CN111235624B - Lanthanum hydroxide nano whisker and preparation method and application thereof - Google Patents
Lanthanum hydroxide nano whisker and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a lanthanum hydroxide nano whisker and a preparation method and application thereof. The method comprises the following steps: (1) dropwise adding alkali liquor into an ethanol-water solution containing lanthanum salt under the condition of stirring to obtain a mixed solution; wherein the alkali liquor is sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, and the pH value of the mixed liquor is not less than 7.5; (2) placing the mixed solution in a closed reaction device, heating to the reaction temperature, and reacting to obtain a reaction mixture; (3) and carrying out post-treatment on the reaction mixture to obtain the lanthanum hydroxide nano whisker. The invention also discloses a polylactic acid composition and a preparation method thereof. The lanthanum hydroxide nano whisker prepared by the method has the advantages of large length-diameter ratio, uniform appearance and good dispersibility.
Description
Technical Field
The invention relates to lanthanum hydroxide nano whisker, a preparation method and application thereof, and a polylactic acid composition and a preparation method thereof.
Background
The rare earth lanthanide has a special atomic structure, and the compound is widely applied to the fields of light, electricity, magnetism, catalysis, agriculture and the like. The lanthanum hydroxide nano whisker is a rare earth compound with a special shape, and can be added into a high polymer material to modify the high polymer material. The lanthanum hydroxide whisker has toughening and reinforcing effects on high molecular materials due to the self crack bridging, the pull-out effect and other mechanisms. Furthermore, lanthanum hydroxide is non-toxic and green, and can improve the electrical insulation of the high polymer material.
However, the lanthanum hydroxide whisker prepared by the existing preparation method has poor control on the uniformity of the shape, size and appearance of the whisker, and the modification effect of lanthanum hydroxide on high polymer materials is seriously influenced.
CN102936028A discloses a method for preparing a flaky lanthanum hydroxide nanocrystal by a microwave-ultrasonic method. Microwave radiation energy penetrates through the extraction medium, microwave electromagnetic energy is converted into heat energy, the heat energy reaches the interior of the material, the temperature in the matrix is rapidly increased, the energy of lanthanum hydroxide growth elements is increased, and accordingly lanthanum hydroxide grows along the orientation direction. The obtained lanthanum hydroxide nanocrystal is of a sheet structure. However, the sheet structure has poor morphology unicity, and the modification effect of the sheet structure applied to the aspects of toughening and strengthening of the high polymer material is not good.
CN102942203B discloses a preparation method of rod-like lanthanum hydroxide nanocrystal. The lanthanum hydroxide prepared by the microwave-ultraviolet synthesis method is of a rod-like structure, and the diameter of the lanthanum hydroxide is about 20-40 nm. The process has poor control on the length of the lanthanum hydroxide crystal, and the preparation process needs components such as a surfactant and the like, so the preparation process is complex and the cost is high.
CN101948128A discloses a method for preparing lanthanum hydroxide crystals by a fluxing agent method. Mixing lanthanum hydroxide and sodium hydroxide or potassium hydroxide, adding the mixture into a closed reaction kettle, and reacting at the temperature of 350-400 ℃ for 0.1-120 h to obtain hexagonal prism-shaped lanthanum hydroxide crystals. The method can control the length-diameter ratio of the lanthanum hydroxide crystal by controlling the proportion of the lanthanum hydroxide and the sodium hydroxide or the potassium hydroxide. However, the obtained hexagonal prism-shaped lanthanum hydroxide crystal has large size, poor appearance unicity and poor toughening and reinforcing modification effects on high polymer materials.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing lanthanum hydroxide nanowhiskers, which has a large aspect ratio, a uniform morphology, and good dispersibility. Furthermore, the preparation method provided by the invention is simple in process and low in preparation cost. The invention also aims to provide the lanthanum hydroxide nano whisker prepared by the method, which has the advantages of small diameter, single appearance and good dispersibility. It is a further object of the present invention to provide the use of the above lanthanum hydroxide nanowhiskers for improving the strength and toughness of polylactic acid. In addition, the invention also provides polylactic acid containing the lanthanum hydroxide nano whisker and a preparation method thereof.
In one aspect, the invention provides a preparation method of lanthanum hydroxide nano whisker, which comprises the following steps:
(1) dropwise adding alkali liquor into an ethanol-water solution containing lanthanum salt under the condition of stirring to obtain a mixed solution; wherein the alkali liquor is sodium hydroxide aqueous solution or potassium hydroxide aqueous solution; the pH value of the mixed solution is not less than 7.5;
(2) placing the mixed solution in a closed reaction device, heating to the reaction temperature, and reacting to obtain a reaction mixture;
(3) and carrying out post-treatment on the reaction mixture to obtain the lanthanum hydroxide nano whisker.
According to the preparation method of the present invention, preferably, in the step (1), the lanthanum salt is one or more of lanthanum chloride, lanthanum nitrate, lanthanum carbonate and lanthanum sulfate.
According to the preparation method provided by the invention, in the step (1), the solvent of the lanthanum salt-containing ethanol-water solution is a mixed solvent formed by ethanol and deionized water in a mass ratio of 1: 1-5.
According to the preparation method of the present invention, preferably, in the step (1), the concentration of lanthanum salt in the lanthanum salt-containing ethanol-water solution is 0.05 to 1 mol/L; the concentration of the alkali liquor is 0.1-10 mol/L; the pH value of the mixed solution is 8-10.
According to the preparation method provided by the invention, preferably, in the step (2), the reaction temperature is 100-200 ℃, and the reaction time is 14-20 h; the closed reaction device is a hydrothermal reaction kettle with a polytetrafluoroethylene lining.
According to the production method of the present invention, preferably, in the step (3), the post-treatment includes a solid-liquid separation step, a washing step, a drying step and a grinding step; the solid-liquid separation step adopts centrifugal separation, and the rotating speed is 2000-8000 r/min; the washing step comprises washing with deionized water and ethanol alternately at least once; and in the drying step, a vacuum drying oven is adopted, the vacuum degree is 0.01-0.1 MPa, the drying temperature is 40-100 ℃, and the drying time is 5-12 hours.
The invention also provides lanthanum hydroxide nano whisker prepared by the preparation method; the diameter of the lanthanum hydroxide nano whisker is 30-50 nm, and the length of the lanthanum hydroxide nano whisker is 700-900 nm.
The invention also provides the application of the lanthanum hydroxide nano whisker in improving the strength and toughness of polylactic acid; the weight ratio of the lanthanum hydroxide nano whisker to the polylactic acid is 0.1-1: 30.
In another aspect, the present invention provides a polylactic acid composition, comprising the following components:
30-50 parts by weight of polylactic acid, 8-20 parts by weight of polyester, 0.1-2.0 parts by weight of nucleating agent, 0.1-2.0 parts by weight of antioxidant, 0.5-3 parts by weight of plasticizer, 0.1-2.0 parts by weight of soybean oil and 0.1-2.0 parts by weight of lanthanum hydroxide nanowhisker prepared by the preparation method according to claims 1-6;
wherein the polyester is selected from one or more of polybutylene adipate-terephthalate, polycaprolactone and polybutylene succinate;
wherein the diameter of the lanthanum hydroxide nano whisker is 30-50 nm, and the length of the lanthanum hydroxide nano whisker is 700-900 nm.
The invention also provides a preparation method of the polylactic acid composition, which comprises the following steps:
(1') preparing lanthanum hydroxide nanowhiskers according to the above preparation method;
(2') uniformly mixing the components, and placing the mixture in a two-roll plastic mixing machine for plastic mixing and molding; wherein the roll temperatures of the two rolls are respectively 90-150 ℃ and 170-200 ℃, and the roll spacing is 0.3-0.8 mm.
The lanthanum hydroxide nano whisker prepared by the preparation method has the advantages of large length-diameter ratio, uniform appearance and good dispersibility. In addition, the preparation method has simple process, does not need additives such as a surfactant, a template agent and the like in the generation process, and reduces the preparation cost. The lanthanum hydroxide nano whisker prepared by the method is added into polylactic acid, is uniformly dispersed, and can well improve the strength and toughness of the polylactic acid.
Drawings
Figure 1 is an SEM image of lanthanum hydroxide nanowhiskers prepared in example 3.
Figure 2 is an XRD pattern of lanthanum hydroxide nanowhiskers prepared in example 3.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
In one aspect, the invention relates to lanthanum hydroxide nanowhiskers, methods of making, and uses thereof. In another aspect, the invention relates to polylactic acid compositions comprising lanthanum hydroxide nanowhiskers and methods of making the same. As described in detail below.
< method for producing whisker >
The preparation method of the lanthanum hydroxide nano whisker comprises the following steps: (1) preparing a mixed solution; (2) a reaction step; (3) and (5) post-processing.
In the preparation step of the mixed solution, an alkali solution is added dropwise to an ethanol-water solution containing a lanthanum salt under stirring to obtain a mixed solution. The stirring conditions are not particularly limited, and mechanical stirring or magnetic stirring may be used. In the invention, after the dropwise addition of the alkali liquor is stopped, the mixed solution is continuously stirred for 10-60 min; preferably, the mixed solution is continuously stirred for 20-50 min; more preferably, the mixed solution is continuously stirred for 30 to 40 min. According to one embodiment of the invention, the alkali liquor is added dropwise into the lanthanum salt-containing ethanol-water solution under magnetic stirring, and stirring is continued for 30min after the dropwise addition is stopped. By adopting the method, the lanthanum salt can be dissolved better, and the later generation of lanthanum hydroxide nanocrystals is facilitated.
In the invention, the alkali liquor is sodium hydroxide aqueous solution or potassium hydroxide aqueous solution; preferably, the alkali liquor is sodium hydroxide aqueous solution; more preferably, the lye is an aqueous sodium hydroxide solution formed by dissolving sodium hydroxide in deionized water. The adoption of the alkali liquor facilitates the control of the form of the lanthanum hydroxide nanocrystal. The concentration of the alkali liquor (namely the concentration of the alkaline substances) can be 0.1-10 mol/L; preferably, the concentration of the alkali liquor can be 0.5-8 mol/L; more preferably, the concentration of the alkali liquor can be 1-5 mol/L. The concentration of the alkali liquor is adopted, so that the size of the lanthanum hydroxide nanocrystal can be controlled conveniently during reaction.
In the invention, the lanthanum salt is one or more of lanthanum chloride, lanthanum nitrate, lanthanum carbonate and lanthanum sulfate; preferably, the lanthanum salt is one or more of lanthanum chloride heptahydrate, lanthanum nitrate hexahydrate, lanthanum carbonate octahydrate and lanthanum sulfate nonahydrate; more preferably, the lanthanum salt is one or more of lanthanum chloride heptahydrate, lanthanum nitrate hexahydrate, and lanthanum sulfate nonahydrate. The lanthanum salt is more favorable for controlling the size of the lanthanum hydroxide nano whisker and improving the purity of the lanthanum hydroxide nano whisker. According to one embodiment of the invention, the lanthanum salt is lanthanum chloride heptahydrate. The solvent in the lanthanum salt-containing ethanol-water solution is a mixed solvent formed by ethanol and deionized water in a mass ratio of 1: 1-5; preferably, the mass ratio of the ethanol to the deionized water is 1: 2-4; more preferably, the mass ratio of the ethanol to the deionized water is 1: 2-3. The concentration of the lanthanum salt in the ethanol-water solution containing the lanthanum salt can be 0.05-1 mol/L; preferably, the concentration of the lanthanum salt in the ethanol-water solution containing the lanthanum salt can be 0.1-0.8 mol/L; more preferably, the concentration of lanthanum salt in the lanthanum salt-containing ethanol-water solution can be 0.1-0.5 mol/L. The mixed solvent can better dissolve lanthanum salt, and is beneficial to the generation of lanthanum hydroxide nano crystal whisker in the later period.
According to one embodiment of the invention, the concentration of lanthanum salt in the lanthanum salt-containing ethanol-water solution is 0.05-1 mol/L; the concentration of the alkali liquor is 0.1-10 mol/L; preferably, the concentration of the lanthanum salt in the ethanol-water solution containing the lanthanum salt is 0.1-0.8 mol/L; the concentration of the alkali liquor is 0.5-8 mol/L; more preferably, the concentration of the lanthanum salt in the ethanol-water solution containing the lanthanum salt is 0.1-0.5 mol/L; the concentration of the alkali liquor is 1-5 mol/L.
In the invention, the pH value of the mixed solution is not less than 7.5; preferably, the pH value of the mixed solution is not less than 8; more preferably, the pH value of the mixed solution is 8-10. The shape of the lanthanum hydroxide nano crystal whisker can be controlled by controlling the pH value of the mixed solution in the range, and the generation rate is improved.
According to one embodiment of the invention, in the step (1), the concentration of the lanthanum salt in the lanthanum salt-containing ethanol-water solution is 0.05-1 mol/L; the concentration of the alkali liquor is 0.1-10 mol/L; the pH value of the mixed solution is 8-10.
In the reaction step, the mixed solution is placed in a closed reaction device and heated to the reaction temperature for reaction, so as to obtain a reaction mixture. In the invention, the reaction temperature can be 100-200 ℃; the reaction temperature can be 120-180 ℃; more preferably, the reaction temperature may be 140 to 180 ℃. The reaction time is 14-20 h; preferably, the reaction time is 16-20 h; more preferably, the reaction time is 16-18 h. The length-diameter ratio and the shape of the lanthanum hydroxide nano whisker can be better controlled and the dispersity of the lanthanum hydroxide nano whisker is improved by the reaction conditions of the method.
In the invention, the closed reaction device can be a hydrothermal reaction kettle; preferably, the closed reaction device can be a hydrothermal reaction kettle with a polytetrafluoroethylene lining; more preferably, the closed reaction device is a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and is placed in an air-blowing drying oven for heating. The polytetrafluoroethylene lining can improve the purity of the generated lanthanum hydroxide nano whisker.
According to one embodiment of the invention, in the step (2), the reaction temperature is 100-200 ℃, and the reaction time is 14-20 h; the closed reaction device is a hydrothermal reaction kettle with a polytetrafluoroethylene lining.
The post-treatment step is to obtain the lanthanum hydroxide nano crystal whisker by post-treating the reaction mixture. The post-treatment comprises a solid-liquid separation step, a washing step, a drying step and a grinding step. The solid-liquid separation step adopts centrifugal separation, and the rotating speed is 2000-8000 r/min; the washing step comprises washing with deionized water and ethanol alternately at least once; and in the drying step, a vacuum drying oven is adopted, the vacuum degree is 0.01-0.1 MPa, the drying temperature is 50-100 ℃, and the drying time is 5-12 hours. In the present invention, the grinding step may be performed by an existing crystal grinding method.
The solid-liquid separation step can adopt centrifugal separation, and the rotating speed can be 2000-8000 r/min; preferably, the rotating speed can be 3000-6000 r/min; more preferably, the rotation speed may be 4000-.
The washing step of the present invention comprises washing with deionized water and ethanol alternately at least once.
The drying step of the invention adopts a vacuum drying oven. The pressure of the vacuum drying oven can be 0.01-0.1 MPa; preferably 0.05 to 0.1 MPa; more preferably 0.05 to 0.08 MPa. The drying temperature is 50-100 ℃; preferably 50-80 ℃; more preferably 60 to 80 ℃. The drying time is 5-12 h; preferably 6-10 h; more preferably 6 to 8 hours.
< lanthanum hydroxide nanowhiskers and uses >
The lanthanum hydroxide nano whisker with the diameter of 30-50 nm and the length of 700-900 nm can be prepared by the preparation method. As shown in figure 1, the lanthanum hydroxide nanowhisker has uniform appearance and large length-diameter ratio.
The lanthanum hydroxide nano whisker can be used in a polylactic acid composition to improve the strength and toughness of the polylactic acid composition. Specifically, the invention provides the application of the lanthanum hydroxide nano whisker in improving the strength and toughness of polylactic acid; wherein the weight ratio of the lanthanum hydroxide nanowhiskers to the polylactic acid is 0.1-1: 30, preferably 0.2-0.8: 30, and more preferably 0.3-0.5: 30.
< polylactic acid composition and Process for producing the same >
The polylactic acid composition comprises the following components: 0.1-1 parts by weight of lanthanum hydroxide nano whisker and 30 parts by weight of polylactic acid. Preferably, the polylactic acid composition of the present invention comprises the following components: 0.2-0.8 parts by weight of lanthanum hydroxide nano whisker and 30 parts by weight of polylactic acid. More preferably, the polylactic acid composition of the present invention comprises the following components: 0.3-0.5 parts by weight of lanthanum hydroxide nano whisker and 30 parts by weight of polylactic acid.
According to one embodiment of the present invention, a polylactic acid composition comprises the following components:
30-50 parts of polylactic acid, 8-20 parts of polyester, 0.1-2.0 parts of nucleating agent, 0.1-2.0 parts of antioxidant, 0.5-3 parts of plasticizer, 0.1-2.0 parts of vegetable oil and 0.1-2.0 parts of lanthanum hydroxide nano whisker prepared by the preparation method. The polyester is selected from one or more of poly (butylene adipate-terephthalate), polycaprolactone and polybutylene succinate. The diameter of the lanthanum hydroxide nano whisker is 30-50 nm, and the length of the lanthanum hydroxide nano whisker is 700-900 nm.
According to one embodiment of the present invention, the polylactic acid composition consists of:
30-50 parts of polylactic acid, 8-20 parts of polyester, 0.1-2.0 parts of nucleating agent, 0.1-2.0 parts of antioxidant, 0.5-3 parts of plasticizer, 0.1-2.0 parts of vegetable oil and 0.1-2.0 parts of lanthanum hydroxide nano whisker prepared by the preparation method. The polyester is selected from one or more of polybutylene adipate-terephthalate, polycaprolactone and polybutylene succinate. The diameter of the lanthanum hydroxide nano whisker is 30-50 nm, and the length of the lanthanum hydroxide nano whisker is 700-900 nm.
In the present invention, the polylactic acid may be used in an amount of 30 to 50 parts by weight, preferably 30 to 38 parts by weight, and more preferably 30 to 35 parts by weight.
In the present invention, the amount of the polyester may be 8 to 20 parts by weight, preferably 10 to 15 parts by weight, and more preferably 10 to 12 parts by weight. The polyester is selected from one or more of polybutylene adipate-terephthalate, polycaprolactone and polybutylene succinate. Preferably, the polyester is selected from one or a mixture of two of polycaprolactone and polybutylene succinate. More preferably, the polyester is polycaprolactone.
In the present invention, the nucleating agent may be used in an amount of 0.1 to 2.0 parts by weight, preferably 0.2 to 1.0 part by weight, and more preferably 0.5 to 0.8 part by weight. The nucleating agent can improve the transparency, impact resistance and the like of the product, and a commercially available product can be used. The nucleating agent is selected from one of acrylate copolymer ACR, hydrazide compound TMC-306, hydrazide compound TMC-328 and phenyl zinc phosphate; preferably, the nucleating agent is selected from one of acrylate copolymer ACR, hydrazide compound TMC-306 and phenyl zinc phosphate; more preferably, the nucleating agent is an acrylate copolymer ACR.
In the present invention, the antioxidant may be used in an amount of 0.1 to 2.0 parts by weight, preferably 0.2 to 1.0 part by weight, and more preferably 0.5 to 0.8 part by weight. The antioxidant comprises one or more of antioxidant 1010, antioxidant 1076, antioxidant 1330, antioxidant 2246, antioxidant 3114, antioxidant 168 and hindered phenol antioxidant; preferably, the antioxidant comprises one or more of antioxidant 1010, antioxidant 1076, and antioxidant 1330; more preferably, the antioxidant comprises antioxidant 1010 or antioxidant 1076. According to one embodiment of the present invention, the antioxidant is antioxidant 1010.
In the present invention, the plasticizer is used in an amount of 0.5 to 3 parts by weight, preferably 0.5 to 2 parts by weight, and more preferably 0.6 to 0.8 part by weight. The plasticizer is selected from one of acetyl tributyl citrate, polyethylene glycol, diphenyl phthalate, triphenyl phosphite and dibutyl sebacate; preferably, the plasticizer is selected from one of acetyl tributyl citrate, diphenyl phthalate and triphenyl phosphite; more preferably, the plasticizer is acetyl tributyl citrate.
In the present invention, the vegetable oil may be used in an amount of 0.1 to 2.0 parts by weight, preferably 0.2 to 1.0 part by weight, and more preferably 0.3 to 0.8 part by weight. The vegetable oil comprises one or more of soybean oil, corn oil, peanut oil, sunflower seed oil, linseed oil, castor oil and rapeseed oil; preferably, the vegetable oil comprises one or more of soybean oil, corn oil, peanut oil, sunflower oil and linseed oil; more preferably, the vegetable oil comprises one or more of soybean oil, corn oil and peanut oil.
In the present invention, the lanthanum hydroxide nanowhiskers in the polylactic acid composition may be used in an amount of 0.1 to 2.0 parts by weight, preferably 0.2 to 1.0 part by weight, and more preferably 0.3 to 0.45 part by weight. In the invention, the diameter of the lanthanum hydroxide nano whisker is 30-50 nm, and the length of the lanthanum hydroxide nano whisker is 700-900 nm.
The preparation method of the polylactic acid composition comprises the following steps: preparing lanthanum hydroxide nano-whisker by adopting the preparation method; the components are uniformly mixed and placed in a double-roller plastic mixing machine for plastic mixing and molding. In the invention, the roller temperatures of the double rollers are respectively 90-150 ℃ and 170-200 ℃; preferably, the roll temperatures of the double rolls are 100-150 ℃ and 170-190 ℃ respectively; more preferably, the roll temperatures of the twin rolls are 120 to 150 ℃ and 170 to 180 ℃ respectively. The roller spacing is 0.3-0.8 mm; preferably 0.4-0.7 mm; more preferably 0.4 to 0.6 mm. The two roller temperatures are controlled within the temperature difference range, so that the forming is facilitated.
The following examples and comparative examples were all prepared using commercially available products:
nucleating agent: acrylate copolymer ACR, Asahi MeiACR 401
Plasticizer: acetyl tributyl citrate
The test methods of the examples and comparative examples are described below:
according to the method for measuring tensile properties of plastics (GB/T1040.1-2006), a sheet-like dumbbell sample was vertically clamped to an electronic universal tester and subjected to a tensile test at 25 ℃.3 samples were taken for each set of experiments and the average was taken to record the sample thickness, elongation at break and tensile strength.
Scanning Electron Microscope (SEM) test method: firstly, adhering a conductive adhesive on a carrying disc of a Scanning Electron Microscope (SEM), then uniformly scattering a small amount of lanthanum hydroxide nanocrystalline sample on the conductive adhesive, spraying gold, and analyzing and testing the appearance of the sample by the SEM; wherein the scanning electron microscope is a scanning electron microscope of Sigma-500 type of Germany Zeiss company.
X-ray powder diffraction (XRD) test method: lanthanum hydroxide nanowhisker samples were analyzed by X-ray powder diffraction (XRD) using an X' PertPRO type diffractometer from parnacco, the netherlands, using Cu Ka radiation ((λ ═ 0.15418nm), a scan velocity of 1 °/min, a scan angle 2 θ of 10 ° to 80 °, a tube current of 40mA, and a tube voltage of 40kV at room temperature.
Example 1
(1) Dissolving lanthanum chloride heptahydrate in a deionized water-ethanol mixed solvent to obtain a solution A with the lanthanum chloride concentration of 0.1 mol/L; in the mixed solvent, the mass ratio of ethanol to deionized water is 3: 1; and dissolving sodium hydroxide in deionized water to obtain a solution B with the concentration of the sodium hydroxide of 1 mol/L.
(2) Dropwise adding the solution B into the solution A under magnetic stirring to obtain a mixed solution, stopping dropwise adding the solution B when the pH value of the mixed solution is adjusted to 8.0, and continuously carrying out magnetic stirring on the mixed solution for 30min to obtain a solution C.
(3) And placing the solution C in a hydrothermal reaction kettle with a polytetrafluoroethylene lining, placing the hydrothermal reaction kettle in an air-blowing drying oven, heating to 140 ℃, and reacting for 20 hours to obtain a reaction mixture.
(4) Cooling the reaction mixture to 25 ℃, then carrying out centrifugal separation at the rotation speed of 5000r/min, alternately washing the solid product obtained by the centrifugal separation for a plurality of times by using deionized water and ethanol, then placing the solid product in a vacuum drying oven, carrying out vacuum drying for 8h under the conditions that the absolute vacuum degree is 0.08MPa and the temperature is 60 ℃, and finally grinding the dried product to obtain the lanthanum hydroxide nano whisker.
Example 2
(1) Dissolving lanthanum chloride heptahydrate in a deionized water-ethanol mixed solvent to obtain a solution A with the lanthanum chloride concentration of 0.3mol/L, wherein the mass ratio of ethanol to deionized water in the mixed solvent is 3: 1; and dissolving sodium hydroxide in deionized water to obtain a solution B with the concentration of the sodium hydroxide of 3 mol/L.
(2) Dropwise adding the solution B into the solution A under magnetic stirring to obtain a mixed solution, stopping dropwise adding the solution B when the pH value of the mixed solution is adjusted to 9.0, and continuously carrying out magnetic stirring on the mixed solution for 30min to obtain a solution C.
(3) And placing the solution C in a hydrothermal reaction kettle with a polytetrafluoroethylene lining, placing the hydrothermal reaction kettle in an air-blowing drying oven, heating to 160 ℃, and reacting for 18h to obtain a reaction mixture.
(4) Cooling the reaction mixture to 25 ℃, then carrying out centrifugal separation at the rotation speed of 5000r/min, alternately washing the solid product obtained by the centrifugal separation for a plurality of times by using deionized water and ethanol, then placing the solid product in a vacuum drying oven, carrying out vacuum drying for 7h under the conditions that the absolute vacuum degree is 0.08MPa and the temperature is 70 ℃, and finally grinding the dried product to obtain the lanthanum hydroxide nano whisker.
Example 3
(1) Dissolving lanthanum chloride heptahydrate in a deionized water-ethanol mixed solvent to obtain a solution A with the lanthanum chloride concentration of 0.5mol/L, wherein the mass ratio of ethanol to deionized water in the mixed solvent is 3: 1; and dissolving sodium hydroxide in deionized water to obtain a solution B with the concentration of the sodium hydroxide of 5 mol/L.
(2) Dropwise adding the solution B into the solution A under magnetic stirring to obtain a mixed solution, stopping dropwise adding the solution B when the pH value of the mixed solution is adjusted to 10.0, and continuously carrying out magnetic stirring on the mixed solution for 30min to obtain a solution C.
(3) And placing the solution C in a hydrothermal reaction kettle with a polytetrafluoroethylene lining, placing the hydrothermal reaction kettle in an air-blowing drying oven, heating to 180 ℃, and reacting for 16 hours to obtain a reaction mixture.
(4) Cooling the reaction mixture to 25 ℃, then carrying out centrifugal separation at the rotation speed of 5000r/min, alternately washing the solid product obtained by the centrifugal separation for a plurality of times by using deionized water and ethanol, then placing the solid product in a vacuum drying oven, carrying out vacuum drying for 6h under the conditions that the absolute vacuum degree is 0.08MPa and the temperature is 80 ℃, and finally grinding the dried product to obtain the lanthanum hydroxide nano whisker.
Scanning Electron Microscope (SEM) tests and X-ray powder diffraction (XRD) were performed on the lanthanum hydroxide nanowhiskers prepared in this example; the SEM picture is shown in figure 1, and the XRD picture is shown in figure 2. As can be seen from FIG. 1, the lanthanum hydroxide nanowhisker has a diameter of about 30 to 50nm, a length of about 700 to 900nm, a large aspect ratio, a uniform morphology, and good dispersibility.
Example 4
30g of polylactic acid, 6g of polycaprolactone, 0.5g of acrylate copolymer ACR, 0.5g of antioxidant 1010, 0.8g of acetyl tributyl citrate, 0.4g of soybean oil and 0.4g of lanthanum hydroxide nanowhisker (example 3) are uniformly mixed, placed in a two-roll plasticator for plastication molding (the roll temperatures of two rolls are 150 ℃ and 180 ℃ respectively, and the roll gap is 0.45mm), and pressed into a sheet dumbbell type sample by an air compressor. The tensile test results are shown in table 1.
Example 5
30g of polylactic acid, 8g of polycaprolactone, 0.5g of acrylate copolymer ACR, 0.5g of antioxidant 1010, 0.8g of acetyl tributyl citrate, 0.4g of soybean oil and 0.4g of lanthanum hydroxide nanowhisker (example 3) are uniformly mixed, placed in a two-roll plasticator for plastic refining and molding (the roll temperatures of two rolls are 150 ℃ and 180 ℃ respectively, and the roll gap is 0.45mm), and pressed into a sheet dumbbell type sample by an air compressor. The tensile test results are shown in table 1.
Example 6
30g of polylactic acid, 10g of polycaprolactone, 0.5g of acrylate copolymer ACR, 0.5g of antioxidant 1010, 1.0g of acetyl tributyl citrate, 0.5g of soybean oil and 0.5g of lanthanum hydroxide nanowhisker (example 3) are uniformly mixed, placed in a two-roll plasticator for plastic refining and molding (the roll temperatures of two rolls are 150 ℃ and 180 ℃ respectively, and the roll gap is 0.45mm), and pressed into a sheet dumbbell type sample by an air compressor. The tensile test results are shown in table 1.
Comparative example
30g of polylactic acid, 8g of polycaprolactone, 0.5g of acrylate copolymer ACR, 0.5g of antioxidant 1010, 0.8g of acetyl tributyl citrate and 0.4g of soybean oil are uniformly mixed, placed in a two-roll plastic mixing machine (the roll temperatures of two rolls are 150 ℃ and 180 ℃ respectively, and the roll distance is 0.45mm) for plastic mixing and molding, and pressed into a sheet dumbbell type sample by an air compressor. The tensile test results are shown in table 1.
TABLE 1 tensile test results
As can be seen from table 1, the strength and toughness of the polylactic acid composition with the lanthanum hydroxide nanowhiskers of the present invention are significantly better than those of the polylactic acid composition without the lanthanum hydroxide nanowhiskers.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (3)
1. A preparation method of lanthanum hydroxide nano whisker is characterized by comprising the following steps:
(1) dropwise adding alkali liquor into an ethanol-water solution containing lanthanum salt under the condition of stirring to obtain a mixed solution; wherein the alkali liquor is a sodium hydroxide aqueous solution with the concentration of 1-5 mol/L; the concentration of lanthanum salt in the lanthanum salt-containing ethanol-water solution is 0.1-0.5 mol/L; the solvent of the lanthanum salt-containing ethanol-water solution is a mixed solvent formed by ethanol and deionized water in a mass ratio of 1: 2-3; the pH value of the mixed solution is 8-10;
(2) placing the mixed solution in a closed reaction device, heating to the reaction temperature, and reacting to obtain a reaction mixture; wherein the reaction temperature is 140-180 ℃, the reaction time is 16-20 h, and the closed reaction device is a hydrothermal reaction kettle with a polytetrafluoroethylene lining;
(3) and carrying out post-treatment on the reaction mixture to obtain the lanthanum hydroxide nano whisker, wherein the diameter of the lanthanum hydroxide nano whisker is 30-50 nm, and the length of the lanthanum hydroxide nano whisker is 700-900 nm.
2. The method according to claim 1, wherein in the step (1), the lanthanum salt is one or more of lanthanum chloride, lanthanum nitrate, lanthanum carbonate and lanthanum sulfate.
3. The production method according to claim 1, wherein in the step (3), the post-treatment comprises a solid-liquid separation step, a washing step, a drying step and a grinding step; the solid-liquid separation step adopts centrifugal separation, and the rotating speed is 2000-8000 r/min; the washing step comprises washing with deionized water and ethanol alternately at least once; and in the drying step, a vacuum drying oven is adopted, the vacuum degree is 0.01-0.1 MPa, the drying temperature is 50-100 ℃, and the drying time is 5-12 hours.
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