheet discharging, and placing the sheet into a flat vulcanizing machine for hot pressing for 30min at 180 ℃ for molding.
Example 2: a lignin composite magnetic thermoplastic elastomer and a preparation method thereof are disclosed:
steps (1) to (3) were the same as in example 1,
(4) plasticating the carboxylated nitrile rubber for 5min at normal temperature, weighing 30g of the carboxylated nitrile rubber, placing the weighed carboxylated nitrile rubber into 300mL of tetrahydrofuran solvent, dissolving the weighed carboxylated nitrile rubber overnight, adding the product obtained in the step (3) with the solid content of 30g, mechanically stirring the mixture at 500rpm for 1h, placing the obtained suspension into a fume hood to volatilize the tetrahydrofuran solvent, and then placing the suspension into an oven to be completely dried;
(5) and (3) adding the material obtained in the step (4) into an internal mixer, mixing for 30min at 120 ℃, thinly passing through an open mill for 20 times of sheet discharging, and placing the sheet into a flat vulcanizing machine for hot pressing for 30min at 180 ℃ for molding.
Example 3: a lignin composite magnetic thermoplastic elastomer and a preparation method thereof are disclosed:
steps (1) to (3) were the same as in example 1,
(4) plasticating the carboxylated nitrile rubber for 5min at normal temperature, weighing 20g of the carboxylated nitrile rubber, placing the weighed carboxylated nitrile rubber into 200mL of tetrahydrofuran solvent, dissolving the weighed carboxylated nitrile rubber overnight, adding the product obtained in the step (3) with the solid content of 40g, mechanically stirring the mixture at 500rpm for 1h, placing the obtained suspension into a fume hood to volatilize the tetrahydrofuran solvent, and then placing the suspension into an oven to be completely dried;
(5) and (3) adding the material obtained in the step (4) into an internal mixer, mixing for 30min at 120 ℃, thinly passing through an open mill for 20 times of sheet discharging, and placing the sheet into a flat vulcanizing machine for hot pressing for 30min at 180 ℃ for molding.
Example 4: a lignin composite magnetic thermoplastic elastomer and a preparation method thereof are disclosed:
steps (1) to (3) were the same as in example 1,
(4) plasticating the carboxylated nitrile rubber for 5min at normal temperature, weighing 15g of the carboxylated nitrile rubber, placing the weighed carboxylated nitrile rubber into 150mL of tetrahydrofuran solvent, dissolving the weighed carboxylated nitrile rubber overnight, adding the product obtained in the step (3) with the solid content of 45g, mechanically stirring the mixture at 500rpm for 1h, placing the obtained suspension into a fume hood to volatilize the tetrahydrofuran solvent, and then placing the suspension into an oven to be completely dried;
(5) and (3) adding the material obtained in the step (4) into an internal mixer, mixing for 30min at 120 ℃, thinly passing through an open mill for 20 times of sheet discharging, and placing the sheet into a flat vulcanizing machine for hot pressing for 30min at 180 ℃ for molding.
Example 5: a lignin composite magnetic thermoplastic elastomer and a preparation method thereof are disclosed:
step (1) As in example 1
(2) 193g of Fe2(SO4)3And 134g FeSO4·7H2Dissolving O in 12L of water, stirring and heating to 65 ℃, stirring for 10min under the protection of nitrogen, dripping 25 percent by weight of concentrated ammonia water at the speed of 10mL/min until black flocculate appears, maintaining the pH value to be above 10, and continuously stirring for 2h at the stirring speed of 500 rpm;
(3) when the temperature of the reaction liquid is reduced to 50 ℃, dripping the lignin tetrahydrofuran solution obtained in the step (1) at the speed of 10mL/min, continuously stirring at 500rpm for 30min, cooling and aging at room temperature for 1h, centrifuging at 4000rpm for 10min to separate a product, washing the solid to be neutral by water, preparing lignin-ferroferric oxide nano particles, and measuring the solid content of the lignin-ferroferric oxide nano particles;
(4) plasticating brominated butyl rubber for 5min at normal temperature, weighing 40g of carboxylated nitrile rubber, placing the weighed carboxylated nitrile rubber into 400mL of tetrahydrofuran solvent, dissolving the weighed carboxylated nitrile rubber overnight, adding a product obtained in the step (3) with the solid content of 20g, mechanically stirring the mixture at 500rpm for 1h, placing the obtained suspension into a fume hood to volatilize the tetrahydrofuran solvent, and then placing the suspension into an oven to be completely dried;
(5) and (3) adding the material obtained in the step (4) into an internal mixer, mixing for 30min at 120 ℃, thinly passing through an open mill for 20 times of sheet discharging, and placing the sheet into a flat vulcanizing machine for hot pressing for 30min at 180 ℃ for molding.
Example 6: a lignin composite magnetic thermoplastic elastomer and a preparation method thereof are disclosed:
step (1) As in example 1
(2) 193g of Fe2(SO4)3And 134g FeSO4·7H2Dissolving O in 12L water, stirring and heating to 65 deg.C, stirring under nitrogen protection for 10min, adding dropwise 25% concentrated ammonia water at a rate of 10mL/min until black flocculate appears, maintaining pH above 10, stirring for 2 hr, and stirringThe stirring speed is 500 rpm;
(3) when the temperature of the reaction liquid is reduced to 50 ℃, dripping the lignin tetrahydrofuran solution obtained in the step (1) at the speed of 10mL/min, continuously stirring at 500rpm for 30min, cooling and aging at room temperature for 1h, centrifuging at 4000rpm for 10min to separate a product, washing the solid to be neutral by water, preparing lignin-ferroferric oxide nano particles, and measuring the solid content of the lignin-ferroferric oxide nano particles;
(4) plasticating brominated butyl rubber for 5min at normal temperature, weighing 20g of carboxylated nitrile rubber, placing the weighed carboxylated nitrile rubber into 200mL of tetrahydrofuran solvent, dissolving the weighed carboxylated nitrile rubber overnight, adding a product obtained in the step (3) with the solid content of 40g, mechanically stirring the mixture at 500rpm for 1h, placing the obtained suspension into a fume hood to volatilize the tetrahydrofuran solvent, and then placing the suspension into an oven to be completely dried;
(5) and (3) adding the material obtained in the step (4) into an internal mixer, mixing for 30min at 120 ℃, thinly passing through an open mill for 20 times of sheet discharging, and placing the sheet into a flat vulcanizing machine for hot pressing for 30min at 180 ℃ for molding.
Comparative example 1
Carboxylated nitrile rubber without lignin-ferroferric oxide magnetic particles was used as comparative example 1.
Comparative example 2: solid state process
(1) Dissolving 110g of lignin in 500mL of tetrahydrofuran solvent, carrying out 40KHz ultrasonic treatment for 10min, and filtering to remove undissolved lignin to obtain filtrate;
(2) 260g of FeCl3·6H2O and 96g FeCl2·4H2Dissolving O in 12L of water, heating to 65 ℃, stirring for 10min under the protection of nitrogen, dropwise adding 25% wt of concentrated ammonia water at the speed of 10mL/min until black flocculate appears, maintaining the pH value to be above 10, and continuously stirring for 2 h; wherein the stirring speed is 500 rpm;
(3) when the temperature of the reaction liquid is reduced to 50 ℃, dropwise adding the filtrate obtained in the step (1) at the speed of 10mL/min, continuously stirring at 500rpm/min for 30min, cooling and aging at room temperature for 1h, centrifuging at 4000rpmn for 10min, separating a product, washing the solid to be neutral by water, preparing lignin-ferroferric oxide nano particles, and drying;
(4) plasticating the carboxylated nitrile rubber for 5min at normal temperature, weighing 40g of carboxylated nitrile rubber and 20g of the product obtained in the step (3), adding the weighed materials into an internal mixer, mixing for 30min at 120 ℃, thinly passing through an open mill for 20 times of sheet discharging, and placing the sheet into a flat plate vulcanizing machine for hot pressing for 30min at 180 ℃ for molding.
Comparative example 3: is molded again
The thermoplastic elastomer prepared in example 1 was cut into pieces and then molded again according to the procedure (5).
Comparative example 4: adding vulcanizing agent
In comparative example 1, 0.6g of sulfur, 0.6g of tetramethylthiuram disulfide, 0.6g of N-cyclohexyl-2-benzothiazole sulfonamide, 2g of zinc oxide and 0.8g of stearic acid are added in the banburying process of the step (5), other conditions are not changed, and the formed elastomer cannot be formed again and has no plasticity.
Performing infrared and electron microscope image detection on the lignin-ferroferric oxide nanoparticles obtained in the above embodiments 1 to 4, wherein an infrared spectrum IS obtained by characterization of a NICLET IS5 modal Id7 Fourier infrared spectrophotometer (FIG. 1); the transmission electron micrographs were obtained by measurement with a transmission electron microscope of model Jem-2100F, manufactured by Japan K.K., with a scale of 100nm (FIG. 2). 628cm can be seen from the infrared spectrogram of the lignin-ferroferric oxide nano particle-1The Fe-O stretching vibration of the ferroferric oxide is nearby, and the prepared nano particles simultaneously have C-H, C-O, O-H stretching vibration peaks of lignin and Fe-O stretching vibration peaks of the ferroferric oxide, which indicates that the lignin is successfully chelated with metal elements. The morphology of the lignin-ferroferric oxide nanoparticles in a transmission electron microscope shows that the prepared lignin-ferroferric oxide nanoparticles are all nanoparticles with the diameter of about 20 nm.
The physical properties and the magnetic properties of the lignin composite magnetic thermoplastic elastomer prepared in the above examples and the carboxyl nitrile rubber in the comparative example were tested. Wherein the tensile property is tested according to GB/T528-2009; the hardness detection method comprises the steps of placing a sample strip on a Shore durometer A, pressing down a handle to enable a hardness gauge to be in horizontal contact with a sample, and reading within 1 s; the saturation induction density and the hysteresis loop were measured by a vibrating magnetometer (VSM) according to the national standard GB 11209-1989.
Table 1: physical and mechanical Properties of examples and comparative examples
Table 2: magnetic Properties of the magnetic thermoplastic Elastomers of the examples
| Saturation magnetization emu/g | Residual magnetization emu/g | Coercive force Oe | |
| Example 1 | 22.01 | 0.51 | 10.68 |
| Example 2 | 24.18 | 0.58 | 10.10 |
| Example 3 | 52.18 | 1.44 | 21.57 |
| Example 4 | 57.57 | 4.15 | 25.68 |
| Comparative example 2 | 20.06 | 0.47 | 9.35 |
| Comparative example 3 | 21.39 | 0.53 | 10.66 |
The tensile strength of the thermoplastic elastomer in the example shown in table 1 is obviously higher than that of the thermoplastic elastomer in the comparative example without the lignin-ferroferric oxide nanoparticles, the stress at definite elongation and the hardness are also obviously improved, and the mechanical property of the comparative example 4 is optimal along with the increase of the addition amount of the lignin-ferroferric oxide nanoparticles.
Table 2 shows the magnetic performance of the comparative example, with the increase of the addition amount of the lignin-ferroferric oxide nano particles, the saturation magnetization of the material can reach 57.57emu/g at most, the residual magnetization reaches 4.15emu/g, and good magnetic performance is shown. The magnetic thermoplastic elastomer prepared by the invention adopts a solution method, so that the magnetic powder is well nano-dispersed in the polymer matrix, and the elastomer has excellent mechanical strength and toughness and good magnetic property, can meet market demands and also provides a brand new idea for the utilization of lignin in the field of materials.
By comparing the data of example 1 and comparative example 2 in tables 1 and 2, it can be seen that the thermoplastic elastomer prepared by the dry method has both lower mechanical properties and magnetic properties than those of the solution method, indicating that the solution method is more advantageous for the dispersion of the magnetic particles than the dry method; by comparing the data of example 1 and comparative example 3, it can be seen that the mechanical and magnetic properties of the thermoplastic elastomer material reshaped after the destruction are not significantly different from those before the destruction, indicating that the thermoplastic elastomer has good re-plasticity, and if a vulcanizing agent is added, the material loses the advantage (comparative example 4).
The present invention provides a lignin-compounded magnetic thermoplastic elastomer and a method for preparing the same, and a plurality of methods and ways for implementing the technical scheme, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. A preparation method of a lignin compounded magnetic thermoplastic elastomer is characterized by comprising the following steps:
(1) putting lignin in a solvent, performing ultrasonic treatment and filtering to obtain a filtrate;
(2) dissolving ferric salt and ferrous salt in water, and stirring at the temperature of 50-80 ℃ and at the rpm of 200-1000 for 5-20 min under the protection of nitrogen; dropwise adding ammonia water with the concentration of 5-25 wt% at the speed of 5-15 mL/min until black flocculate appears, maintaining the pH value to be above 10, and continuously stirring at 200-1000 rpm for 1-5 h to obtain a reaction solution;
(3) after the temperature of the reaction liquid obtained in the step (2) is reduced, dropwise adding the filtrate obtained in the step (1), stirring, cooling at room temperature, aging, centrifuging to obtain a solid product and a filtrate, and washing the solid product to be neutral to obtain lignin-ferroferric oxide nanoparticles;
(4) plasticating rubber, placing the rubber into a solvent, adding the lignin-ferroferric oxide nano particles obtained in the step (3) after dissolving, and stirring to obtain a suspension; volatilizing the solvent in the suspension, and drying;
(5) adding the material obtained in the step (4) into an internal mixer for mixing, performing thin-pass through by using an open mill after discharging, and performing hot-press molding by using a flat vulcanizing machine to obtain the lignin composite magnetic thermoplastic elastomer;
in the step (1), the solvent is tetrahydrofuran;
in the step (2), the amount of water is controlled to enable the amount concentration of the ferric ion substance to be 0.05-0.15 mol/L.
2. The method for preparing lignin-compounded magnetic thermoplastic elastomer according to claim 1, wherein in step (1), the lignin is any one or more of herbaceous lignin, hardwood lignin, softwood lignin and lignin modified by the lignin.
3. The method for preparing the lignin composite magnetic thermoplastic elastomer according to claim 1, wherein in the step (1), the amount of the tetrahydrofuran solvent is 200-1000 mL for each amount of lignin of 50-200 g; the frequency of the ultrasonic wave is 20 KHz-130 KHz, and the time is 1-30 min.
4. The method for preparing the lignin composite magnetic thermoplastic elastomer according to claim 1, wherein in the step (2), the ferric salt is any one or a combination of ferric chloride and ferric sulfate; the ferrous salt is any one or the combination of ferrous chloride and ferrous sulfate.
5. The method for preparing lignin-compounded magnetic thermoplastic elastomer according to claim 1, wherein in the step (2), ferric ions and ferrous ions are dissolved in water in a mass ratio of ferric salts to ferrous salts of 2: 1.
6. The preparation method of the lignin composite magnetic thermoplastic elastomer, according to claim 1, is characterized in that in the step (3), when the temperature of the reaction liquid obtained in the step (2) is reduced to below 50 ℃, the filtrate obtained in the step (1) is dripped at a rate of 1.5-35 mL/min, and the volume ratio of the filtrate to the reaction liquid is 1: 8-1: 120; stirring at 200-1000 rpm for 0.5-2 h, cooling and aging at room temperature for 1-2 h, centrifuging at 2000-10000 rpm for 5-30 min to obtain a solid product and a filtrate, and washing the solid product with water to be neutral to obtain the lignin-ferroferric oxide nanoparticles.
7. The method for preparing lignin-compounded magnetic thermoplastic elastomer according to claim 1, wherein in the step (4), the rubber is any one or more of nitrile rubber, carboxylated nitrile rubber, chlorinated butyl rubber and brominated butyl rubber; the solvent is tetrahydrofuran.
8. The preparation method of the lignin composite magnetic thermoplastic elastomer according to claim 1, wherein in the step (4), rubber is plasticated at room temperature for 1-10 min and placed in a solvent, and the mass-to-volume ratio of the rubber to the solvent is 0.1-0.02 g/L; after dissolving, adding the lignin-ferroferric oxide nanoparticles obtained in the step (3) into the solution, wherein the mass ratio of the rubber to the lignin-ferroferric oxide nanoparticles is 5: 1-1: 5; stirring at 200-1000 rpm for 0.5-2 h to obtain a suspension, placing the suspension in a fume hood to volatilize the solvent, and drying.
9. The method for preparing the lignin composite magnetic thermoplastic elastomer according to claim 1, wherein in the step (5), the mixing temperature is 80-180 ℃ and the mixing time is 5-20 min; the open milling and thin passing times are 5-20 times; the temperature of the plate vulcanizing machine is 120-250 ℃; the hot-press forming time is 5-30 min.
10. A lignin-compounded magnetic thermoplastic elastomer prepared by the method of any one of claims 1 to 9.
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| CN104875445A (en) * | 2015-04-30 | 2015-09-02 | 西南科技大学 | Magnetic and conductive rubber elastic body composite material and preparation method thereof |
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