CN115678240A - MMT/hBN composite modified PC wear-resistant material and preparation method thereof - Google Patents
MMT/hBN composite modified PC wear-resistant material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an MMT/hBN composite modified PC wear-resistant material and a preparation method thereof, wherein the MMT/hBN composite modified PC wear-resistant material comprises the following components in percentage by mass: 75-85% of PC resin, 5-10% of modified hBN treated by surface silane and 5-10% of quaternary ammonium salt modified MMT. The MMT/hBN composite modified PC wear-resistant material has excellent wear resistance and lubricating property.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an MMT/hBN composite modified PC wear-resistant material and a preparation method thereof.
Background
Polycarbonate (PC) is one of the most commonly used engineering plastics and is widely used in automobile parts, gears and bearings. The PC has high transparency and light specific gravity, and has the advantages of excellent mechanical strength, impact toughness, electric insulation, light transmittance, weather resistance, free dyeing property, high strength, elastic coefficient, high impact strength, wide application temperature range and the like. However, the melt viscosity of PC is high, the forming processing is difficult under the injection molding and pressing methods, especially the large-scale product is easy to generate stress cracking phenomenon, the mechanical property is poor, the wear resistance is not high, and the price is high, so that the application of PC is limited to a certain extent. In order to improve the wear resistance of PC materials, modification treatment is often performed. The modified PC is a polycarbonate product which is processed and modified by filling, blending, reinforcing and other methods on the basis of polycarbonate and has improved flame retardance, strength, impact resistance, toughness and other aspects.
At present, hexagonal boron nitride (hBN) is often adopted to modify a PC material so as to improve the heat-conducting property and the heat-resistant property of the PC composite material; the PC material is modified by montmorillonite (MMT) to improve the flame retardant property and tensile strength of the PC material. However, there is a recent research report on the improvement of wear resistance of PC materials by inorganic-organic composite modification.
Therefore, the development of the MMT/hBN composite modified PC wear-resistant material is urgently needed by the technical personnel in the field to improve the wear resistance and the lubricating property of PC plastic.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides an MMT/hBN composite modified PC wear-resistant material, wherein the MMT/hBN composite modified PC wear-resistant material comprises, by mass: 75-85% of PC resin, 5-10% of modified hBN treated by surface silane and 5-10% of quaternary ammonium salt modified MMT.
In the first aspect, the modified hBN is prepared by dispersing a KH560 silane coupling agent in deionized water, placing the mixture in an ultrasonic cleaning machine for ultrasonic treatment for 10 to 20min, and preparing 0.5 to 1.0g/100ml of silane coupling agent aqueous solution after sufficient hydrolysis; adding 1-2g of hBN powder into the silane coupling agent aqueous solution, placing the silane coupling agent aqueous solution into a constant-temperature magnetic stirrer to be stirred for 10-30min, then placing the silane coupling agent aqueous solution into ultrasonic waves to be oscillated for 30min, then placing the silane coupling agent aqueous solution into a vacuum drying oven at 60 ℃ to be dried for 60min, and drying the silane coupling agent aqueous solution to obtain the modified hBN.
In the first aspect, montmorillonite powder is added into deionized water, dispersion liquid with the concentration of 30-60g/L is obtained after full stirring, esterquat-containing surfactant is added into the dispersion liquid, the temperature is raised to 70-85 ℃, the mixture is fully stirred and condensed for reflux reaction for 2-4 hours, and uniform suspension liquid is obtained; and (3) carrying out ultrasonic treatment on the suspension to uniformly disperse the suspension, then carrying out centrifugal separation to remove supernatant to obtain a precipitate, and washing, drying and grinding the precipitate to obtain the quaternary ammonium salt modified MMT.
In a second aspect, the application provides a preparation method of an MMT/hBN composite modified PC wear-resistant material, which is characterized by comprising the following steps: drying the PC resin, the modified hBN and the modified MMT; sequentially pouring the dried PC resin, the modified hBN and the modified MMT into a stirring barrel, premixing the materials, and uniformly mixing to obtain an initial mixture; and heating, melting and granulating the initial mixture by using a double-screw extruder to obtain the MMT/hBN composite modified PC wear-resistant material.
In a second aspect, the modified hBN is surface silane treated hBN.
In a second aspect, the method of making the modified hBN comprises: dispersing a KH560 silane coupling agent in deionized water, placing the deionized water in an ultrasonic cleaning machine for ultrasonic treatment for 10-20min, and preparing 0.5-1.0g/100ml of silane coupling agent aqueous solution after full hydrolysis; adding 1-2g of hBN powder into the silane coupling agent aqueous solution, placing the silane coupling agent aqueous solution into a constant-temperature magnetic stirrer to be stirred for 10-30min, then placing the silane coupling agent aqueous solution into ultrasonic waves to be oscillated for 30min, then placing the silane coupling agent aqueous solution into a vacuum drying oven at 60 ℃ to be dried for 60min, and drying the silane coupling agent aqueous solution to obtain the modified hBN powder with the surface treated by silane.
In a second aspect, the modified MMT is a quaternary ammonium salt modified MMT.
In a second aspect, a method of making the quaternary ammonium salt-modified MMT comprises: adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding an esterquat-containing surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, and carrying out condensation reflux reaction for 2-4 hours to obtain a uniform suspension liquid; and (3) carrying out ultrasonic treatment on the suspension to uniformly disperse the suspension, then carrying out centrifugal separation to remove supernatant to obtain a precipitate, and washing, drying and grinding the precipitate to obtain the quaternary ammonium salt modified MMT.
In a second aspect, the pre-mixing of the materials is carried out for a mixing time of 3-5min.
In a second aspect, the twin screw extruder has an extrusion temperature of 240 to 260 ℃.
Has the advantages that: the invention provides an MMT/hBN composite modified PC wear-resistant material, which consists of 75-85% of PC resin, 5-10% of modified hBN subjected to surface silane treatment and 5-10% of quaternary ammonium salt modified MMT by mass fraction. The invention selects hBN treated by surface silane and quaternary ammonium salt modified MMT as the wear-resistant modifier, and has good compatibility with the base material. The hBN particles can improve the hardness of PC plastic and can form a transfer film more easily so as to reduce the adhesive abrasion of the material; the lamellar blocking and lubricating functions of the modified MMT reduce the mobility of molecular chain segments and the crack propagation, and the wear resistance and the lubricating property of the PC plastic are improved by the synergistic mechanism of the molecular chain segments and the crack propagation.
Drawings
In order to more clearly illustrate the embodiments of the present disclosure or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present disclosure, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a preparation method of the MMT/hBN composite modified PC wear-resistant material in the embodiment of the invention;
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Meanwhile, throughout the specification, unless otherwise specifically stated, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present invention may be commercially available or may be prepared by existing methods.
Example 1
The MMT/hBN composite modified PC wear-resistant material is obtained by the following method:
(1) According to a material formula, the material comprises the following components in percentage by mass: 80% of PC resin, 10% of modified hBN treated by surface silane and 10% of modified MMT of quaternary ammonium salt; accurately weighing each component;
wherein, the modified hBN is prepared into 0.5-1.0g/100ml silane coupling agent aqueous solution by dispersing KH560 silane coupling agent in deionized water, placing in an ultrasonic cleaning machine for ultrasonic treatment for 10-20min, and after full hydrolysis; adding 1-2g of hBN powder into the silane coupling agent aqueous solution, putting the silane coupling agent aqueous solution into a constant-temperature magnetic stirrer, stirring for 10-30min, then putting the silane coupling agent aqueous solution into ultrasonic waves, oscillating for 30min, then putting the silane coupling agent aqueous solution into a vacuum drying oven at 60 ℃ for drying for 60min, and drying to obtain the modified hBN; adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding ester-group-containing quaternary ammonium salt surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, and carrying out condensation reflux reaction for 2-4 hours to obtain a uniform suspension liquid; performing ultrasonic treatment on the suspension to uniformly disperse the suspension, then performing centrifugal separation to remove supernatant to obtain a precipitate, washing, drying and grinding the precipitate to obtain the quaternary ammonium salt modified MMT;
(2) Drying the PC resin, the modified hBN and the modified MMT;
(3) Sequentially pouring the dried PC resin, the modified hBN and the modified MMT into a stirring barrel, premixing the materials for 3-5min, and uniformly mixing to obtain an initial mixture;
(4) Heating, melting and granulating the initial mixture by using a double-screw extruder to obtain the MMT/hBN composite modified PC wear-resistant material; the extrusion temperature of the double-screw extruder is 240-260 ℃.
Example 2
The MMT/hBN composite modified PC wear-resistant material is obtained by the following method:
(1) According to a material formula, the material comprises the following components in percentage by mass: 85% of PC resin, 7.5% of modified hBN treated by surface silane and 7.5% of quaternary ammonium salt modified MMT; accurately weighing each component;
wherein, the modified hBN is prepared into 0.5-1.0g/100ml of silane coupling agent aqueous solution by dispersing KH560 silane coupling agent in deionized water, placing the deionized water in an ultrasonic cleaner for ultrasonic treatment for 10-20min, and fully hydrolyzing; adding 1-2g of hBN powder into the silane coupling agent aqueous solution, putting the silane coupling agent aqueous solution into a constant-temperature magnetic stirrer, stirring for 10-30min, then putting the silane coupling agent aqueous solution into ultrasonic waves, oscillating for 30min, then putting the silane coupling agent aqueous solution into a vacuum drying oven at 60 ℃ for drying for 60min, and drying to obtain the modified hBN; adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding ester-group-containing quaternary ammonium salt surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, and carrying out condensation reflux reaction for 2-4h to obtain a uniform suspension liquid; performing ultrasonic treatment on the suspension to uniformly disperse the suspension, then performing centrifugal separation to remove supernatant to obtain a precipitate, washing, drying and grinding the precipitate to obtain the quaternary ammonium salt modified MMT;
(2) Drying the PC resin, the modified hBN and the modified MMT;
(3) Sequentially pouring the dried PC resin, the modified hBN and the modified MMT into a stirring barrel, premixing the materials for 3-5min, and uniformly mixing to obtain an initial mixture;
(4) Heating, melting and granulating the initial mixture by a double-screw extruder to obtain the MMT/hBN composite modified PC wear-resistant material; the extrusion temperature of the double-screw extruder is 240-260 ℃.
Example 3
The MMT/hBN composite modified PC wear-resistant material is obtained by the following method:
(1) According to a material formula, the material comprises the following components in percentage by mass: 82% of PC resin, 12% of modified hBN treated by surface silane and 6% of quaternary ammonium salt modified MMT; accurately weighing each component;
wherein, the modified hBN is prepared into 0.5-1.0g/100ml silane coupling agent aqueous solution by dispersing KH560 silane coupling agent in deionized water, placing in an ultrasonic cleaning machine for ultrasonic treatment for 10-20min, and after full hydrolysis; adding 1-2g of hBN powder into the silane coupling agent aqueous solution, putting the silane coupling agent aqueous solution into a constant-temperature magnetic stirrer, stirring for 10-30min, then putting the silane coupling agent aqueous solution into ultrasonic waves, oscillating for 30min, then putting the silane coupling agent aqueous solution into a vacuum drying oven at 60 ℃ for drying for 60min, and drying to obtain the modified hBN; adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding ester-group-containing quaternary ammonium salt surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, and carrying out condensation reflux reaction for 2-4h to obtain a uniform suspension liquid; performing ultrasonic treatment on the suspension to uniformly disperse the suspension, then performing centrifugal separation to remove supernatant to obtain a precipitate, washing, drying and grinding the precipitate to obtain the quaternary ammonium salt modified MMT;
(2) Drying the PC resin, the modified hBN and the modified MMT;
(3) Sequentially pouring the dried PC resin, the modified hBN and the modified MMT into a stirring barrel, premixing the materials for 3-5min, and uniformly mixing to obtain an initial mixture;
(4) Heating, melting and granulating the initial mixture by a double-screw extruder to obtain the MMT/hBN composite modified PC wear-resistant material; the extrusion temperature of the double-screw extruder is 240-260 ℃.
In order to further demonstrate the inventive step of the present invention, the following comparative examples 1-3 and examples 1-3 were used to form a control test.
Comparative example 1
The PC material was obtained as follows:
(1) According to a material formula, the material comprises the following components in percentage by mass: 100% of PC resin; accurately weighing each component;
(2) Drying the PC resin;
(3) Heating, melting and granulating the PC resin by a double-screw extruder to obtain a PC material; the extrusion temperature of the double-screw extruder is 240-260 ℃.
Comparative example 2
The modified PC material is obtained by the following method:
(1) According to the material formula, the material comprises the following components in percentage by mass: 90% of PC resin and 10% of modified hBN treated by surface silane; accurately weighing each component;
wherein, the modified hBN is prepared into 0.5-1.0g/100ml silane coupling agent aqueous solution by dispersing KH560 silane coupling agent in deionized water, placing in an ultrasonic cleaning machine for ultrasonic treatment for 10-20min, and after full hydrolysis; adding 1-2g of hBN powder into the silane coupling agent aqueous solution, putting the silane coupling agent aqueous solution into a constant-temperature magnetic stirrer, stirring for 10-30min, then putting the silane coupling agent aqueous solution into ultrasonic waves, oscillating for 30min, then putting the silane coupling agent aqueous solution into a vacuum drying oven at 60 ℃ for drying for 60min, and drying to obtain the modified hBN;
(2) Drying the PC resin and the modified hBN;
(3) Sequentially pouring the dried PC resin and the modified hBN into a stirring barrel, premixing the materials for 3-5min, and uniformly mixing to obtain an initial mixture;
(4) Heating, melting and granulating the initial mixture by a double-screw extruder to obtain the hBN modified PC material; the extrusion temperature of the double-screw extruder is 240-260 ℃.
Comparative example 3
The modified PC material is obtained by the following method:
(1) According to a material formula, the material comprises the following components in percentage by mass: 90% of PC resin and 10% of quaternary ammonium salt modified MMT; accurately weighing each component;
adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding an ester-group-containing quaternary ammonium salt surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, and carrying out condensation reflux reaction for 2-4 hours to obtain a uniform suspension liquid; performing ultrasonic treatment on the suspension to uniformly disperse the suspension, then performing centrifugal separation to remove supernatant to obtain a precipitate, washing, drying and grinding the precipitate to obtain the quaternary ammonium salt modified MMT;
(2) Drying the PC resin and the modified MMT;
(3) Sequentially pouring the dried PC resin and the modified MMT into a stirring barrel, premixing the materials for 3-5min, and uniformly mixing to obtain an initial mixture;
(4) Heating, melting and granulating the initial mixture by a double-screw extruder to obtain an MMT modified PC material; the extrusion temperature of the double-screw extruder is 240-260 ℃.
Effects of the embodiment
The materials obtained in examples 1 to 3 and comparative examples 1 to 3 were subjected to the property test, and the test results are shown in Table 1.
TABLE 1 test results of Material Properties of examples 1 to 3 and comparative examples 1 to 3
As can be seen from Table 1, the MMT/hBN composite modified PC wear-resistant materials developed by the PC resin, the modified hBN and the modified MMT in different proportions in the embodiments 1-3 of the invention have excellent wear resistance and lubricating property. The modified hBN has good compatibility with the PC base material and a layered structure, van der Waals force exists between layers, the modified hBN can bear external pressure perpendicular to the layered direction, and the shearing force in the sliding direction is extremely small, so that an interface can slide more easily, and the modified PC material has a lower friction coefficient; carrying out organic modification on montmorillonite to improve the dispersion of montmorillonite in a PC substrate; the obtained montmorillonite and PC have good compatibility effect and large interlayer spacing, and the montmorillonite layer has good barrier property, lubricity and compatibility, so that the mobility of molecular chain segments and the expansion modification of cracks are reduced, and the wear resistance of the PC material is improved.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The MMT/hBN composite modified PC wear-resistant material is characterized by comprising the following components in mass fraction:
75-85% of PC resin, 5-10% of modified hBN treated by surface silane and 5-10% of quaternary ammonium salt modified MMT.
2. The MMT/hBN composite modified PC wear-resistant material according to claim 1, wherein the modified hBN is prepared by dispersing KH560 silane coupling agent in deionized water, placing the mixture in an ultrasonic cleaning machine for 10-20min of ultrasonic treatment, and after sufficient hydrolysis, preparing 0.5-1.0g/100ml of silane coupling agent aqueous solution; and (2) adding 1-2g of hBN powder into the silane coupling agent aqueous solution, putting the silane coupling agent aqueous solution into a constant-temperature magnetic stirrer, stirring for 10-30min, then putting the silane coupling agent aqueous solution into ultrasonic waves, oscillating for 30min, then putting the silane coupling agent aqueous solution into a vacuum drying oven at 60 ℃ for drying for 60min, and drying to obtain the modified hBN.
3. The low-gloss PC/ABS flame-retardant material according to claim 2, wherein the quaternary ammonium salt modified MMT is prepared by adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with a concentration of 30-60g/L, adding esterquat-containing surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, and carrying out condensation reflux reaction for 2-4h to obtain a uniform suspension liquid; and (3) carrying out ultrasonic treatment on the suspension to uniformly disperse the suspension, then carrying out centrifugal separation to remove supernatant to obtain a precipitate, and washing, drying and grinding the precipitate to obtain the quaternary ammonium salt modified MMT.
4. A preparation method of the MMT/hBN composite modified PC wear-resistant material is characterized by comprising the following steps:
drying the PC resin, the modified hBN and the modified MMT;
sequentially pouring the dried PC resin, the modified hBN and the modified MMT into a stirring barrel, premixing the materials, and uniformly mixing to obtain an initial mixture;
and heating, melting and granulating the initial mixture by using a double-screw extruder to obtain the MMT/hBN composite modified PC wear-resistant material.
5. The method for preparing the MMT/hBN composite modified PC wear-resistant material according to claim 4, wherein the modified hBN is surface silane treated modified hBN.
6. The method for preparing the MMT/hBN composite modified PC wear-resistant material according to claim 5, wherein the method for preparing the modified hBN comprises the following steps: dispersing a KH560 silane coupling agent in deionized water, placing the deionized water in an ultrasonic cleaning machine for ultrasonic treatment for 10-20min, and preparing 0.5-1.0g/100ml of silane coupling agent aqueous solution after full hydrolysis; adding 1-2g of hBN powder into the silane coupling agent aqueous solution, placing the silane coupling agent aqueous solution into a constant-temperature magnetic stirrer to be stirred for 10-30min, then placing the silane coupling agent aqueous solution into ultrasonic waves to be oscillated for 30min, then placing the silane coupling agent aqueous solution into a vacuum drying oven at 60 ℃ to be dried for 60min, and drying the silane coupling agent aqueous solution to obtain the modified hBN powder with the surface treated by silane.
7. The method for preparing the MMT/hBN composite modified PC wear-resistant material according to claim 6, wherein the modified MMT is quaternary ammonium salt modified MMT.
8. The method for preparing the MMT/hBN composite modified PC wear-resistant material according to claim 7, wherein the method for preparing the quaternary ammonium salt modified MMT comprises the following steps: adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding an esterquat-containing surfactant into the dispersion liquid, heating to 70-85 ℃, fully stirring, and carrying out condensation reflux reaction for 2-4 hours to obtain a uniform suspension liquid; and (3) carrying out ultrasonic treatment on the suspension to uniformly disperse the suspension, then carrying out centrifugal separation to remove supernatant to obtain a precipitate, and washing, drying and grinding the precipitate to obtain the quaternary ammonium salt modified MMT.
9. The method for preparing the MMT/hBN composite modified PC wear-resistant material according to claim 8, wherein the premixing of the materials is performed for 3-5min.
10. The method for preparing the MMT/hBN composite modified PC wear-resistant material according to claim 9, wherein the extrusion temperature of the twin-screw extruder is 240-260 ℃.
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