CN108467528B - Preparation method of polyolefin nano composite material - Google Patents
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Abstract
A preparation method of polyolefin nano composite material is characterized by comprising the following steps: providing polyolefin particles; secondly, mixing the precursor of the inorganic nano filler with a solvent, and adding the mixture into polyolefin particles for dipping to obtain a mixture; thirdly, freezing the mixture, then carrying out vacuum drying, and then freezing and drying again for 5-20 times to obtain a dried granular substance; steaming the hydrochloric acid/ethanol solution into the dried granular substances in a steam mode to obtain steam-fumigated granular substances; washing the particles fumigated by the steam with water for 1-5 times, and fully drying to obtain solid particles; sixthly, stirring the solid particles at the temperature of 120-260 ℃ at the speed of 10-300 rpm for 1-60 min, and forming to obtain the polyolefin nano composite material. When the addition amount of the nano filler is more than 10% and less than 30%, the polyolefin nano composite material with uniform nano filler dispersion and excellent mechanical property can be obtained.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a preparation method of a polyolefin nano composite material.
Background
The polyolefin nano composite material is a composite material with inorganic filler dispersed in a polyolefin matrix in a nano-scale manner, has excellent performances of impact resistance, mechanical strength, friction and wear resistance and the like, and is an important lightweight material. However, due to the nanometer size effect of the nanometer filler, the filler is easy to agglomerate, and the mechanical property of the polyolefin nanometer composite material is greatly reduced.
The preparation method of the polyolefin nano composite material mainly comprises two types, namely a physical blending method and a chemical blending method, wherein in the physical blending method, in order to strengthen the interface action of polyolefin and nano filler and obtain the nano filler which is uniformly dispersed in a polyolefin matrix, the nano filler needs to be modified, such as surface alkylation, carbonylation and the like, or a compatilizer needs to be used. For example, patent publication No. CN100393620C entitled "Process for preparing polyolefin nanocomposites" discloses a process for preparing polyolefin nanocomposites comprising melt mixing a mixture of a polyolefin, a filler and a nonionic surfactant. Nonionic surfactants interact with fillers, such as layered silicate clays, to modify the filler. When added to clay in a polyolefin melt, the nonionic surfactant intercalates and partially exfoliates the clay structure without the need to pre-intercalate the clay with other additives. The mechanical properties of the obtained polyolefin nanocomposite are improved.
The chemical blending method is mainly characterized in that a catalyst is loaded on the surface of the nano filler, and the polyolefin nano composite material which is uniformly dispersed is obtained by utilizing the in-situ polymerization of olefin. For example, the preparation method disclosed in patent application CN1510058A for polyolefin nanocomposite and preparation method thereof comprises: drying montmorillonite to prepare montmorillonite carrier, adding the montmorillonite carrier into an alcoholic solution of a magnesium compound, adding the mixed solution into a solution of a titanium compound, adding acid anhydride and the same amount of the titanium compound for reaction, filtering, washing with an anhydrous nonpolar solvent in a hot mode, and drying to obtain the montmorillonite-supported catalyst. Adding anhydrous hexane or heptane into a reaction kettle in the atmosphere of ethylene or propylene monomers, sequentially adding heptane solution of an aluminum compound, organic silicon and a montmorillonite-supported catalyst for polymerization, and adding acidified ethanol to terminate the reaction to obtain the polyolefin nanocomposite. The application obtains the composite material with montmorillonite layers uniformly dispersed in a polyolefin matrix by organically treating montmorillonite. However, chemical blending, in addition to having a lower production efficiency, will also produce a significant amount of ash, which is detrimental to subsequent processing of the nanocomposite.
In addition, in the existing methods for preparing polyolefin nanocomposites (including physical blending method and chemical blending method), the mixing amount of the inorganic nano-filler cannot exceed 10 wt%, otherwise, a large amount of micron-sized agglomeration is generated in the polyolefin due to the nano-size effect of the nano-filler, which severely restricts the material use performance.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a preparation method of a polyolefin nano composite material, so that the nano filler can be uniformly dispersed while the addition amount of the nano filler is increased.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of polyolefin nano composite material is characterized by comprising the following steps:
firstly, providing polyolefin particles with the pore volume of 0.01-100 mL/g;
secondly, mixing a precursor of the inorganic nano filler with a solvent, adding the mixture into the polyolefin particles, and soaking for 24-108 hours to obtain a mixture of the precursor of the inorganic nano filler/the polyolefin particles/the solvent, wherein the ratio of the polyolefin particles to the solvent is 0.01-100 g/mL;
freezing the mixture, then carrying out vacuum drying, freezing again, drying, and circulating for 5-20 times to obtain a dried granular substance;
steaming hydrochloric acid/ethanol solution with the concentration of 0.1-20.0 mol/L into the dried granular substance obtained in the step (c) in a steam mode, wherein the steam entering speed is 0.1-10 mL/min, and the granular substance after steam fumigation is obtained, wherein the ratio of polyolefin particles to the hydrochloric acid/ethanol solution is 0.001-1 g/mL;
fifthly, washing the particulate matter fumigated by the steam in the step IV with water for 1-5 times, and fully drying to obtain solid particles;
sixthly, stirring the solid particles at the temperature of 120-260 ℃ at the speed of 10-300 rpm for 1-60 min, and forming to obtain the polyolefin nanocomposite, wherein in the polyolefin nanocomposite, the weight ratio of the product obtained after hydrolysis of the precursor, namely the inorganic nano filler to the polyolefin particles, is 10-30 wt%.
As a refinement, the polyolefin particles comprise at least one of polyethylene, polypropylene, polyisoprene.
The precursor of the inorganic nano filler comprises at least one of titanium tetrachloride, titanium trichloride, magnesium ethoxide, aluminum ethoxide, alkyl aluminum and ethyl silicate.
In the improvement, the solvent is at least one of toluene, n-heptane and tetrahydrofuran.
The inorganic nano-filler in the polyolefin nano-composite material prepared by the step (sixthly) is uniformly distributed, and the average particle size of the inorganic nano-filler is 5-800 nm.
In each scheme, the solid particles in the step (sixthly) are stirred in a screw extruder and are extruded and molded.
Compared with the prior art, the invention has the advantages that: during the polymerization process, the particle crushing process of the heterogeneous catalyst causes the nascent polyolefin particles to have a porous structure inside. According to the porosity of nascent polyolefin particles, the technology provided by the invention can enable the precursor of the inorganic nano-filler to be adsorbed on the wall of the polyolefin hole; then, introducing acid into the polyolefin particles in a steam form to control the hydrolysis rate of the precursor of the inorganic nano-filler, so that the precursor is hydrolyzed to obtain the inorganic nano-filler; because the hydrolysis of the inorganic nano-filler precursor is a strong exothermic reaction, the crystalline region of the polyolefin is destroyed by local heat generated during hydrolysis, so that the inorganic nano-filler generated after hydrolysis is drilled into the amorphous region of the polyolefin to form effective pre-dispersion of the nano-filler; finally, the preparation of the polyolefin inorganic nano composite material is completed through melting, shearing and molding. The preparation method can solve the bottleneck problem of the existing polyolefin nano composite material preparation, namely, when the addition amount of the nano filler is 10-30 wt%, the polyolefin nano composite material with uniform nano filler dispersion and excellent mechanical property can be obtained.
Drawings
FIG. 1 is a cross-sectional view of polyethylene pellets used in examples 1, 2, 5, 6 of the present invention and comparative example;
FIG. 2 is a transmission electron microscope image of the polyolefin nanocomposite prepared in example 1 of the present invention;
FIG. 3 is a transmission electron microscope image of a polyolefin nanocomposite prepared in example 2 of the present invention;
FIG. 4 is a transmission electron microscope image of the polyolefin nanocomposite prepared in the comparative example.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1:
the preparation method of the polyolefin nano composite material comprises the following steps:
(1) providing 10g of polyethylene particles with the pore volume of 1.5mL/g, wherein the porous structure in the primary particles is shown in figure 1; (2) 7.125g of TiCl4Mixing with 10mL of toluene, adding the polyethylene particles obtained in the step (1), and soaking for 108h to obtain TiCl4A mixture of/polyethylene particles/toluene; (3) mixing TiCl4The mixture of/polyethylene particles/toluene was frozen with liquid nitrogen and dried under vacuum toAfter the mixture is unfrozen, freezing the mixture by using liquid nitrogen again and slowly drying the mixture for 20 times in a circulating way to obtain dried particles; (4) steaming 100mL of hydrochloric acid/ethanol solution with the concentration of 2mol/L into the dried particles obtained in the step (3) in a steam mode, wherein the steam inlet speed is 0.1mL/min, and obtaining steam-fumigated particles; (5) washing the steam-fumigated particles with water for 5 times, and fully drying to obtain solid particles; (6) stirring the solid particles in a screw extruder for 10min at the stirring temperature of 200 ℃ and the stirring speed of 20rpm to obtain the polyolefin nano composite material; the transmission electron microscope image of the obtained polyolefin nanocomposite is shown in FIG. 2, wherein the inorganic filler is dispersed in nano-scale and is uniformly distributed, and the average particle size of the nanoparticles is 153.5 nm. The tensile strength of the composite material is 50.5MPa, and the elongation at break is 100.3%.
Example 2:
the preparation method of the polyolefin nano composite material comprises the following steps:
(1) providing 10g of polyethylene particles with the pore volume of 1.5mL/g, wherein the porous structure in the primary particles is shown in figure 1; (2) 2.375g of TiCl4Mixing with 5mL of toluene, adding the polyethylene particles obtained in the step (1), and soaking for 24h to obtain TiCl4A mixture of/polyethylene particles/toluene; (3) mixing TiCl4Freezing the mixture of polyethylene particles and toluene by using liquid nitrogen, then carrying out vacuum drying, freezing again by using liquid nitrogen after the mixture is unfrozen, and slowly drying for 5 times to obtain dried particles; (4) steaming 100mL of hydrochloric acid/ethanol solution with the concentration of 0.1mol/L into the dried particles obtained in the step (3) in a steam mode, wherein the steam inlet speed is 0.1mL/min, and obtaining steam-fumigated particles; (5) washing the steam-fumigated particles with water for 1 time, and fully drying to obtain solid particles; (6) stirring the solid particles in a screw extruder for 10min at the stirring temperature of 200 ℃ and the stirring speed of 20rpm to obtain the polyolefin nano composite material; the transmission electron microscope image of the obtained polyolefin nanocomposite is shown in fig. 3, wherein the inorganic filler is dispersed in a nano-scale manner and is uniformly distributed, the particle size of the nano-particles is smaller, and the average particle size is 5 nm. The tensile strength of the composite material is 60.5MPa, and the elongation at break is 150.3%.
Example 3:
the preparation method of the polyolefin nano composite material comprises the following steps:
(1) providing 10g of polypropylene particles having a pore volume of 0.01 mL/g; (2) 4.0g of TiCl3Mixing with 0.1mL tetrahydrofuran, adding the polypropylene particles obtained in step (1), and soaking for 76h to obtain TiCl3A mixture of/polypropylene particles/tetrahydrofuran; (3) mixing TiCl3Freezing the mixture of polypropylene particles and tetrahydrofuran with liquid nitrogen, vacuum drying, thawing the mixture, freezing again with liquid nitrogen, slowly drying, and circulating for 7 times to obtain dried particles; (4) steaming 10mL of hydrochloric acid/ethanol solution with the concentration of 20mol/L into the dried particles obtained in the step (3) in a steam mode, wherein the steam inlet speed is 10mL/min, and obtaining steam-fumigated particles; (5) washing the steam-fumigated particles with water for 3 times, and fully drying to obtain solid particles; (6) stirring the solid particles in a screw extruder for 1min at the stirring temperature of 260 ℃ and the stirring speed of 300rpm to obtain the polyolefin nano composite material; the inorganic filler in the polyolefin nano composite material is dispersed in a nano-scale manner and is uniformly distributed, and the average particle size of nano particles is 800 nm. The tensile strength of the composite material is 100.5MPa, and the elongation at break is 70.3%.
Example 4:
the preparation method of the polyolefin nano composite material comprises the following steps:
(1) providing 10g of polyisoprene particles having a pore volume of 100 mL/g; (2) mixing 5.0g of magnesium ethoxide with 1mL of n-heptane, adding the polyisoprene particles obtained in the step (1), and soaking for 76h to obtain a mixture of magnesium ethoxide/polyisoprene particles/n-heptane; (3) freezing the mixture of magnesium ethoxide/polyisoprene particles/n-heptane by using liquid nitrogen, then carrying out vacuum drying, thawing the mixture, freezing again by using the liquid nitrogen, slowly drying, and circulating for 7 times to obtain dried particles; (4) steaming 1000mL of hydrochloric acid/ethanol solution with the concentration of 0.2mol/L into the dried particles obtained in the step (3) in a steam mode, wherein the steam entering speed is 1mL/min, and obtaining steam-fumigated particles; (5) washing the steam-fumigated particles with water for 3 times, and fully drying to obtain solid particles; (6) stirring the solid particles in a screw extruder for 60min at the stirring temperature of 120 ℃ and the stirring speed of 10rpm to obtain the polyolefin nano composite material; the inorganic filler in the polyolefin nano composite material is dispersed in a nano-scale manner and is uniformly distributed, and the average particle size of nano particles is 200 nm. The tensile strength of the composite material is 30.5MPa, and the elongation at break is 722.8%.
Example 5:
the preparation method of the polyolefin nano composite material comprises the following steps:
(1) providing 10g of polyethylene particles having a pore volume of 1.5 mL/g; (2) mixing 4g of aluminum ethoxide with 5mL of toluene, adding the polyethylene particles obtained in the step (1), and soaking for 24 hours to obtain a mixture of aluminum ethoxide/polyethylene particles/toluene; (3) freezing the mixture of aluminum ethoxide/polyethylene particles/toluene by using liquid nitrogen, then carrying out vacuum drying, thawing the mixture, freezing again by using the liquid nitrogen, slowly drying, and circulating for 5 times to obtain dried particles; (4) steaming 100mL of hydrochloric acid/ethanol solution with the concentration of 0.1mol/L into the dried particles obtained in the step (3) in a steam mode, wherein the steam inlet speed is 0.1mL/min, and obtaining steam-fumigated particles; (5) washing the steam-fumigated particles with water for 1 time, and fully drying to obtain solid particles; (6) stirring the solid particles in a screw extruder for 10min at the stirring temperature of 200 ℃ and the stirring speed of 20rpm to obtain the polyolefin nano composite material; the inorganic filler in the polyolefin nano composite material is dispersed in a nano-scale manner and is uniformly distributed, and the average particle size of nano particles is 100 nm. The tensile strength of the composite material is 50.5MPa, and the elongation at break is 232.8%.
Example 6:
the preparation method of the polyolefin nano composite material comprises the following steps:
(1) providing 5g of polyethylene particles having a pore volume of 1.5mL/g and 5g of polypropylene particles having a pore volume of 2.0 mL/g; (2) mixing 3.2g of triethylaluminum, 0.5g of ethyl silicate and 5mL of toluene, adding the polyethylene particles and the polypropylene particles obtained in the step (1), and soaking for 24 hours to obtain a mixture of triethylaluminum/ethyl silicate/polyethylene particles/polypropylene particles/toluene; (3) freezing a mixture of triethyl aluminum/ethyl silicate/polyethylene particles/polypropylene particles/toluene by using liquid nitrogen, then carrying out vacuum drying, thawing the mixture, freezing again by using the liquid nitrogen, slowly drying, and circulating for 5 times to obtain dried particles; (4) steaming 100mL of hydrochloric acid/ethanol solution with the concentration of 0.1mol/L into the dried particles obtained in the step (3) in a steam mode, wherein the steam inlet speed is 0.1mL/min, and obtaining steam-fumigated particles; (5) washing the steam-fumigated particles with water for 1 time, and fully drying to obtain solid particles; (6) stirring the solid particles in a screw extruder for 20min at the stirring temperature of 230 ℃ and the stirring speed of 100rpm to obtain the polyolefin nano composite material; the inorganic filler in the polyolefin nano composite material is dispersed in a nano-scale manner and is uniformly distributed, and the average particle size of nano particles is 300 nm. The tensile strength of the composite material is 57.5MPa, and the elongation at break is 132.8%.
Example 7:
substantially the same as example 1, except that the solvent toluene in this example was 1000mL, the hydrochloric acid/ethanol solution was 10000mL, and the inorganic filler in the polyolefin nanocomposite material prepared in this example was nano-dispersed and uniformly distributed, and the average particle size of the nanoparticles was 56.7 nm. The tensile strength of the composite material is 75.3MPa, and the elongation at break is 101.2%.
Comparative example:
the preparation method of the polyolefin nano composite material comprises the following steps:
(1) providing 10g of polyethylene particles with the pore volume of 1.5mL/g, wherein the porous structure in the primary particles is shown in figure 1; (2) 3.0g of TiO2And (3) uniformly mixing the polyethylene particles, and stirring in a screw extruder for 10min at the stirring temperature of 200 ℃ and the stirring speed of 20rpm to obtain the polyolefin nano composite material. The transmission electron micrograph of the obtained polyolefin nanocomposite is shown in fig. 4, which contains a large amount of micron-sized agglomerates. The polyolefin nanocomposite had a tensile strength of 5.5MPa and an elongation at break of 1.0%.
Claims (6)
1. A preparation method of polyolefin nano composite material is characterized by comprising the following steps:
firstly, providing polyolefin particles with the pore volume of 0.01-100 mL/g;
secondly, mixing a precursor of the inorganic nano filler with a solvent, adding the mixture into the polyolefin particles, and soaking for 24-108 hours to obtain a mixture of the precursor of the inorganic nano filler/the polyolefin particles/the solvent, wherein the ratio of the polyolefin particles to the solvent is 0.01-100 g/mL;
freezing the mixture, then carrying out vacuum drying, freezing again, drying, and circulating for 5-20 times to obtain a dried granular substance;
steaming hydrochloric acid/ethanol solution with the concentration of 0.1-20.0 mol/L into the dried granular substance obtained in the step (c) in a steam mode, wherein the steam entering speed is 0.1-10 mL/min, and the granular substance after steam fumigation is obtained, wherein the ratio of polyolefin particles to the hydrochloric acid/ethanol solution is 0.001-1 g/mL;
fifthly, washing the particulate matter fumigated by the steam in the step IV with water for 1-5 times, and fully drying to obtain solid particles;
sixthly, stirring the solid particles at the temperature of 120-260 ℃ at the speed of 10-300 rpm for 1-60 min, and forming to obtain the polyolefin nanocomposite, wherein in the polyolefin nanocomposite, the weight ratio of the product obtained after hydrolysis of the precursor, namely the inorganic nano filler to the polyolefin particles, is 10-30 wt%.
2. The method of claim 1, wherein: the polyolefin particles comprise at least one of polyethylene, polypropylene and polyisoprene.
3. The method of claim 1, wherein: the precursor of the inorganic nano filler comprises at least one of titanium tetrachloride, titanium trichloride, magnesium ethoxide, aluminum ethoxide, alkyl aluminum and ethyl silicate.
4. The method of claim 1, wherein: the solvent is at least one of toluene, n-heptane and tetrahydrofuran.
5. The method of claim 1, wherein: the inorganic nano-filler in the polyolefin nano-composite material prepared by the step (sixthly) is uniformly distributed, and the average particle size of the inorganic nano-filler is 5-800 nm.
6. The production method according to any one of claims 1 to 5, characterized in that: stirring the solid particles in the step (sixthly) in a screw extruder and extruding and molding.
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