CN107151321A - A kind of fluorinated graphene/MC nylon composite materials and its preparation method and application - Google Patents
A kind of fluorinated graphene/MC nylon composite materials and its preparation method and application Download PDFInfo
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- CN107151321A CN107151321A CN201710419753.XA CN201710419753A CN107151321A CN 107151321 A CN107151321 A CN 107151321A CN 201710419753 A CN201710419753 A CN 201710419753A CN 107151321 A CN107151321 A CN 107151321A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
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Abstract
The present invention discloses a kind of fluorinated graphene/MC nylon composite materials, to solve the dimensional stability that current MC nylon products are present, the defect such as heat endurance and low-temperature flexibility difference, and the preparation method of fluorinated graphene/MC nylon composite materials is provided, the fluorinated graphene/MC nylon composite materials are by fluorinated graphene, caprolactam monomer, catalyst, initiator and aprotic polar solvent reaction are prepared, the preparation method causes fluorinated graphene to realize good disperse in polymeric matrix, while the excellent properties that fluorinated graphene possesses are remained, and cause the tensile strength of composite, impact strength is substantially improved；The Volume erosion rate of material is substantially reduced, dimensional stability, anti-wear performance and the toughness of product are significantly improved, and the preparation method of the material is simple, equipment requirement is low, pollution-free, suitable industrialization, available for production automobile, the accessory of heavy duty equipment, bearing wheel or bearing block is made.
Description
Technical field
The present invention relates to MC nylon composite materials and its preparation and application, more particularly, to a kind of fluorinated graphene/MC
Nylon composite materials and its preparation method and application.
Background technology
It is product because it has good physical stability, chemical corrosion resistance and high-wearing feature to pour nylon (MC nylon)
The advantages of, the metal material such as alternative steel, copper, aluminium within the specific limits, it is adaptable to chemical industry, machinery, weaving, oil, electrically etc.
Application field.But pure MC nylon products have dimensional stability, heat endurance and the defect, certain journey such as low-temperature flexibility is poor
Its application is limited on degree.At present, domestic modification to MC nylon, prepare composite and carried out many-side and grind
Study carefully, and with inorganic modified and organically-modified more concentrate.The Main Means of wherein inorganic modified method are added such as into nylon
The one or more inorganic filling material such as red phosphorus, glass microsphere, carbon fiber, titanium dioxide nano-particle, and achieve preferably
Dimensional stability and toughness.And since finding graphene from Novoselov in 2004, due to the unique nanostructured of graphite alkenes
And performance, the physics for being remarkably improved polymeric material, mechanical performance and hot property etc. are added in polymer.Domestic
Scientific research institution such as Hefei Genius Advanced Materials Co., Ltd. are in CN105622929A patents, first by graphene in melting
It is pre-dispersed in monomer of polyamide, catalyst, activator and other auxiliary agents are added, finally using anionic ring-opening polymerization work in situ
Skill casting is prepared into nylon/graphene nanocomposite material.Sichuan University in CN105254870A patents, using coupling and
The graphene oxide of reduction treatment is added into caprolactam monomer, and polymerization prepares monomer casting Buddhist nun after reduced vacuum dehydration
Dragon/graphene nanocomposite material.At the same time, Hangzhou Pedagogic University passes through graphene in CN105295028A patents
In-situ modified polycaprolactam composite material, improves dimensional stability, abrasion resistance and the toughness of composite.Invent above
The various excellent properties that graphene possesses in itself are being remained, and modified polyamide meets the intensity of material, modulus
It is obtained for and significantly improves with thermal property.
After fluorinated graphene was reported first from 2010 by A.K.Geim groups, compared with the derivative of other graphenes,
The safe derivative of this brand-new insulation of fluorinated graphene has compared with broad stopband energy level, in a solvent with good dispersiveness, no
Easily reunite, and with the strong nucleopilic reagent such as primary amine necleophilic reaction can occur for the C-F keys of fluorinated graphene, be fluorinated graphene and poly-
Covalent bond is formed between compound base and provides condition.Fluorinated graphene possesses graphite as a kind of two-dimentional derivative graphene
The architectural feature of alkene and carbon fluoride and a series of new physicochemical properties are shown, so as to provide reason for production application
By basis.
However, the research on this kind of material is mostly focused on by adding unmodified graphene or surface modified
Graphene oxide, to improve the interaction between Nano filling and polymeric matrix.Not yet find to prepare in MC nylon at present
During doping fluorinated graphene research and report.
The content of the invention
The primary and foremost purpose of the present invention is dimensional stability, heat endurance and low-temperature flexibility for MC nylon prior arts
The defect such as poor, by adding high fluorine carbon ratio, there is provided one for the fluorinated graphene with excellent heat resistance, wearability and dispersiveness
Plant fluorinated graphene/MC nylon composite materials that there is more excellent physics, mechanical performance and anti-wear performance than MC nylon.
Another object of the present invention is to provide a kind of preparation method of fluorinated graphene/MC nylon composite materials.
Another object of the present invention is to provide a kind of application of fluorinated graphene/MC nylon composite materials.
The present invention is achieved by the following technical programs：
A kind of fluorinated graphene/MC nylon composite materials, by fluorinated graphene, caprolactam monomer, catalyst, initiator
Prepared with aprotic polar solvent reaction, the mass ratio of fluorinated graphene and the caprolactam monomer gross mass is
0.5%~5%:1；The mass ratio of the catalyst and fluorinated graphene is 1~5:1；The initiator and fluorinated graphene
Mass ratio is 1~5:1；The liquid-solid ratio of the aprotic solvent and fluorinated graphene is 2~10:1.
Further, the Oil repellent of the fluorinated graphene is 51%~68%；F/C ＞ 1, weightless peak temperature is higher than
400 DEG C, resistance is more than 1000 Ω.
Further, the catalyst is NaOH, KOH, LiOH, Na2CO3, at least one of NaH, LiH.
Further, the aprotic polar solvent is dimethylformamide, dimethyl acetamide, acetone, acetonitrile, 1,3-
At least one of dimethyl-2-imidazolinone.
Further, the initiator is PIC, dodecyl isocyanate, hexadecyl isocyanate, uncle
Butyl isocyanate, nonyl isocyanates, decyl isocyanates, octyl group isocyanates or a toluene diisocyanate it is any one
Kind.
Further, the mass ratio of fluorinated graphene and the caprolactam monomer gross mass is 3%~5%:1；It is described
The mass ratio of catalyst and fluorinated graphene is 4~5:1；The mass ratio of the initiator and fluorinated graphene is 2.5~5:1；
The mass ratio of the aprotic solvent and fluorinated graphene is that liquid-solid ratio is 2~2.5:1.
It is contemplated that by crosslinking technology realize nylon with the fluorinated graphene of high Oil repellent being total on nanoscale
Valency is combined, and what the nano material of gained can be by the dimensional stability of fluorinated graphene, heat endurance and wearability and polymer can
Processability and dielectricity combine, and have wide practical use in terms of the machinery and friction, wear resistant damage property of enhancing polymer,
It can especially process and be prepared into bearing wheel, bearing block and be applied in automobile, heavy duty equipment accessory.
Fluorinated graphene used in the present invention has good dispersiveness in a solvent, is difficult to reunite, in caprolactam
Under molten monomer state, using high-speed stirred, by the shearing force of agitating solution, realize fluorinated graphene in caprolactam monomer
In it is dispersed, and effective combination of fluorinated graphene and caprolactam monomer is realized by chemical bonding.By fluorination stone
The excellent skin effect of black alkene, bulk effect and quantum size effect and laminated structure, improve fluorinated graphene/MC nylon and are combined
Tensile strength, impact strength and the crocking resistance of material.
It is a further object of the present invention to provide the preparation method of fluorinated graphene/MC nylon composite materials, its fluorographite
The preparation method of alkene comprises the following steps：
S1. under condition of ice bath, 10g graphite powders are added to 250mL, 64wt% H2SO4In, during stirring, it is slowly added
50g KMnO4Powder, at 10~15 DEG C, after reaction 2h, is continuously heating to 35 DEG C, continues stirring reaction 4h；Obtain solution one；
S2. by the solution one described in step S1,800mL deionized waters are added, 80 DEG C of reaction 30min are warming up to；Will be anti-
The temperature of solution is cooled to room temperature after answering, and adds 50~200mL, 38wt% H2O2Solution to bubble-free is produced, and is transferred to dialysis
Dialysed in bag to neutrality, freeze-drying obtains graphene oxide；
S3. the graphene oxide 20g described in step S2 is weighed in reactor, is passed through N2 displacements into reactor at room temperature
The air gone out in kettle, is then passed through 80~100KPa F again2/N2Mixed gas, the F2/N2The F of mixed gas2Account for gaseous mixture
The 10~20% of body cumulative volume；Fluorinated graphene is made after being warming up to 180~200 DEG C, 12~36h of fluorination；The fluorination stone
The F/C of black alkene is 1.01~1.22.
In the present invention, the oxidation of precursor graphene of fluorinated graphene is prepared by classical Hummers oxidizing process
, fluorination reaction further occurs under inert gas and F2 mixed atmospheres and is prepared from for graphene oxide.
It is a further object of the present invention to provide the preparation method of fluorinated graphene/MC nylon composite materials, the fluorination stone
The preparation method of black alkene/MC nylon composite materials comprises the following steps：
Y1. weigh fluorinated graphene according to the above ratio, add it in non-polar solven, by high-shear mixer with
18000~20000r/min, shears 0.5~1h, then handle 1.5~3h with ultrasonic cell disrupte machine；Form stable fluorination stone
Black alkene dispersion soln；
Y2. caprolactam monomer is divided into two parts, is individually placed in reactor A that 50%~90% caprolactam monomer is housed
The caprolactam list of 10%~50% caprolactam monomer gross mass is housed in the caprolactam monomer one and reactor B of gross mass
Body two；
Y21., fluorinated graphene dispersion soln described in step Y1 is added drop-wise to the reactor A equipped with caprolactam monomer
In, stirred under 400~800r/min, be progressively heated to 100~120 DEG C, treat the caprolactam monomer one in the reactor A
Completely after melting, the reactor A is evacuated to 0.1MPa, rotating speed is heightened and stirs 30min to 8000~10000r/min, make
The fluorinated graphene is dispersed in caprolactam monomer one；NaOH solution is added, 130~140 DEG C are warming up to；
Under 0.1MPa, 140 DEG C, under the conditions of 10000~20000r/min, vacuum distillation water removal；
Y22. by the caprolactam monomer two of the reactor B, warming while stirring begins to vacuumize to 70~80 DEG C,
After adding initiator after molten monomer, continue to be evacuated to 0.1MPa and be warming up to 130~140 DEG C, in 10000r/min conditions
Under, continue to vacuumize 10min；
Y3. after the material obtained A kettles and B kettles is mixed, 150~180 DEG C of in-site polymerizations is poured into and are molded, reaction 50~
80min, continues 10~30min of insulation reaction；Natural cooling, produces fluorinated graphene/MC nylon composite materials.
Compared with prior art, the present invention has the advantages that：
The fluorinated graphene that the present invention is provided/MC nylon composite materials, it is creative by fluorinated graphene in pouring MC Buddhist nun
In imperial system, the covalent bond of the fluorinated graphene of MC nylon and high Oil repellent on nanoscale, prepare dimensional stability,
Heat endurance and wearability are high, the good fluorinated graphene of combination property/MC nylon composite materials.
Fluorinated graphene used in the present invention not only has the excellent physics of grapheme material, chemistry and mechanical performance,
And due to interlayer energy very little, still it be able to can be kept outstanding as kollag, under high temperature, high pressure and high load capacity
Lubricity, is added in MC nylon, can strengthen bearing capacity, the heat that reduction material surface is produced by friction.
Fluorinated graphene used in the present invention has good dispersiveness in a solvent, is difficult to reunite, in caprolactam
Under molten monomer state, using high-speed stirred, by the shearing force of agitating solution, realize fluorinated graphene in caprolactam monomer
In it is dispersed, and effective combination of fluorinated graphene and caprolactam monomer is realized by chemical bonding.By fluorination stone
The excellent skin effect of black alkene, bulk effect and quantum size effect and laminated structure, improve fluorinated graphene/MC nylon and are combined
Tensile strength, impact strength and the crocking resistance of material.
The method provided by the present invention for preparing fluorinated graphene/MC nylon composite materials is simple, equipment requirement is low, without dirt
, available for production automobile, the accessory of heavy duty equipment, bearing wheel or bearing block is made in dye, suitable industrialization.
Brief description of the drawings
The fluorinated graphene TEM figures that Fig. 1 present invention is prepared.
Embodiment
The present invention is further described with specific embodiment below in conjunction with the accompanying drawings.Unless stated otherwise, the present invention is implemented
The various raw materials that example is used can be obtained by the way that routine is purchased in market, or be prepared according to the conventional method of this area, used to set
Standby is experiment common equipment.Unless otherwise defined or described herein, all specialties used herein and scientific words and this area
Meaning is identical known to person skilled in the art.
The invention by fluorinated graphene in pouring in MC nylon systems, the fluorographite of nylon and high Oil repellent
Covalent bond of the alkene on nanoscale, prepares dimensional stability, heat endurance and wearability height, the good fluorine of combination property
Graphite alkene/MC nylon composite materials.
The Oil repellent of fluorinated graphene is 51%~68%；F/C ＞ 1, weightless peak temperature is higher than 400 DEG C, and resistance is more than
1000Ω.In fluorinated graphene, fluorine carbon ratio is bigger, and the physical property of fluorinated graphene is better.Therefore, select in this patent
The fluorinated graphene of high fluorine carbon ratio is used as reinforcing material.
Initiator selects PIC, dodecyl isocyanate, hexadecyl isocyanate, tert-butyl group isocyanic acid
Any one of ester, nonyl isocyanates, decyl isocyanates, octyl group isocyanates or a toluene diisocyanate.
Catalyst is NaOH, KOH, LiOH, Na2CO3, at least one of NaH, LiH；It is preferred that NaOH.
Aprotic polar solvent is dimethylformamide, dimethyl acetamide, acetone, acetonitrile, 1,3- dimethyl -2- imidazoles
At least one of quinoline ketone.
Embodiment 1
(1) preparation of fluorinated graphene
S1. under condition of ice bath, 10g graphite powders are added to 250mL, 64wt% H2SO4In, during stirring, it is slowly added
50g KMnO4Powder, at 10~15 DEG C, after reaction 2h, is continuously heating to 35 DEG C, continues stirring reaction 4h；Obtain solution one；
S2. by the solution one obtained by step S1,800mL deionized waters are added, 80 DEG C of reaction 30min are warming up to；Will be anti-
The temperature of solution is cooled to room temperature after answering, and adds 50mL, 38wt% H2O2Solution to bubble-free is produced, and is transferred in bag filter
Dialysis to neutrality, freeze-drying obtains graphene oxide；
S3. the graphene oxide 20g obtained by step S2 is weighed in reactor, is passed through N into reactor at room temperature2Displacement
The air gone out in kettle, is then passed through 80KPa F again2/N2Mixed gas, F2/N2The F of mixed gas2Account for mixed gas cumulative volume
10%；Fluorinated graphene is made after being warming up to 180 DEG C, fluorination 12h；Tested by x-ray photoelectron power spectrum, fluorinated graphene
The F/C on surface is 1.01.
(2) preparation of fluorinated graphene/MC nylon composite materials
Y1. fluorinated graphene is weighed in the ratio of table 1, in the non-polar solven for adding it to 99%, is stirred by high shear
Device is mixed with 18000r/min, 0.5h is sheared, then 1.5h is handled with ultrasonic cell disrupte machine；Stable fluorinated graphene is formed to disperse
Solution；
Y2. caprolactam monomer is divided into two parts, is individually placed to 5Kg caprolactam monomers one are housed and anti-in reactor A
Answer and 5Kg caprolactam monomers two are housed in kettle B；
Y21. by step Y1 fluorinated graphene dispersion soln be added drop-wise in the reactor A equipped with caprolactam monomer,
Stirred under 400r/min, be progressively heated to 100 DEG C, will after the caprolactam monomer one in the reactor A is melted completely
Reactor A is evacuated to 0.1MPa, heightens rotating speed and stirs 30min to 8000r/min, makes the fluorinated graphene in caprolactam
It is dispersed in monomer one；125mL 40wt% NaOH solution is added, 130 DEG C are warming up to；Under 0.1MPa, 140 DEG C,
Under the conditions of 10000r/min, vacuum distillation water removal；
Y22. by reactor B caprolactam monomer two, warming while stirring begins to vacuumize to 70 DEG C, treats that monomer melts
Initiator is added after melting, continues to be evacuated to 0.1MPa and is warming up to 130 DEG C, under the conditions of 10000r/min, continues to vacuumize
10min；
Y3. after the material obtained A kettles and B kettles is mixed, 150 DEG C of in-site polymerization shapings is poured into, 80min is reacted, continues
Insulation reaction 10min；Natural cooling, produces fluorinated graphene/MC nylon composite materials.
Embodiment 2
(1) preparation of fluorinated graphene
The method of the preparation of fluorinated graphene is same as Example 1 in embodiment 2, and its difference is, in step S3
The F for being passed through 85KPa2/N2Mixed gas, F2/N2The F of mixed gas2Account for the 14% of mixed gas cumulative volume；185 DEG C are warming up to,
It is fluorinated after 18h and fluorinated graphene is made；Tested by x-ray photoelectron power spectrum, the F/C on fluorinated graphene surface is
1.06。
(2) preparation of fluorinated graphene/MC nylon composite materials
Y1. fluorinated graphene is weighed in the ratio of table 1, in the non-polar solven for adding it to 99%, is stirred by high shear
Device is mixed with 20000r/min, 1h is sheared, then 3h is handled with ultrasonic cell disrupte machine；Form stable fluorinated graphene and disperse molten
Liquid；
Y2. caprolactam monomer is divided into two parts, is individually placed to 6Kg caprolactam monomers one are housed and anti-in reactor A
Answer and 4Kg caprolactam monomers two are housed in kettle B；
Y21. by step Y1 fluorinated graphene dispersion soln be added drop-wise in the reactor A equipped with caprolactam monomer,
Stirred under 600r/min, be progressively heated to 120 DEG C, will after the caprolactam monomer one in the reactor A is melted completely
Reactor A is evacuated to 0.1MPa, heightens rotating speed and stirs 30min to 8000r/min, makes the fluorinated graphene in caprolactam
It is dispersed in monomer one；250mL 40wt% NaOH solution is added, 140 DEG C are warming up to；Under 0.1MPa, 140 DEG C,
Under the conditions of 10000r/min, vacuum distillation water removal；
Y22. by reactor B caprolactam monomer two, warming while stirring begins to vacuumize to 80 DEG C, treats that monomer melts
Initiator is added after melting, continues to be evacuated to 0.1MPa and is warming up to 140 DEG C, under the conditions of 15000r/min, continues to vacuumize
10min；
Y3. after the material obtained A kettles and B kettles is mixed, 180 DEG C of in-site polymerization shapings is poured into, 50min is reacted, continues
Insulation reaction 10min；Natural cooling, produces fluorinated graphene/MC nylon composite materials.
Embodiment 3
(1) preparation of fluorinated graphene
The method of the preparation of fluorinated graphene is same as Example 2 in embodiment 3.
(2) preparation of fluorinated graphene/MC nylon composite materials
Y1. fluorinated graphene is weighed in the ratio of table 1, in the non-polar solven for adding it to 99%, is stirred by high shear
Device is mixed with 20000r/min, 0.5h is sheared, then 2h is handled with ultrasonic cell disrupte machine；Form stable fluorinated graphene and disperse molten
Liquid；
Y2. caprolactam monomer is divided into two parts, is individually placed to 6Kg caprolactam monomers one are housed and anti-in reactor A
Answer and 4Kg caprolactam monomers two are housed in kettle B；
Y21. by step Y1 fluorinated graphene dispersion soln be added drop-wise in the reactor A equipped with caprolactam monomer,
Stirred under 600r/min, be progressively heated to 120 DEG C, will after the caprolactam monomer one in the reactor A is melted completely
Reactor A is evacuated to 0.1MPa, heightens rotating speed and stirs 30min to 9000r/min, makes the fluorinated graphene in caprolactam
It is dispersed in monomer one；500mL 60wt% NaOH solution is added, 140 DEG C are warming up to；Under 0.1MPa, 140 DEG C,
Under the conditions of 10000r/min, vacuum distillation water removal；
Y22. by reactor B caprolactam monomer two, warming while stirring begins to vacuumize to 80 DEG C, treats that monomer melts
Initiator is added after melting, continues to be evacuated to 0.1MPa and is warming up to 140 DEG C, under the conditions of 10000r/min, continues to vacuumize
10min；
Y3. after the material obtained A kettles and B kettles is mixed, 170 DEG C of in-site polymerization shapings is poured into, 60min is reacted, continues
Insulation reaction 20min；Natural cooling, produces fluorinated graphene/MC nylon composite materials.
Embodiment 4
(1) preparation of fluorinated graphene
The method of the preparation of fluorinated graphene is same as Example 1 in embodiment 4, and its difference is, in step S3
The F for being passed through 90KPa2/N2Mixed gas, F2/N2The F of mixed gas2Account for the 16% of mixed gas cumulative volume；190 DEG C are warming up to,
It is fluorinated after 24h and fluorinated graphene is made；Tested by x-ray photoelectron power spectrum, the F/C on fluorinated graphene surface is
1.16。
(2) the preparation of fluorinated graphene/MC nylon composite materials
Y1. fluorinated graphene is weighed in the ratio of table 1, in the non-polar solven for adding it to 99%, is stirred by high shear
Device is mixed with 20000r/min, 0.5h is sheared, then 1.5h is handled with ultrasonic cell disrupte machine；Stable fluorinated graphene is formed to disperse
Solution；
Y2. caprolactam monomer is divided into two parts, is individually placed to 6Kg caprolactam monomers one are housed and anti-in reactor A
Answer and 4Kg caprolactam monomers two are housed in kettle B；
Y21. by step Y1 fluorinated graphene dispersion soln be added drop-wise in the reactor A equipped with caprolactam monomer,
Stirred under 600r/min, be progressively heated to 120 DEG C, will after the caprolactam monomer one in the reactor A is melted completely
Reactor A is evacuated to 0.1MPa, heightens rotating speed and stirs 30min to 9000r/min, makes the fluorinated graphene in caprolactam
It is dispersed in monomer one；1000mL 60wt% NaOH solution is added, 140 DEG C are warming up to；Under 0.1MPa, 140 DEG C,
Under the conditions of 10000r/min, vacuum distillation water removal；
Y22. by reactor B caprolactam monomer two, warming while stirring begins to vacuumize to 80 DEG C, treats that monomer melts
Initiator is added after melting, continues to be evacuated to 0.1MPa and is warming up to 140 DEG C, under the conditions of 10000r/min, continues to vacuumize
10min；
Y3. after the material obtained A kettles and B kettles is mixed, 170 DEG C of in-site polymerization shapings is poured into, 70min is reacted, continues
Insulation reaction 20min；Natural cooling, produces fluorinated graphene/MC nylon composite materials.
Embodiment 5
(1) preparation of fluorinated graphene
The method of the preparation of fluorinated graphene is same as Example 4 in embodiment 5.
(2) preparation of fluorinated graphene/MC nylon composite materials
Y1. fluorinated graphene is weighed in the ratio of table 1, in the non-polar solven for adding it to 99%, is stirred by high shear
Device is mixed with 20000r/min, 0.5h is sheared, then 2h is handled with ultrasonic cell disrupte machine；Form stable fluorinated graphene and disperse molten
Liquid；
Y2. caprolactam monomer is divided into two parts, is individually placed to 8Kg caprolactam monomers one are housed and anti-in reactor A
Answer and 2Kg caprolactam monomers two are housed in kettle B；
Y21. by step Y1 fluorinated graphene dispersion soln be added drop-wise in the reactor A equipped with caprolactam monomer,
Stirred under 600r/min, be progressively heated to 120 DEG C, will after the caprolactam monomer one in the reactor A is melted completely
Reactor A is evacuated to 0.1MPa, heightens rotating speed and stirs 30min to 10000r/min, makes fluorinated graphene acyl in oneself
It is dispersed in amine monomers one；1000mL 80wt% NaOH solution is added, 140 DEG C are warming up to；Under 0.1MPa, 140
DEG C, under the conditions of 10000r/min, vacuum distillation water removal；
Y22. by reactor B caprolactam monomer two, warming while stirring begins to vacuumize to 80 DEG C, treats that monomer melts
Initiator is added after melting, continues to be evacuated to 0.1MPa and is warming up to 140 DEG C, under the conditions of 20000r/min, continues to vacuumize
10min；
Y3. after the material obtained A kettles and B kettles is mixed, 170 DEG C of in-site polymerization shapings is poured into, 70min is reacted, continues
Insulation reaction 20min；Natural cooling, produces fluorinated graphene/MC nylon composite materials.
Embodiment 6
(1) preparation of fluorinated graphene
The method of the preparation of fluorinated graphene is same as Example 1 in embodiment 6.Its difference is, in step S3
The F for being passed through 100KPa2/N2Mixed gas, F2/N2The F of mixed gas2Account for the 20% of mixed gas cumulative volume；It is warming up to 200
DEG C, fluorinated graphene is made after fluorination 36h；Tested by x-ray photoelectron power spectrum, the F/C on fluorinated graphene surface is
1.22。
(2) preparation of fluorinated graphene/MC nylon composite materials
Y1. fluorinated graphene is weighed in the ratio of table 1, in the non-polar solven for adding it to 99%, is stirred by high shear
Device is mixed with 20000r/min, 0.5h is sheared, then 2h is handled with ultrasonic cell disrupte machine；Form stable fluorinated graphene and disperse molten
Liquid；
Y2. caprolactam monomer is divided into two parts, is individually placed to 9Kg caprolactam monomers one are housed and anti-in reactor A
Answer and 1Kg caprolactam monomers two are housed in kettle B；
Y21. by step Y1 fluorinated graphene dispersion soln be added drop-wise in the reactor A equipped with caprolactam monomer,
Stirred under 800r/min, be progressively heated to 120 DEG C, will after the caprolactam monomer one in the reactor A is melted completely
Reactor A is evacuated to 0.1MPa, heightens rotating speed and stirs 30min to 10000r/min, makes fluorinated graphene acyl in oneself
It is dispersed in amine monomers one；3125mL 80wt% NaOH solution is added, 140 DEG C are warming up to；Under 0.1MPa, 140
DEG C, under the conditions of 10000r/min, vacuum distillation water removal；
Y22. by reactor B caprolactam monomer two, warming while stirring begins to vacuumize to 80 DEG C, treats that monomer melts
Initiator is added after melting, continues to be evacuated to 0.1MPa and is warming up to 140 DEG C, under the conditions of 10000r/min, continues to vacuumize
10min；
Y3. after the material obtained A kettles and B kettles is mixed, 170 DEG C of in-site polymerization shapings is poured into, 70min is reacted, continues
Insulation reaction 20min；Natural cooling, produces fluorinated graphene/MC nylon composite materials.
Comparative example 1
Weigh quantitative caprolactam and be added to sealing in reactor, be warming up to 100~120 DEG C, treat caprolactam monomer
Vacuumized completely after melting, moisture and low boiling impurity are removed at 120 DEG C；Add in the NaOH of addition, every 100ml caprolactams
Enter 0.3mol NaOH, continue to stir, vacuumize and be warming up to 160 DEG C, then add polymeric isocyanate glue, the acyl in oneself per 100ml
0.3mol PIC is added in amine, continues stirring reaction 15min；In the mould of last fast transfer to 170 DEG C, constant temperature
Polyase 13 0min, MC nylon materials are obtained after the demoulding after natural cooling.
Table 1
In order to further illustrate, the fluorinated graphene material prepared in embodiment 1~6 is carried out transmission electricity by the present invention
Sub- microscopic analysis, as shown in Figure 1, fluorinated graphene that is of the invention prepared and using still have good sheet knot
Structure, and good transparent form is showed, different from graphene oxide, fluorinated graphene is that rigid molecule is not in accordion
State, it is adaptable to the application of composite.
Any gained fluorinated graphene/MC nylon composite materials and comparative example in 1~embodiment of embodiment 6 in the present invention
Material in 1 carries out the measure of tensile strength, impact strength, coefficient of friction and Volume erosion rate.Specific measurement result such as table 2
It is shown.
Table 2
As known to table 2, fluorinated graphene/MC nylon composite materials that the present invention is prepared are connect by fluorinated graphene
The modified caprolactam of branch prepares fluorinated graphene/MC nylon composite materials, by the excellent skin effect of fluorinated graphene, body
Product effect and quantum size effect and laminated structure, tensile strength, the impact for improving fluorinated graphene/MC nylon composite materials are strong
Degree and crocking resistance.Impact strength improves more than 2 times than prior art products, and product wear rate is also substantially reduced, with very
Good mechanical performance.
Fluorinated graphene used in the present invention not only has the excellent physics of grapheme material, chemistry and mechanical performance,
And due to interlayer energy very little, still it be able to can be kept outstanding as kollag, under high temperature, high pressure and high load capacity
Lubricity, is added in MC nylon, can strengthen bearing capacity, the heat that reduction material surface is produced by friction.
Inventor states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (9)
1. a kind of fluorinated graphene/MC nylon composite materials, it is characterised in that the fluorinated graphene/MC nylon composite materials
Prepared by the reaction of fluorinated graphene, caprolactam monomer, catalyst, initiator and aprotic polar solvent, the fluorination
Graphene and the mass ratio of caprolactam monomer gross mass are 0.5% ~ 5%：1；The mass ratio of the catalyst and fluorinated graphene
For 1 ~ 5:1；The mass ratio of the initiator and fluorinated graphene is 1 ~ 5:1；The liquid of the aprotic solvent and fluorinated graphene
Gu than being 2 ~ 10：1.
2. fluorinated graphene/MC nylon composite materials according to claim 1, it is characterised in that the fluorinated graphene
Oil repellent is 51% ~ 68%；F/C ＞ 1, weightless peak temperature is higher than 400 DEG C, and resistance is more than 1000 Ω.
3. fluorinated graphene/MC nylon composite materials according to claim 1, it is characterised in that the catalyst be NaOH,
KOH、LiOH、Na2CO3, at least one of NaH, LiH.
4. fluorinated graphene/MC nylon composite materials according to claim 1, it is characterised in that the aprotonic polar is molten
Agent is dimethylformamide, dimethyl acetamide, acetone, acetonitrile, at least one of 1,3- dimethyl-2-imidazolinones.
5. fluorinated graphene/MC nylon composite materials according to claim 1, it is characterised in that the initiator is poly- different
Cyanate, dodecyl isocyanate, hexadecyl isocyanate, t-butylisocyanate, nonyl isocyanates, decyl isocyanide
Any one of acid esters, octyl group isocyanates or a toluene diisocyanate.
6. fluorinated graphene/MC nylon composite materials according to claim 1, it is characterised in that the fluorinated graphene and
The mass ratio of caprolactam monomer gross mass is 3% ~ 5%:1；The mass ratio of the catalyst and fluorinated graphene is 4 ~ 5:1；Institute
The mass ratio for stating initiator and fluorinated graphene is 2.5 ~ 5:1；The mass ratio of the aprotic solvent and fluorinated graphene is liquid
Gu than being 2 ~ 2.5:1.
7. a kind of preparation method of fluorinated graphene/MC nylon composite materials according to claim 1, it is characterised in that institute
The preparation method for stating fluorinated graphene comprises the following steps：
S1. under condition of ice bath, 10g graphite powders are added to 250mL, 64 wt% H2SO4In, during stirring, it is slowly added 50g
KMnO4Powder, at 10 ~ 15 DEG C, after reaction 2h, is continuously heating to 35 DEG C, continues stirring reaction 4h；Obtain solution one；
S2. by the solution one described in step S1,800mL deionized waters are added, 80 DEG C of reaction 30min are warming up to；Will reaction
The temperature of solution is cooled to room temperature afterwards, adds 50 ~ 200mL, 38wt% H2O2Solution to bubble-free is produced, and is transferred in bag filter
Dialysis to neutrality, freeze-drying obtains graphene oxide；
S3. the graphene oxide 20g described in step S2 is weighed in reactor, is passed through N into reactor at room temperature2Displace kettle
In air, 80 ~ 100KPa F is then passed through again2/N2Mixed gas, the F2/N2The F of mixed gas2Account for mixed gas overall
Long-pending 10 ~ 20%；Fluorinated graphene is made after being warming up to 180 ~ 200 DEG C, 12 ~ 36h of fluorination；The F/C of the fluorinated graphene
For 1.01 ~ 1.22.
8. a kind of preparation method of fluorinated graphene/MC nylon composite materials according to claim 1 ~ 7 any one, it is special
Levy and be, the preparation method of the fluorinated graphene/MC nylon composite materials comprises the following steps：Y1. weigh according to the above ratio
Fluorinated graphene, is added it in non-polar solven, by high-shear mixer with 18000 ~ 20000r/min, and shearing 0.5 ~
1h, then handle 1.5 ~ 3h with ultrasonic cell disrupte machine；Form stable fluorinated graphene dispersion soln；
Y2. caprolactam monomer is divided into two parts, is individually placed in reactor A that 50% ~ 90% caprolactam monomer gross mass is housed
Caprolactam monomer one and reactor B in be equipped with 10% ~ 50% caprolactam monomer gross mass caprolactam monomer two；
Y21. the fluorinated graphene dispersion soln described in step Y1 is added drop-wise in the reactor A equipped with caprolactam monomer,
Stirred under 400 ~ 800r/min, be progressively heated to 100 ~ 120 DEG C, treat that the caprolactam monomer one in the reactor A melts completely
After melting, the reactor A is evacuated to 0.1MPa, rotating speed is heightened and stirs 30min to 8000 ~ 10000r/min, make the fluorine
Graphite alkene is dispersed in caprolactam monomer one；Sodium hydroxide solution is added, 130 ~ 140 DEG C are warming up to；
Under 0.1MPa, 140 DEG C, under the conditions of 10000 ~ 20000r/min, vacuum distillation water removal；
Y22. by the caprolactam monomer two of the reactor B, warming while stirring begins to vacuumize to 70 ~ 80 DEG C, treats list
Initiator is added after body melting, continues to be evacuated to 0.1MPa and is warming up to 130 ~ 140 DEG C, under the conditions of 10000r/min, after
It is continuous to vacuumize 10min；
Y3. after the material obtained A kettles and B kettles is mixed, 150~180 DEG C of in-site polymerizations is poured into and are molded, reaction 50~
80min, continues 10 ~ 30min of insulation reaction；Natural cooling, produces the fluorinated graphene/MC nylon composite materials.
9. a kind of fluorinated graphene that preparation method according to claim 8 is prepared/MC nylon composite materials are used to give birth to
Steam the accessory of car, heavy duty equipment, and bearing wheel or bearing block is made.
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