CN107151321B - Fluorinated graphene/MC nylon composite material and preparation method and application thereof - Google Patents
Fluorinated graphene/MC nylon composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorinated graphene/MC nylon composite material, which aims to overcome the defects of poor dimensional stability, thermal stability, low-temperature toughness and the like of the existing MC nylon product and provides a preparation method of the fluorinated graphene/MC nylon composite material, wherein the fluorinated graphene/MC nylon composite material is prepared by reacting fluorinated graphene, a caprolactam monomer, a catalyst, an initiator and an aprotic polar solvent, and the preparation method enables the fluorinated graphene to be well dispersed in a polymer matrix, so that the excellent performance of the fluorinated graphene is kept, and the tensile strength and the impact strength of the composite material are greatly improved; the volume wear rate of the material is obviously reduced, the dimensional stability, wear resistance and toughness of a workpiece are obviously improved, the preparation method of the material is simple, the equipment requirement is low, no pollution is caused, and the material is suitable for industrialization and can be used for producing accessories of automobiles and heavy mechanical equipment to prepare bearing wheels or bearing seats.
Description
Technical Field
The invention relates to an MC nylon composite material, and preparation and application thereof, and more particularly relates to a fluorinated graphene/MC nylon composite material, and a preparation method and application thereof.
Background
The casting nylon (MC nylon) is a product, and can replace metal materials such as steel, copper, aluminum and the like in a certain range due to the advantages of good physical stability, chemical corrosion resistance, high wear resistance and the like, and is suitable for the application fields of chemical industry, machinery, textile, petroleum, electricity and the like. However, pure MC nylon products have the defects of poor dimensional stability, thermal stability, low-temperature toughness and the like, and the application range of the pure MC nylon products is limited to a certain extent. At present, various researches on modification and preparation of MC nylon composite materials are carried out in China, and inorganic modification and organic modification are more concentrated. The main means of the inorganic modification method is to add one or more inorganic filling materials such as red phosphorus, glass microspheres, carbon fibers, titanium dioxide nanoparticles and the like into nylon, and obtain better dimensional stability and toughness. Since Novoselov discovered graphene in 2004, due to the unique nanostructure and properties of graphene, the addition of graphene to polymers can significantly improve the physical, mechanical and thermal properties of polymer materials. In a domestic research institution such as Feijiejie New materials GmbH in a patent No. CN105622929A, graphene is pre-dispersed in a molten polyamide monomer, a catalyst, an activator and other auxiliaries are added, and finally, the nylon/graphene nano composite material is prepared by adopting an in-situ anion ring-opening polymerization process for casting. In patent No. CN105254870A of Sichuan university, graphene oxide subjected to coupling and reduction treatment is added into a caprolactam monomer, and the monomer-cast nylon/graphene nanocomposite is prepared by polymerization after vacuum dehydration under reduced pressure. Meanwhile, in patent No. CN105295028A of Hangzhou university of teachers and universities, the graphene in-situ modified polycaprolactam composite material improves the dimensional stability, the wear resistance and the toughness of the composite material. The invention reserves various excellent performances of graphene, and the strength, modulus and thermal properties of the modified polyamide composite material are remarkably improved.
Since the fluorinated graphene is reported for the first time by an A.K. Geim group in 2010, compared with other graphene derivatives, the fluorinated graphene, a brand-new insulating tai derivative, has a wider forbidden band energy level, has good dispersibility in a solvent, is not easy to agglomerate, and a C-F bond of the fluorinated graphene can perform a nucleophilic reaction with a strong nucleophilic reagent such as primary amine, so that a condition is provided for forming a covalent bond between the fluorinated graphene and a polymer base. The fluorinated graphene serving as a two-dimensional derivative graphene has the structural characteristics of graphene and carbon fluoride and shows a series of new physical and chemical properties, so that a theoretical basis is provided for practical production and application.
However, much of the research on such materials has focused on improving the interaction between the nanofiller and the polymer matrix by adding unmodified graphene or surface-modified graphene oxide. At present, research and report of doping fluorinated graphene in the preparation process of MC nylon are not found.
Disclosure of Invention
The invention aims to overcome the defects of poor dimensional stability, thermal stability, low-temperature toughness and the like of the MC nylon in the prior art, and provides a fluorinated graphene/MC nylon composite material which has better physical and mechanical properties and wear resistance than the MC nylon by adding the fluorinated graphene with high fluorine-carbon ratio, excellent heat resistance, wear resistance and dispersity.
The invention also aims to provide a preparation method of the fluorinated graphene/MC nylon composite material.
The invention also aims to provide application of the fluorinated graphene/MC nylon composite material.
The invention is realized by the following technical scheme:
a fluorinated graphene/MC nylon composite material is prepared by reacting fluorinated graphene, a caprolactam monomer, a catalyst, an initiator and an aprotic polar solvent, wherein the mass ratio of the total mass of the fluorinated graphene to the total mass of the caprolactam monomer is 0.5-5: 1; the mass ratio of the catalyst to the fluorinated graphene is 1-5: 1; the mass ratio of the initiator to the fluorinated graphene is 1-5: 1; the liquid-solid ratio of the aprotic solvent to the fluorinated graphene is 2-10: 1.
Further, the fluorine content of the fluorinated graphene is 51-68%; F/C is more than 1, the weight loss peak temperature is higher than 400 ℃, and the resistance is more than 1000 omega.
Further, the catalyst is NaOH, KOH, L iOH, Na2CO3And NaH, L iH.
Further, the aprotic polar solvent is at least one of dimethylformamide, dimethylacetamide, acetone, acetonitrile, and 1, 3-dimethyl-2-imidazolidinone.
Further, the initiator is any one of polyisocyanate, dodecyl isocyanate, hexadecyl isocyanate, tert-butyl isocyanate, nonyl isocyanate, decyl isocyanate, octyl isocyanate or m-toluene isocyanate.
Further, the mass ratio of the total mass of the fluorinated graphene to the caprolactam monomer is 3-5% to 1; the mass ratio of the catalyst to the fluorinated graphene is 4-5: 1; the mass ratio of the initiator to the fluorinated graphene is 2.5-5: 1; the mass ratio of the aprotic solvent to the fluorinated graphene is 2-2.5: 1.
The invention aims to realize covalent bonding of nylon and fluorinated graphene with high fluorine content on a nanoscale through a grafting technology, and the obtained nano material can combine the dimensional stability, thermal stability and wear resistance of the fluorinated graphene with the processability and dielectricity of a polymer, has wide application prospect in the aspect of enhancing the mechanical and frictional wear resistance of the polymer, and can be particularly processed and prepared into bearing wheels and bearing seats to be applied to automobile and heavy machinery equipment accessories.
The fluorinated graphene used in the invention has good dispersibility in a solvent, is not easy to agglomerate, is uniformly dispersed in a caprolactam monomer by high-speed stirring and depending on the shearing force of a stirring solution under the condition of the caprolactam monomer melting, and realizes effective combination of the fluorinated graphene and the caprolactam monomer by chemical bonding. By means of the excellent surface effect, volume effect, quantum size effect and sheet structure of the fluorinated graphene, the tensile strength, impact strength and friction resistance of the fluorinated graphene/MC nylon composite material are improved.
The invention also aims to provide a preparation method of the fluorinated graphene/MC nylon composite material, which comprises the following steps:
s1, adding 10g of graphite powder into 250m L of 64 wt% of H under the ice bath condition2SO4While stirring, 50g of KMnO was slowly added4Reacting the powder at 10-15 ℃ for 2h, then continuously heating to 35 ℃, and continuously stirring for reacting for 4 h; obtaining a first solution;
s2, adding 800m of L deionized water into the solution I obtained in the step S1, heating to 80 ℃, reacting for 30min, cooling the temperature of the reacted solution to room temperature, adding 50-200 m of L and 38wt% of H2O2Transferring the solution until no bubbles are generated, dialyzing to neutrality in dialysis bag, and freeze drying to obtain the final productTo graphene oxide;
s3, weighing 20g of graphene oxide in the step S2 into a reaction kettle, introducing N2 into the reaction kettle at room temperature to replace air in the kettle, and then introducing F of 80-100 KPa2/N2Mixed gas of said F2/N2F of mixed gas2Accounting for 10-20% of the total volume of the mixed gas; heating to 180-200 ℃, and fluorinating for 12-36 h to obtain fluorinated graphene; the F/C of the fluorinated graphene is 1.01-1.22.
In the invention, the precursor graphene oxide of fluorinated graphene is prepared by a classical Hummers oxidation method, and the graphene oxide is further subjected to fluorination reaction in a mixed atmosphere of inert gas and F2.
Another object of the present invention is to provide a method for preparing a fluorinated graphene/MC nylon composite material, wherein the method for preparing the fluorinated graphene/MC nylon composite material comprises the following steps:
y1., weighing the fluorinated graphene according to the proportion, adding the fluorinated graphene into a nonpolar solvent, shearing for 0.5-1 h at 18000-20000 r/min through a high-shear stirrer, and then processing for 1.5-3 h through an ultrasonic cell crusher; forming a stable fluorinated graphene dispersion solution;
y2. dividing caprolactam monomer into two parts, respectively placing caprolactam monomer I with 50-90% of total mass of caprolactam monomer in reaction kettle A and caprolactam monomer II with 10-50% of total mass of caprolactam monomer in reaction kettle B;
y21, dropwise adding the fluorinated graphene dispersion solution obtained in the step Y1 into a reaction kettle A filled with caprolactam monomer, stirring at 400-800 r/min, gradually heating to 100-120 ℃, vacuumizing the reaction kettle A to 0.1MPa after the caprolactam monomer in the reaction kettle A is completely melted, increasing the rotating speed to 8000-10000 r/min, and stirring for 30min to uniformly disperse the fluorinated graphene in the caprolactam monomer; then adding NaOH solution, and heating to 130-140 ℃; performing reduced pressure distillation to remove water at the temperature of 10000-20000 r/min and under the pressure of 0.1MPa and 140 ℃;
y22, pumping vacuum to caprolactam monomer II in the reaction kettle B when the temperature is raised to 70-80 ℃ while stirring, adding an initiator after the monomer is melted, continuously pumping vacuum to 0.1MPa, raising the temperature to 130-140 ℃, and continuously pumping vacuum for 10min under the condition of 10000 r/min;
y3. mixing the materials obtained from the kettle A and the kettle B, pouring the mixture into a mold at 150-180 ℃ for polymerization molding, reacting for 50-80 min, and continuing to perform heat preservation reaction for 10-30 min; and naturally cooling to obtain the fluorinated graphene/MC nylon composite material.
Compared with the prior art, the invention has the following beneficial effects:
according to the fluorinated graphene/MC nylon composite material provided by the invention, fluorinated graphene is creatively placed in an MC nylon pouring system, and MC nylon and fluorinated graphene with high fluorine content are covalently combined on a nanoscale, so that the fluorinated graphene/MC nylon composite material with high dimensional stability, thermal stability and wear resistance and good comprehensive performance is prepared.
The fluorinated graphene used in the invention not only has excellent physical, chemical and mechanical properties of the graphene material, but also can be used as a solid lubricant due to small interlayer energy, can still maintain excellent lubricity under high temperature, high pressure and high load, and can enhance bearing capacity and reduce heat generated by friction on the surface of the material when added into MC nylon.
The fluorinated graphene used in the invention has good dispersibility in a solvent, is not easy to agglomerate, is uniformly dispersed in a caprolactam monomer by high-speed stirring and depending on the shearing force of a stirring solution under the condition of the caprolactam monomer melting, and realizes effective combination of the fluorinated graphene and the caprolactam monomer by chemical bonding. By means of the excellent surface effect, volume effect, quantum size effect and sheet structure of the fluorinated graphene, the tensile strength, impact strength and friction resistance of the fluorinated graphene/MC nylon composite material are improved.
The method for preparing the fluorinated graphene/MC nylon composite material provided by the invention is simple, low in equipment requirement, free of pollution and suitable for industrialization, and can be used for producing accessories of automobiles and heavy machinery equipment to prepare bearing wheels or bearing seats.
Drawings
FIG. 1 is a TEM image of fluorinated graphene prepared by the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific examples. Unless otherwise indicated, the various starting materials used in the examples of the present invention are either conventionally available commercially or prepared according to conventional methods in the art using equipment commonly used in the laboratory. Unless defined or stated 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.
According to the invention, the fluorinated graphene is creatively placed in a casting MC nylon system, and the nylon and the fluorinated graphene with high fluorine content are covalently combined on a nanoscale, so that the fluorinated graphene/MC nylon composite material with high dimensional stability, thermal stability and wear resistance and good comprehensive performance is prepared.
The fluorine content of the fluorinated graphene is 51-68%; F/C is more than 1, the weight loss peak temperature is higher than 400 ℃, and the resistance is more than 1000 omega. In the fluorinated graphene, the larger the fluorocarbon ratio is, the better the physical properties of the fluorinated graphene are. Therefore, fluorinated graphene with a high fluorine-carbon ratio is selected as a reinforcing material in the present patent.
The initiator is any one of polyisocyanate, dodecyl isocyanate, hexadecyl isocyanate, tert-butyl isocyanate, nonyl isocyanate, decyl isocyanate, octyl isocyanate or m-toluene isocyanate.
The catalyst is NaOH, KOH, L iOH and Na2CO3At least one of NaH, L iH, preferably NaOH.
The aprotic polar solvent is at least one of dimethylformamide, dimethylacetamide, acetone, acetonitrile, and 1, 3-dimethyl-2-imidazolidinone.
Example 1
(1) Preparation of fluorinated graphene
S1, adding 10g of graphite powder into 250m L of 64 wt% of H under the ice bath condition2SO4While stirring, 50g of KMnO was slowly added4Powder of 1Reacting for 2 hours at the temperature of 0-15 ℃, then continuously heating to 35 ℃, and continuously stirring for reacting for 4 hours; obtaining a first solution;
s2, adding 800m of L deionized water into the solution I obtained in the step S1, heating to 80 ℃, reacting for 30min, cooling the temperature of the reacted solution to room temperature, adding 50m of L and 38wt% of H2O2Transferring the solution until no bubbles are generated, dialyzing the solution to be neutral in a dialysis bag, and freeze-drying the solution to obtain graphene oxide;
s3, weighing 20g of graphene oxide obtained in the step S2 into a reaction kettle, and introducing N into the reaction kettle at room temperature2Displacing the air in the kettle, and then introducing 80KPa of F2/N2Mixed gas of F2/N2F of mixed gas2Accounting for 10 percent of the total volume of the mixed gas; heating to 180 ℃, and fluorinating for 12h to obtain fluorinated graphene; the F/C of the fluorinated graphene surface is 1.01 through an X-ray photoelectron spectroscopy test.
(2) Preparation of fluorinated graphene/MC nylon composite material
Y1. weighing the fluorinated graphene according to the proportion in the table 1, adding the fluorinated graphene into 99% of a nonpolar solvent, shearing for 0.5h at 18000r/min by a high-shear stirrer, and then processing for 1.5h by an ultrasonic cell crusher; forming a stable fluorinated graphene dispersion solution;
y2. dividing caprolactam monomer into two parts, placing them in reactor A with 5Kg caprolactam monomer I and reactor B with 5Kg caprolactam monomer II respectively;
y21, dropwise adding the fluorinated graphene dispersion solution obtained in the step Y1 into a reaction kettle A containing caprolactam monomer, stirring at 400r/min, gradually heating to 100 ℃, vacuumizing to 0.1MPa after the caprolactam monomer in the reaction kettle A is completely melted, increasing the rotating speed to 8000r/min, stirring for 30min to uniformly disperse the fluorinated graphene in the caprolactam monomer, adding a 40 wt% NaOH solution of 125m L, heating to 130 ℃, distilling at 0.1MPa at 140 ℃ and 10000r/min under reduced pressure to remove water;
y22, pumping vacuum when the temperature of the caprolactam monomer II in the reaction kettle B is raised to 70 ℃ while stirring, adding an initiator after the monomer is melted, continuously pumping vacuum to 0.1MPa, raising the temperature to 130 ℃, and continuously pumping vacuum for 10min under the condition of 10000 r/min;
y3. mixing the materials obtained from the A kettle and the B kettle, pouring into a mold at 150 ℃ for polymerization molding, reacting for 80min, and continuing to react for 10min under heat preservation; and naturally cooling to obtain the fluorinated graphene/MC nylon composite material.
Example 2
(1) Preparation of fluorinated graphene
The method for preparing fluorinated graphene in example 2 is the same as in example 1, except that 85KPa F is introduced in step S32/N2Mixed gas of F2/N2F of mixed gas2Accounts for 14 percent of the total volume of the mixed gas; heating to 185 ℃, and fluorinating for 18h to obtain fluorinated graphene; the F/C of the fluorinated graphene surface is 1.06 through an X-ray photoelectron spectroscopy test.
(2) Preparation of fluorinated graphene/MC nylon composite material
Y1. weighing the fluorinated graphene according to the proportion in the table 1, adding the fluorinated graphene into 99% of a nonpolar solvent, shearing for 1h at 20000r/min through a high-shear stirrer, and then processing for 3h by using an ultrasonic cell crusher; forming a stable fluorinated graphene dispersion solution;
y2. dividing caprolactam monomer into two parts, placing them in reactor A with 6Kg caprolactam monomer I and reactor B with 4Kg caprolactam monomer II respectively;
y21, dropwise adding the fluorinated graphene dispersion solution obtained in the step Y1 into a reaction kettle A containing caprolactam monomer, stirring at 600r/min, gradually heating to 120 ℃, vacuumizing to 0.1MPa after the caprolactam monomer in the reaction kettle A is completely melted, increasing the rotating speed to 8000r/min, stirring for 30min to uniformly disperse the fluorinated graphene in the caprolactam monomer, adding a 40 wt% NaOH solution of 250m L, heating to 140 ℃, distilling at 0.1MPa to remove water under reduced pressure at 140 ℃ and 10000 r/min;
y22, pumping vacuum to caprolactam monomer II in the reaction kettle B when the temperature is raised to 80 ℃ while stirring, adding an initiator after the monomer is melted, continuously pumping vacuum to 0.1MPa and raising the temperature to 140 ℃, and continuously pumping vacuum for 10min under the condition of 15000 r/min;
y3. mixing the materials obtained from the A kettle and the B kettle, pouring into a 180 ℃ mold for polymerization molding, reacting for 50min, and continuing to react for 10min with heat preservation; and naturally cooling to obtain the fluorinated graphene/MC nylon composite material.
Example 3
(1) Preparation of fluorinated graphene
The method for preparing fluorinated graphene in example 3 is the same as in example 2.
(2) Preparation of fluorinated graphene/MC nylon composite material
Y1. weighing the fluorinated graphene according to the proportion in the table 1, adding the fluorinated graphene into 99% of a nonpolar solvent, shearing for 0.5h at 20000r/min through a high-shear stirrer, and then processing for 2h by using an ultrasonic cell crusher; forming a stable fluorinated graphene dispersion solution;
y2. dividing caprolactam monomer into two parts, placing them in reactor A with 6Kg caprolactam monomer I and reactor B with 4Kg caprolactam monomer II respectively;
y21, dropwise adding the fluorinated graphene dispersion solution obtained in the step Y1 into a reaction kettle A containing caprolactam monomer, stirring at 600r/min, gradually heating to 120 ℃, vacuumizing to 0.1MPa after the caprolactam monomer in the reaction kettle A is completely melted, increasing the rotating speed to 9000r/min, stirring for 30min to uniformly disperse the fluorinated graphene in the caprolactam monomer, adding a 60 wt% NaOH solution of 500m L, heating to 140 ℃, and distilling under reduced pressure at 0.1MPa, 140 ℃ and 10000r/min to remove water;
y22, pumping vacuum to caprolactam monomer II in the reaction kettle B when the temperature is raised to 80 ℃ while stirring, adding an initiator after the monomer is melted, continuously pumping vacuum to 0.1MPa and raising the temperature to 140 ℃, and continuously pumping vacuum for 10min under the condition of 10000 r/min;
y3. mixing the materials obtained from the A kettle and the B kettle, pouring into a 170 ℃ mold for polymerization molding, reacting for 60min, and continuing to react for 20min under heat preservation; and naturally cooling to obtain the fluorinated graphene/MC nylon composite material.
Example 4
(1) Preparation of fluorinated graphene
The method for preparing fluorinated graphene in example 4 is the same as in example 1, except that 90KPa F is introduced in step S32/N2Mixed gas of F2/N2F of mixed gas216% of the total volume of the mixed gas; heating to 190 ℃, and fluorinating for 24 hours to obtain fluorinated graphene; the F/C of the fluorinated graphene surface is 1.16 through an X-ray photoelectron spectroscopy test.
(2) And (3) preparing the fluorinated graphene/MC nylon composite material.
Y1. weighing the fluorinated graphene according to the proportion in the table 1, adding the fluorinated graphene into 99% of a nonpolar solvent, shearing for 0.5h at 20000r/min through a high-shear stirrer, and then processing for 1.5h by using an ultrasonic cell crusher; forming a stable fluorinated graphene dispersion solution;
y2. dividing caprolactam monomer into two parts, placing them in reactor A with 6Kg caprolactam monomer I and reactor B with 4Kg caprolactam monomer II respectively;
y21, dropwise adding the fluorinated graphene dispersion solution obtained in the step Y1 into a reaction kettle A containing caprolactam monomer, stirring at 600r/min, gradually heating to 120 ℃, vacuumizing the reaction kettle A to 0.1MPa after the caprolactam monomer in the reaction kettle A is completely melted, increasing the rotating speed to 9000r/min, stirring for 30min to uniformly disperse the fluorinated graphene in the caprolactam monomer, adding 1000m of L of 60 wt% NaOH solution, heating to 140 ℃, and distilling under reduced pressure at 0.1MPa, 140 ℃ and 10000r/min to remove water;
y22, pumping vacuum to caprolactam monomer II in the reaction kettle B when the temperature is raised to 80 ℃ while stirring, adding an initiator after the monomer is melted, continuously pumping vacuum to 0.1MPa and raising the temperature to 140 ℃, and continuously pumping vacuum for 10min under the condition of 10000 r/min;
y3. mixing the materials obtained from the A kettle and the B kettle, pouring into a 170 ℃ mold for polymerization molding, reacting for 70min, and continuing to react for 20min under heat preservation; and naturally cooling to obtain the fluorinated graphene/MC nylon composite material.
Example 5
(1) Preparation of fluorinated graphene
The method for preparing fluorinated graphene in example 5 is the same as in example 4.
(2) Preparation of fluorinated graphene/MC nylon composite material
Y1. weighing the fluorinated graphene according to the proportion in the table 1, adding the fluorinated graphene into 99% of a nonpolar solvent, shearing for 0.5h at 20000r/min through a high-shear stirrer, and then processing for 2h by using an ultrasonic cell crusher; forming a stable fluorinated graphene dispersion solution;
y2. dividing caprolactam monomer into two parts, placing them in reactor A with 8Kg caprolactam monomer I and reactor B with 2Kg caprolactam monomer II respectively;
y21, dropwise adding the fluorinated graphene dispersion solution obtained in the step Y1 into a reaction kettle A containing caprolactam monomer, stirring at 600r/min, gradually heating to 120 ℃, vacuumizing to 0.1MPa after the caprolactam monomer in the reaction kettle A is completely melted, increasing the rotating speed to 10000r/min, stirring for 30min to uniformly disperse the fluorinated graphene in the caprolactam monomer, adding 80 wt% of 1000m L of NaOH solution, heating to 140 ℃, distilling at 0.1MPa to remove water under reduced pressure at 140 ℃ and 10000 r/min;
y22, pumping vacuum when the temperature of the caprolactam monomer II in the reaction kettle B is raised to 80 ℃ while stirring, adding an initiator after the monomer is melted, continuously pumping vacuum to 0.1MPa and raising the temperature to 140 ℃, and continuously pumping vacuum for 10min under the condition of 20000 r/min;
y3. mixing the materials obtained from the A kettle and the B kettle, pouring into a 170 ℃ mold for polymerization molding, reacting for 70min, and continuing to react for 20min under heat preservation; and naturally cooling to obtain the fluorinated graphene/MC nylon composite material.
Example 6
(1) Preparation of fluorinated graphene
The method for preparing fluorinated graphene in example 6 is the same as in example 1. The difference is that in step S3, F with 100KPa is introduced2/N2Mixed gas of F2/N2F of mixed gas2Mixing of20% of the total volume of gas; heating to 200 ℃, and fluorinating for 36 hours to obtain fluorinated graphene; the F/C of the fluorinated graphene surface is 1.22 through an X-ray photoelectron spectroscopy test.
(2) Preparation of fluorinated graphene/MC nylon composite material
Y1. weighing the fluorinated graphene according to the proportion in the table 1, adding the fluorinated graphene into 99% of a nonpolar solvent, shearing for 0.5h at 20000r/min through a high-shear stirrer, and then processing for 2h by using an ultrasonic cell crusher; forming a stable fluorinated graphene dispersion solution;
y2. dividing caprolactam monomer into two parts, putting them into reactor A with 9Kg caprolactam monomer I and reactor B with 1Kg caprolactam monomer II respectively;
y21, dropwise adding the graphene fluoride dispersion solution obtained in the step Y1 into a reaction kettle A containing a caprolactam monomer, stirring at 800r/min, gradually heating to 120 ℃, vacuumizing to 0.1MPa after the caprolactam monomer in the reaction kettle A is completely melted, increasing the rotating speed to 10000r/min, stirring for 30min to uniformly disperse the graphene fluoride in the caprolactam monomer, adding 3125m of 80 wt% NaOH solution, heating to 140 ℃, and distilling under reduced pressure at 0.1MPa, 140 ℃ and 10000r/min to remove water;
y22, pumping vacuum to caprolactam monomer II in the reaction kettle B when the temperature is raised to 80 ℃ while stirring, adding an initiator after the monomer is melted, continuously pumping vacuum to 0.1MPa and raising the temperature to 140 ℃, and continuously pumping vacuum for 10min under the condition of 10000 r/min;
y3. mixing the materials obtained from the A kettle and the B kettle, pouring into a 170 ℃ mold for polymerization molding, reacting for 70min, and continuing to react for 20min under heat preservation; and naturally cooling to obtain the fluorinated graphene/MC nylon composite material.
Comparative example 1
Weighing a certain amount of caprolactam, adding the caprolactam into a reaction kettle, sealing, heating to 100-120 ℃, vacuumizing after caprolactam monomers are completely melted, and removing water and low-boiling-point impurities at 120 ℃; adding 0.3mol of NaOH into each 100ml of caprolactam, continuously stirring, vacuumizing, heating to 160 ℃, adding polyisocyanate adhesive, adding 0.3mol of polyisocyanate into each 100ml of caprolactam, and continuously stirring for reacting for 15 min; and finally, quickly transferring the mixture into a mold at 170 ℃, polymerizing for 30min at constant temperature, and demolding after natural cooling to obtain the MC nylon material.
TABLE 1
To further illustrate, the graphene fluoride materials prepared in embodiments 1 to 6 are analyzed by a transmission electron microscope, as can be seen from fig. 1, the graphene fluoride prepared and used in the present invention still has a good lamellar structure and exhibits a good transparent state, and unlike graphene oxide, the graphene fluoride is a rigid molecule which does not have a wrinkled state, and is suitable for application of a composite material.
The fluorinated graphene/MC nylon composite material obtained in any of examples 1 to 6 in the present invention and the material in comparative example 1 were subjected to measurement of tensile strength, impact strength, friction coefficient and volumetric wear rate. Specific measurement results are shown in table 2.
TABLE 2
As shown in table 2, according to the fluorinated graphene/MC nylon composite material prepared by the method, the fluorinated graphene/MC nylon composite material is prepared by fluorinated graphene graft-modified caprolactam, and the tensile strength, the impact strength and the friction resistance of the fluorinated graphene/MC nylon composite material are improved by virtue of the excellent surface effect, the volume effect, the quantum size effect and the sheet structure of the fluorinated graphene. Compared with the prior art, the impact strength is improved by more than 2 times, the abrasion rate is obviously reduced, and the mechanical property is good.
The fluorinated graphene used in the invention not only has excellent physical, chemical and mechanical properties of the graphene material, but also can be used as a solid lubricant due to small interlayer energy, can still maintain excellent lubricity under high temperature, high pressure and high load, and can enhance bearing capacity and reduce heat generated by friction on the surface of the material when added into MC nylon.
The inventor states that the invention is illustrated by the above embodiments, but the invention is not limited to the above detailed process equipment and process flow, i.e. the invention is not meant to be dependent on the above detailed process equipment and process flow. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (7)
1. The fluorinated graphene/MC nylon composite material is characterized by being prepared by the following steps:
y1, weighing the fluorinated graphene according to the proportion, adding the fluorinated graphene into a nonpolar solvent, shearing for 0.5-1 h at 18000-20000 r/min through a high-shear stirrer, and then processing for 1.5-3 h through an ultrasonic cell crusher; forming a stable fluorinated graphene dispersion solution;
y2, dividing the caprolactam monomer into two parts, respectively placing the caprolactam monomer I with the total mass of 50-90% of the caprolactam monomer in the reaction kettle A and the caprolactam monomer II with the total mass of 10-50% of the caprolactam monomer in the reaction kettle B;
y21, dropwise adding the fluorinated graphene dispersion solution obtained in the step Y1 into a reaction kettle A filled with caprolactam monomer, stirring at 400-800 r/min, gradually heating to 100-120 ℃, vacuumizing the reaction kettle A to 0.1MPa after the caprolactam monomer in the reaction kettle A is completely melted, increasing the rotation speed to 8000-10000 r/min, and stirring for 30min to uniformly disperse the fluorinated graphene in the caprolactam monomer; then adding a sodium hydroxide solution, and heating to 130-140 ℃; performing reduced pressure distillation to remove water at the temperature of 10000-20000 r/min and under the pressure of 0.1MPa and 140 ℃;
y22, stirring and heating the caprolactam monomer II in the reaction kettle B to 70-80 ℃, starting vacuumizing, adding an initiator after the monomer is molten, continuously vacuumizing to 0.1MPa, heating to 130-140 ℃, and continuously vacuumizing for 10min under the condition of 10000 r/min;
y3, mixing the materials obtained from the kettle A and the kettle B, pouring the mixture into a mold at 150-180 ℃ for polymerization molding, reacting for 50-80 min, and continuing to perform heat preservation reaction for 10-30 min; naturally cooling to obtain the fluorinated graphene/MC nylon composite material;
the mass ratio of the total mass of the fluorinated graphene to the total mass of the caprolactam monomer is 0.5-5%: 1; the mass ratio of the catalyst to the fluorinated graphene is 1-5: 1; the mass ratio of the initiator to the fluorinated graphene is 1-5: 1; the liquid-solid ratio of the aprotic solvent to the fluorinated graphene is 2-10: 1; the fluorine content of the fluorinated graphene is 51% -68%; F/C is more than 1, the weight loss peak temperature is higher than 400 ℃, and the resistance is more than 1000 omega.
2. The fluorinated graphene/MC nylon composite of claim 1, wherein the catalyst is NaOH, KOH, L iOH, Na2CO3And NaH, L iH.
3. The fluorinated graphene/MC nylon composite of claim 1, wherein the aprotic polar solvent is at least one of dimethylformamide, dimethylacetamide, acetone, acetonitrile, 1, 3-dimethyl-2-imidazolidinone.
4. The fluorinated graphene/MC nylon composite of claim 1, wherein the initiator is any one of polyisocyanate, dodecyl isocyanate, hexadecyl isocyanate, tert-butyl isocyanate, nonyl isocyanate, decyl isocyanate, octyl isocyanate or m-toluene isocyanate.
5. The fluorinated graphene/MC nylon composite material as claimed in claim 1, wherein the mass ratio of the total mass of the fluorinated graphene and caprolactam monomers is 3-5: 1; the mass ratio of the catalyst to the fluorinated graphene is 4-5: 1; the mass ratio of the initiator to the fluorinated graphene is 2.5-5: 1; the mass ratio of the aprotic solvent to the fluorinated graphene is 2-2.5: 1.
6. The fluorinated graphene/MC nylon composite material according to claim 1, wherein the preparation method of the fluorinated graphene comprises the following steps:
s1, under the ice bath condition, 10g of graphite powder is added into 250m L of 64 wt% of H2SO4While stirring, slowly adding 50g of KMnO4Reacting the powder at 10-15 ℃ for 2h, then continuously heating to 35 ℃, and continuously stirring for reacting for 4 h; obtaining a first solution;
s2, adding 800m of L deionized water into the solution I obtained in the step S1, heating to 80 ℃, reacting for 30min, cooling the reacted solution to room temperature, adding 50-200 m of L and 38wt% of H2O2Transferring the solution until no bubbles are generated, dialyzing the solution to be neutral in a dialysis bag, and freeze-drying the solution to obtain graphene oxide;
s3, weighing 20g of graphene oxide obtained in the step S2 into a reaction kettle, and introducing N into the reaction kettle at room temperature2Displacing air in the kettle, and then introducing F of 80-100 KPa2/N2Mixed gas of said F2/N2F of mixed gas2Accounting for 10-20% of the total volume of the mixed gas; heating to 180-200 ℃, and fluorinating for 12-36 h to obtain fluorinated graphene; the F/C of the fluorinated graphene is 1.01-1.22.
7. The fluorinated graphene/MC nylon composite material as claimed in claim 1 is applied to production of accessories of automobiles and heavy machinery equipment to form bearing wheels or bearing seats.
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