CN107298833B - Preparation method of high-dispersion PBT (polybutylene terephthalate) nano composite material - Google Patents
Preparation method of high-dispersion PBT (polybutylene terephthalate) nano composite material Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K3/2279—Oxides; Hydroxides of metals of antimony
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C08K5/00—Use of organic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/544—Silicon-containing compounds containing nitrogen
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to a preparation method of a high-dispersion PBT (polybutylene terephthalate) nano composite material, which comprises the steps of adding PBT particles, inorganic nano particles, an antioxidant and a coupling agent into a planetary ball mill, carrying out circulating ball milling under the condition that the rotating speed is 300-500 rpm, and obtaining composite powder after 0.5-15 hours; and extruding and granulating the composite powder at 215-235 ℃ by using a double-screw extruder, and then performing injection molding at 235 ℃ to obtain the high-dispersion PBT nano composite material. The method has the advantages of simple process, short production period, high efficiency, high product yield and no environmental pollution, effectively improves the interface compatibility of the inorganic nanoparticles and the PBT, and finally improves the physical and chemical properties of the PBT nanocomposite.
Description
Technical Field
The invention relates to the technical field of high dispersion of inorganic nanoparticles in polymer composite materials, in particular to a preparation method of a high-dispersion PBT (polybutylene terephthalate) nano composite material.
Background
For inorganic/polymer nanocomposites, the dispersion of inorganic nanoparticles in the polymer matrix material is an important factor affecting the properties of the nanocomposite. If the inorganic nanoparticles can be well dispersed in the polymer matrix, a strong interaction interface is formed between the inorganic nanoparticles and the polymer matrix, so that the mechanical property and the optical property of the inorganic substance/polymer nanocomposite material are improved. However, the nanoparticles have small particle size, large specific surface area, high surface energy and high surface activity, and can easily form aggregates in the polymer matrix, so that the application of the nanoparticles is greatly limited. At present, methods for improving the dispersibility of nanoparticles in a polymer matrix mainly include in-situ polymerization, melt blending, and surface treatment of nanoparticles. However, when the amount of nanoparticles added in the polymer exceeds 5%, it is difficult for these conventional dispersion methods to obtain a uniformly dispersed composite material. In addition, in the process of preparing the composite material, the methods are mainly completed in a solution and molten state, so that the problems of environmental pollution, high production cost and the like are inevitably caused. Particularly polymers that are sensitive to processing temperatures, such as PBT, tend to decompose when dispersed by conventional methods resulting in a decrease in composite performance.
The high-energy ball milling dispersion method is a solid method, does not need to use auxiliary agents and consider the problem of dissolution or melting of polymers in the process of preparing the composite material, and is a novel method for preparing the polymer nano composite material with high efficiency and environmental protection. The mechanochemical effect in the high-energy ball milling process can induce physical and chemical reactions among the components to improve the dispersion uniformity and compatibility among the components, and further improve the performance of the composite material, so that the method is widely used for preparing metal and alloy materials, amorphous materials, nano materials, ceramic materials, composite materials and the like.
At present, the application of high-energy ball milling in the field of polymers is less, and the high-energy ball milling is mainly used for preparing polymer alloys and recycling polymer wastes, while the research on preparing polymer/inorganic nano composite materials is less.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a high-dispersion PBT nano composite material with simple process and no pollution.
In order to solve the problems, the preparation method of the high-dispersion PBT nano composite material is characterized by comprising the following steps: the method comprises the steps of mixing PBT particles, inorganic nanoparticles, an antioxidant and a coupling agent according to a ratio of 4: 1-10: adding the ball material mass ratio of 1 into a planetary ball mill, performing circulating ball milling at the rotating speed of 300-500 rpm for 0.5-15 h to obtain composite powder; extruding and granulating the composite powder at 215-235 ℃ by a double-screw extruder, and then performing injection molding at 235 ℃ to obtain the high-dispersion PBT nano composite material; the inorganic nano particles account for 1-20% of the mass of the PBT particles, the antioxidant accounts for 0.1-0.5% of the mass of the PBT particles, and the coupling agent accounts for 1-10% of the mass of the inorganic nano particles.
The planet ball mill adopts a GGr15 steel ball with the diameter of 6mm and a GGr15 steel ball with the diameter of 10mm, and the number ratio of the large steel ball to the small steel ball is 2: 1-1: 5.
the circulation mode of the planetary ball mill is positive rotation for 6min, stop for 3 min and reverse rotation for 6 min.
The inorganic nano particles are any one of nano antimony trioxide particles, nano silicon dioxide particles and nano calcium carbonate particles with the average particle size of 20-50 nm.
The antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
The coupling agent is gamma-methacryloxypropyltrimethoxysilane or gamma-aminopropyltriethoxysilane.
Compared with the prior art, the invention has the following advantages:
1. the PBT particles and the inorganic nanoparticles are uniformly mixed by adopting a high-energy ball milling method, the inorganic nanoparticles are uniformly dispersed in the PBT matrix by a mechanochemical effect in the ball milling process, and meanwhile, the interface compatibility of the inorganic nanoparticles and the PBT is effectively improved, so that the physicochemical property of the PBT nanocomposite is finally improved.
The back scattering electron of TM3030 scanning electron microscope is used to observe the dispersibility of the nano antimony trioxide in the PBT matrix in example 5 (see figure 1), and the figure shows that the average particle size of the nano antimony trioxide particles is about 40nm and the nano antimony trioxide particles have better dispersibility in the PBT matrix, which shows that the nano antimony trioxide nano composite material can overcome the agglomeration phenomenon of the nano particles in the polymer matrix and obtain the nano composite material with uniform dispersion. FIG. 2 shows the tensile fracture morphology of example 5, from which it can be seen that a wire drawing phenomenon appears on the fracture surface, which indicates that the nano antimony trioxide particles and PBT obtain better interface compatibility in the ball milling dispersion process.
2. The invention has the advantages of simple process, short production period, high efficiency, high product yield and no environmental pollution.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a scanning electron microscope image of backscattered electrons of the PBT nanocomposite obtained by the invention.
FIG. 2 is a scanning electron microscope image of a tensile fracture of the PBT nanocomposite obtained by the invention.
Detailed Description
Example 1 a process for preparing a highly dispersed PBT nanocomposite, which comprises mixing PBT particles, inorganic nanoparticles, an antioxidant and a coupling agent in a ratio of 4: adding the ball material mass ratio of 1 into a planetary ball mill, performing circulating ball milling at the rotation speed of 500rpm for 0.5h to obtain composite powder; and extruding and granulating the composite powder at 215-235 ℃ by a double-screw extruder, and then performing injection molding at 235 ℃ to obtain the high-dispersion PBT nano composite material.
Wherein: the using amount of the inorganic nano particles is 5 percent of the mass of the PBT particles, the using amount of the antioxidant is 0.1 percent of the mass of the PBT particles, and the using amount of the coupling agent is 10 percent of the mass of the inorganic nano particles.
40 steel balls (each ball weight 0.8 g) of GGr15 with a diameter of 6mm and 20 steel balls (each ball weight 4.0 g) of GGr15 with a diameter of 10mm were used in the planetary ball mill.
The circulation mode of the planetary ball mill is positive rotation for 6min, stop for 3 min and reverse rotation for 6 min.
The inorganic nanoparticles are nano antimony trioxide particles with the average particle size of 20-50 nm.
The antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010).
The coupling agent is gamma-aminopropyl triethoxysilane (KH 550).
Example 2 a method for preparing a highly dispersed PBT nanocomposite, which is a method of mixing PBT particles, an inorganic nanoparticle antioxidant and a coupling agent in a ratio of 4: adding the ball material mass ratio of 1 into a planetary ball mill, performing circulating ball milling under the condition that the rotating speed is 500rpm, and obtaining composite powder after 1.0 h; and extruding and granulating at 215-235 ℃ by using a composite powder double-screw extruder, and then performing injection molding at 235 ℃ to obtain the high-dispersion PBT nano composite material.
Wherein: the using amount of the inorganic nano particles is 5 percent of the mass of the PBT particles, the using amount of the antioxidant is 0.1 percent of the mass of the PBT particles, and the using amount of the coupling agent is 10 percent of the mass of the inorganic nano particles.
The steel balls in the planetary ball mill were the same as in example 1.
The planetary ball mill cycle was the same as in example 1.
The inorganic nanoparticles, antioxidant and coupling agent were the same as in example 1.
Example 3 a method for preparing a highly dispersed PBT nanocomposite, which is a method of mixing PBT particles, inorganic nanoparticles, an antioxidant, and a coupling agent in a ratio of 4: adding the ball material mass ratio of 1 into a planetary ball mill, performing circulating ball milling at the rotation speed of 500rpm for 3.0h to obtain composite powder; and extruding and granulating the composite powder at 215-235 ℃ by a double-screw extruder, and then performing injection molding at 235 ℃ to obtain the high-dispersion PBT nano composite material.
Wherein: the using amount of the inorganic nano particles is 5 percent of the mass of the PBT particles, the using amount of the antioxidant is 0.1 percent of the mass of the PBT particles, and the using amount of the coupling agent is 10 percent of the mass of the inorganic nano particles.
The steel balls in the planetary ball mill were the same as in example 1.
The planetary ball mill cycle was the same as in example 1.
The inorganic nanoparticles, antioxidant and coupling agent were the same as in example 1.
Example 4 a method for preparing a highly dispersed PBT nanocomposite, which is a method of mixing PBT particles, inorganic nanoparticles, an antioxidant, and a coupling agent in a ratio of 4: adding the ball material mass ratio of 1 into a planetary ball mill, performing circulating ball milling under the condition that the rotating speed is 500rpm, and obtaining composite powder after 6.0 h; and extruding and granulating the composite powder at 215-235 ℃ by a double-screw extruder, and then performing injection molding at 235 ℃ to obtain the high-dispersion PBT nano composite material.
Wherein: the using amount of the inorganic nano particles is 5 percent of the mass of the PBT particles, the using amount of the antioxidant is 0.1 percent of the mass of the PBT particles, and the using amount of the coupling agent is 10 percent of the mass of the inorganic nano particles.
The steel balls in the planetary ball mill were the same as in example 1.
The planetary ball mill cycle was the same as in example 1.
The inorganic nanoparticles, antioxidant and coupling agent were the same as in example 1.
Example 5 a method for preparing a highly dispersed PBT nanocomposite, which is a method of mixing PBT particles, inorganic nanoparticles, an antioxidant, and a coupling agent in a ratio of 4: adding the ball material mass ratio of 1 into a planetary ball mill, performing circulating ball milling at the rotation speed of 500rpm for 10 hours to obtain composite powder; and extruding and granulating the composite powder at 215-235 ℃ by a double-screw extruder, and then performing injection molding at 235 ℃ to obtain the high-dispersion PBT nano composite material.
Wherein: the using amount of the inorganic nano particles is 5 percent of the mass of the PBT particles, the using amount of the antioxidant is 0.1 percent of the mass of the PBT particles, and the using amount of the coupling agent is 10 percent of the mass of the inorganic nano particles.
The steel balls in the planetary ball mill were the same as in example 1.
The planetary ball mill cycle was the same as in example 1.
The inorganic nanoparticles, antioxidant and coupling agent were the same as in example 1.
Example 6 a method for preparing a highly dispersed PBT nanocomposite, which is a method of mixing PBT particles, inorganic nanoparticles, an antioxidant, and a coupling agent in a ratio of 4: adding the ball material mass ratio of 1 into a planetary ball mill, performing circulating ball milling at the rotation speed of 400rpm for 10 hours to obtain composite powder; and extruding and granulating the composite powder at 215-235 ℃ by a double-screw extruder, and then performing injection molding at 235 ℃ to obtain the high-dispersion PBT nano composite material.
Wherein: the using amount of the inorganic nano particles is 5 percent of the mass of the PBT particles, the using amount of the antioxidant is 0.1 percent of the mass of the PBT particles, and the using amount of the coupling agent is 10 percent of the mass of the inorganic nano particles.
The steel balls in the planetary ball mill were the same as in example 1.
The planetary ball mill cycle was the same as in example 1.
The inorganic nanoparticles, antioxidant and coupling agent were the same as in example 1.
Example 7 a method for preparing a highly dispersed PBT nanocomposite, which is a method of mixing PBT particles, inorganic nanoparticles, an antioxidant, and a coupling agent in a ratio of 4: adding the ball material mass ratio of 1 into a planetary ball mill, performing circulating ball milling at the rotation speed of 400rpm for 10 hours to obtain composite powder; and extruding and granulating the composite powder at 215-235 ℃ by a double-screw extruder, and then performing injection molding at 235 ℃ to obtain the high-dispersion PBT nano composite material.
Wherein: the using amount of the inorganic nano particles is 10 percent of the mass of the PBT particles, the using amount of the antioxidant is 0.1 percent of the mass of the PBT particles, and the using amount of the coupling agent is 10 percent of the mass of the inorganic nano particles.
The steel balls in the planetary ball mill were the same as in example 1.
The planetary ball mill cycle was the same as in example 1.
The inorganic nanoparticles, antioxidant and coupling agent were the same as in example 1.
Example 8 a method for preparing a highly dispersed PBT nanocomposite, which is a method of mixing PBT particles, inorganic nanoparticles, an antioxidant, and a coupling agent in a ratio of 4: adding the ball material mass ratio of 1 into a planetary ball mill, performing circulating ball milling at the rotation speed of 500rpm for 10 hours to obtain composite powder; and extruding and granulating the composite powder at 215-235 ℃ by a double-screw extruder, and then performing injection molding at 235 ℃ to obtain the high-dispersion PBT nano composite material.
Wherein: the using amount of the inorganic nano particles is 18 percent of the mass of the PBT particles, the using amount of the antioxidant is 0.1 percent of the mass of the PBT particles, and the using amount of the coupling agent is 10 percent of the mass of the inorganic nano particles.
The steel balls in the planetary ball mill were the same as in example 1.
The planetary ball mill cycle was the same as in example 1.
The inorganic nanoparticles, antioxidant and coupling agent were the same as in example 1.
Example 9 a process for preparing a highly dispersed PBT nanocomposite, which comprises mixing PBT particles, inorganic nanoparticles, an antioxidant and a coupling agent in a ratio of 10: adding the ball material mass ratio of 1 into a planetary ball mill, performing circulating ball milling at the rotating speed of 300rpm for 15 hours to obtain composite powder; and extruding and granulating the composite powder at 215-235 ℃ by a double-screw extruder, and then performing injection molding at 235 ℃ to obtain the high-dispersion PBT nano composite material.
Wherein: the using amount of the inorganic nano particles is 1 percent of the mass of the PBT particles, the using amount of the antioxidant is 0.5 percent of the mass of the PBT particles, and the using amount of the coupling agent is 1 percent of the mass of the inorganic nano particles.
The planetary ball mill adopts GGr15 steel balls with the diameter of 6mm and GGr15 steel balls with the diameter of 10mm, and the number ratio of the large steel balls to the small steel balls is 1: 5.
the circulation mode of the planetary ball mill is positive rotation for 6min, stop for 3 min and reverse rotation for 6 min.
The inorganic nanoparticles are silica nanoparticles having an average particle diameter of 20 to 50 nm.
The antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010).
The coupling agent is gamma-methacryloxypropyltrimethoxysilane (KH 570).
Example 10 a method of preparing a highly dispersed PBT nanocomposite, which is a method of mixing PBT particles, inorganic nanoparticles, an antioxidant, and a coupling agent in a ratio of 7: adding the ball material mass ratio of 1 into a planetary ball mill, performing circulating ball milling at the rotating speed of 300rpm for 1.0h to obtain composite powder; and extruding and granulating the composite powder at 215-235 ℃ by a double-screw extruder, and then performing injection molding at 235 ℃ to obtain the high-dispersion PBT nano composite material.
Wherein: the using amount of the inorganic nano particles is 20 percent of the mass of the PBT particles, the using amount of the antioxidant is 0.3 percent of the mass of the PBT particles, and the using amount of the coupling agent is 5 percent of the mass of the inorganic nano particles.
The planetary ball mill adopts GGr15 steel balls with the diameter of 6mm and GGr15 steel balls with the diameter of 10mm, and the number ratio of the large steel balls to the small steel balls is 1.5: 3.
the circulation mode of the planetary ball mill is positive rotation for 6min, stop for 3 min and reverse rotation for 6 min.
The inorganic nanoparticles are nano calcium carbonate particles with the average particle size of 20-50 nm.
The antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010).
The coupling agent is gamma-aminopropyl triethoxysilane (KH 550).
Claims (2)
1. A preparation method of a high-dispersion PBT nano composite material is characterized by comprising the steps of adding PBT particles, inorganic nanoparticles, an antioxidant and a coupling agent into a planetary ball mill according to a ball material mass ratio of 4: 1-10: 1, carrying out circular ball milling at a rotating speed of 300-500 rpm for 0.5-15 hours to obtain a composite powder, extruding and granulating the composite powder at 215-235 ℃ through a double-screw extruder, and carrying out injection molding at 235 ℃ to obtain the high-dispersion PBT nano composite material, wherein the using amount of the inorganic nanoparticles is 1-20% of the mass of the PBT particles, the using amount of the antioxidant is 0.1-0.5% of the mass of the PBT particles, the using amount of the coupling agent is 1-10% of the mass of the inorganic nanoparticles, a GGr15 steel ball with the diameter of 6mm and a GGr15 steel ball with the diameter of 10mm are adopted in the planetary ball mill, the number ratio of the steel balls is 2: 1-1: 5, the inorganic nanoparticles are antimony trioxide nanoparticles with the average particle size of 20-50 nm, and the antioxidant is 4-gamma-propyl-2-trimethoxy silane coupling agent.
2. The method for preparing the high-dispersion PBT nanocomposite material of claim 1, wherein the method comprises the following steps: the circulation mode of the planetary ball mill is positive rotation for 6min, stop for 3 min and reverse rotation for 6 min.
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